LIGHT-STORING FIBER WITH HIGH LUMINANCE

Abstract

A high-luminance light-storing fiber is provided. A modified light-storing powder and a dispersing agent are added to a polyester material, and then prepared by kneading, granulating and spinning to obtain the light-storing fiber having fiber fineness of 1-10 dpf. The fiber luminance satisfies the following conditions: (1) after irradiation with a D65 light source at 2001 ux for 20 minutes, the initial luminance can reach 150 mcd/m2 or more; (2) after irradiation with a D65 light source at 251 ux for 25 minutes, the initial luminance can reach 50 mcd/m2 or more.

Claims

1. A light-storing fiber with high luminance produced by melt spinning with a light-storing masterbatch, characterized in that the light-storing masterbatch includes the following components, the sum of the components being 100 wt % based on the total amount: a) 50% to 95 wt % of thermoplastic polymer selected from polyester powder and polyester granules having an intrinsic viscosity (IV) of 0.2 to 2.0; b) 1% to 30 wt % of modified light-storing powder which is an aluminate doped with rare-earth elements, represented as the general formula M.sub.1-xAl.sub.2O.sub.4.Math.Eu.sub.YN.sub.Z; wherein M is Sr, Mg, Ca or Ba, N is Td, Dy, La, Ce, Mn, Sm, Gd, Pr, Lu, Ho, Y, Yb, Tm or Er; and 0.33X0.6,0.008Y0.002, 0.002Z0.005; and c) 0.01 to 5 wt % of antioxidants; wherein the light-storing fiber satisfies the following conditions: (1) after irradiation with a D65 light source at 2001 ux for 20 minutes, the initial luminance can reach 150 mcd/m2 or more; (2) after irradiation with a D65 light source at 25 LUX for 25 minutes, the initial luminance can reach 50 mcd/m2 or more.

2. The light-storing fiber according to claim 1, wherein the light-storing masterbatch has a pressure rise value less than or equal to 0.5 bar/g.

3. The light-storing fiber according to claim 1, wherein the light-storing fiber has a fiber fineness of 1 to 10 dpf.

4. The light-storing fiber according to claim 3, wherein the light-storing fiber has a core-sheath structure, a core is a light-storing masterbatch, a sheath is a polyester, and a core-sheath ratio is between 40/60 to 60/40.

5. The light-storing fiber according to claim 3, wherein the light-storing fiber has a diameter of 10 to 30 micrometers (m).

6. The light-storing fiber according to claim 1, wherein the modified light-storing powder contains a silane coupling agent or a phthalate modifier in an amount of 0.1 to 20% by weight based on the total amount of the light-storing powder.

7. The light-storing fiber according to claim 1, wherein the modified light-storing powder contains 3-propenyloxypropyltrimethoxysilane or pyrophosphate titanate in an amount of 1% to 10% by weight based on the total amount of light-storing powder.

8. The light-storing fiber according to claim 1, wherein the thermoplastic polymer has an intrinsic viscosity (IV) of 1.2.

9. The light-storing fiber according to claim 1, wherein the antioxidant is selected from the group consisting of a hindered phenol type antioxidant and a phosphite type antioxidant.

10. The light-storing fiber according to claim 1, wherein the antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

Description

DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS

[0018] The present disclosure is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. Like numbers in the drawings indicate like components throughout the views. As used in the description herein and throughout the claims that follow, unless the context clearly dictates otherwise, the meaning of a, an, and the includes plural reference, and the meaning of in includes in and on. Titles or subtitles can be used herein for the convenience of a reader, which shall have no influence on the scope of the present disclosure.

[0019] The terms used herein generally have their ordinary meanings in the art. In the case of conflict, the present document, including any definitions given herein, will prevail. The same thing can be expressed in more than one way. Alternative language and synonyms can be used for any term(s) discussed herein, and no special significance is to be placed upon whether a term is elaborated or discussed herein. A recital of one or more synonyms does not exclude the use of other synonyms. The use of examples anywhere in this specification including examples of any terms is illustrative only, and in no way limits the scope and meaning of the present disclosure or of any exemplified term. Likewise, the present disclosure is not limited to various embodiments given herein. Numbering terms such as first, second or third can be used to describe various components, signals or the like, which are for distinguishing one component/signal from another one only, and are not intended to, nor should be construed to impose any substantive limitations on the components, signals or the like.

[0020] The present disclosure provides a modified light-storing powder, which is an aluminate doped rare-earth element, and has the general formula M.sub.1-xAl.sub.2O.sub.4.Math.Eu.sub.YN.sub.Z, wherein M is Sr, Mg, Ca or Ba, N is Td, Dy, La, Ce, Mn, Sm, Gd, Pr, Lu, Ho, Y, Yb, Tm or Er and 0.33X0.6, 0.008Y0.002, 0.002Z0.005. The surface of the powder is modified by a powder surface modification technique, that is, using a modifier such as a silane coupling agent or a phthalate modifier added in an amount of 0.1% to 20% by weight based on the total amount of the light-storing powder, and preferably of 1% to 10% by weight based on the total amount of the light-storing powder.

[0021] The silane coupling agent of the present disclosure is selected from vinyl chloroform, vinyltrimethoxysilane,vinyl triethoxysilane, vinyltris(-methoxyethoxy)silane, -(3,4-epoxycyclohexypethyltrimethoxysilane, -(2-aza-propanering aminopropyltrimethoxysilane, -glycidoxypropyltrimethoxysilane,-glycidoxypropyltrimethyldiethoxysilane, -glycidoxypropyl triethoxy silane, -methacryl propyl methyl dimethoxy silane, -methyl propyl propyl trimethoxy silane, -methyl propyl propyl methyl diethoxy silane, -methacryl propyl triethoxy silane, n- (aza-propyl) -aminopropyl methyl dimethoxy silane, n- (aza-propyl) -aminopropyltrimethyloxysilane,n-(aziridine)-aminopropyltriethoxysilane,3 -propenyloxypropyltrimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,n-phenyl--aminopropyltrimethoxysilane,-chloropropyltrimethoxysilane, -hydrothiopropyltrimethoxysilane, bis-(3-[triethoxynonyl]-propyl)-tetrasulfide (tespt) or bis-(3-[triethoxydecyl]propyl)-disulfide; preferably 3-propenylmethoxypropyltrimethoxy silane.

[0022] The titanate of the present disclosure is selected from isostearyl titanate, stearyl titanate, oleyl titanate and pyrophosphate titanate; preferably selected from pyrophosphate titanate.

[0023] The modification process of the light-storing powder of the present disclosure includes the following steps:

[0024] The light-storing powder is placed in a stirring tank and stirred at 200 rpm. The stirring blade is an anchor blade. The modifier 3-propyleneoxypropyltrimethoxydecane is taken by weight relative to the weight of the light-storing powder, diluted and dissolved with the volume ratio of modifier/isopropyl alcohol=1/6, and gradually added to the light-storing powder. A stirring rate of the blade is adjusted to 1000 rpm, and a dropping acceleration rate is 1 ml/min. After the completion of dropping addition, the stirring tank is heated to 120 C. and the light-storing powder is stirred for 2 hours to volatilize isopropyl alcohol to obtain a modified light-storing powder.

[0025] The method for preparing the light-storing masterbatch of the present disclosure includes the following steps:

[0026] Based on the total amount of the light-storing masterbatch, 1% to 30 wt % of the light-storing powder is taken, 50% to 95 wt % of a thermoplastic polymer is taken, and 0.01% to 5 wt % of an antioxidant is taken as raw materials. The thermoplastic polymer may be selected from polyester powder and polyester particles, and the polyester powder or particles have an intrinsic viscosity (IV) of 0.2 to 2.0, preferably 1.2. After the above raw materials are uniformly mixed into a mixed powder, the mixture is kneaded by a twin-screw extruder. The thermoplastic polymer (or resin) is molten at a kneading temperature of 180 C. to 280 C. and a rotation speed of 250 rpm. At this point, a terminal group of the modifier on the light-storing powder is excellent in compatibility with the resin, so that the light-storing powder is dispersed uniformly in the resin substrate. After cooling with water, pellets were dried at 140 C. for 4 to 6 hours to obtain the light-storing masterbatch of the present disclosure.

[0027] More specifically, the modified light-storing powder of the present disclosure is an inorganic material, and the powder is modified on the surface to be completely uniformly dispersed in the resin to improve dispersibility. Therefore, the light-storing masterbatch of the present disclosure has no pressure rise in a spinning process, has good spinning condition, and can be subjected to spinning production for a long time.

[0028] The antioxidant of the present disclosure may be selected from hindered phenol antioxidants and phosphite antioxidants.

[0029] The phosphite antioxidant may be selected from dimethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5 -di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, dipropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dibutyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert dipentyl butyl-4-hydroxybenzylphosphonate, dihexyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diheptyl ester, dioctyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, double manganate of diethyl 3,5 -di-t-butyl-4-hydroxybenzyl)phosphonate, magnesium diethyl bis(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, bis(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate calcate, and bis(3,5-di-t-butyl-4-hydroxybenzyl)phosphonic acid diethyl ester zincate; preferably bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

[0030] The light-storing fiber of the present disclosure is prepared by melt spinning a light-storing masterbatch after drying. Fiber structure of the light-storing fiber can be formed by composite spinning to form a core-sheath structure, the core is a light-storing masterbatch, the sheath is a polyester, and the core-sheath ratio (core/sheath) is varied, which is between 40/60 to 60/40.

[0031] The light-storing fiber manufacturing method of the present disclosure comprises the following steps:

[0032] The light-storing masterbatch of the present disclosure is taken as a raw material, at a spinning temperature of 230-290 C. and a spinning take-up speed of 1000-3000 m/min, partially oriented yarn (POY) of the core-sheath structure is formed by composite spinning, and drawn textured yarn (DTY) is formed by false twisting process, that is the light-storing fiber of the present disclosure. The light-storing fiber has a diameter of 10 to 30 micrometers (m) and a fiber fineness of 1 to 10 dpf.

[0033] The light-storing fiber of the present disclosure has a fiber structure of a core-sheath design, and the core light-storing powder is wrapped in the core of the fiber, and after being washed for 50 times, the light luminance of the light-storing fiber can be maintained. Therefore, the light-storing fiber of the present disclosure can be widely applied to the fiber application industry, including clothing, home furnishings and outdoor safety products.

[0034] Hereinafter, a plurality of specific embodiments (embodiment 1 to 4) for producing modified light-storing powder and processing the modified light-storing powder into light-storing masterbatch and light-storing fiber are provided, and a comparative example is provided to help explain the purpose, efficacy and principle of the present disclosure.

[0035] The modified light-storing powder and light-storing fiber produced by each embodiment and the comparative example are evaluated for physical properties according to the following methods: 1. Pressure test: the light-storing masterbatch is diluted to 8% and the pressure rise thereof is evaluated by a filter tester (label: LabTech, model: LTF34-GP) with a screen pack size of 15 m. The lower the pressure rise is, the better the dispersion of the light-storing powder in the polyester resin is.

[0036] 2. Luminance test: according to JIS Z9107 as the standard, a sample garter diameter is 35 mm, the sample is placed in a black box, standing for 48 h, at temperature of 232 C., and RH of 5010%. After being radiated with the D65 light source at 2001 ux for 20 min and 251 ux for 15 min, a test is performed with a luminance meter (label: KONICA MINOLTA model: LS-100), and luminance of 2, 10, 20, 30, and 60 minutes are recorded.

First Embodiment

[0037] 1. Light-storing powder modification: the light-storing powder is placed in a stirring tank, stirred at 200 rpm, and the stirring blade is anchored. The modifier 3-propyleneoxypropyltrimethoxydecane is taken 1% by weight relative to the weight of the light-storing powder, diluted and dissolved with the volume ratio of modifier/isopropyl alcohol=1/6, and gradually added to the light-storing powder. A blade stirring rate is adjusted to 1000 rpm, and a dropping acceleration rate is 1 ml/min. After the completion of dropping addition, the stirring tank is heated to 120 C. and stirred for 2 hours to volatilize isopropyl alcohol to obtain a modified light-storing powder.

[0038] 2. Light-storing masterbatch production: according to raw material formula of Table 2, 79.5 wt % of PET polyester resin, 20 wt % of modified light-storing powder A1, and 0.5 wt % of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (hereinafter referred to as antioxidant RCPEP36) are taken as a raw material, and melt granulated by a twin-screw extruder.

[0039] 3. Light-storing fiber production: Fiber specification is 75D/72F. A core is the light-storing masterbatch after drying, a sheath is dry polyester, a core-sheath ratio is 50/50, a spinning temperature is 280 C., and a spinning speed is 2500 m/min. The POY is produced, and processed into DTY, which is then woven into a garter.

[0040] The pressure rise value of the light-storing masterbatch prepared is tested, and the results are shown in Table 2. After the light-storing masterbatch is spun and woven, the test luminance is shown in Tables 3 and 4. After the garter has been washed for 50 times, the luminance test results are as shown in Table 5. The light-storing effect is maintained at the initial level, and the luminance of the yarn before and after washing has not been affected.

Second Embodiment

[0041] 1. A modified light-storing powder is prepared in the same method as in the embodiment 1, but the modifier is added in an amount of 5 wt % of the weight of the light-storing powder (Table 1, Formula No. A2).

[0042] 2. According to raw material formula of Table 2, 79.5 wt % PET polyester resin, 20 wt % of modified light-storing powder A2, and 0.5 wt % antioxidant RCPEP36 are taken as a raw material, and melt granulated by a twin-screw extruder so as to obtain the light-storing masterbatch.

[0043] The pressure rise value of the light-storing masterbatch prepared is tested, and the results are shown in Table 2. After the light-storing masterbatch is spun and woven, the test luminance is shown in Tables 3 and 4. After the garter has been washed for 50 times, the luminance test results are as shown in Table 5. The light-storing effect is maintained at the initial level, and the luminance of the yarn before and after washing has not been affected.

Third Embodiment

[0044] 1. A modified light-storing powder is prepared in the same method as in the embodiment 1, but the modifier is added in an amount of 10 wt % of the weight of the light-storing powder (Table 1, Formula No. A3).

[0045] 2. According to raw material formula of Table 2, 79.5 wt % PET polyester resin, 20 wt % modified light-storing powder A3, and 0.5 wt % of antioxidant RCPEP36 are taken as a raw material, and melt granulated by a twin-screw extruder so as to obtain the light-storing masterbatch.

[0046] The pressure rise value of the light-storing masterbatch prepared is tested, and the results are shown in Table 2. After the light-storing masterbatch is spun and woven, the test luminance is shown in Tables 3 and 4. After the garter has been washed for 50 times, the luminance test results are as shown in Table 5. The light-storing effect is maintained at the initial level, and the luminance of the yarn before and after washing has not been affected.

Fourth Embodiment

[0047] 1. A modified light-storing powder is prepared in the same method as in the embodiment 1, but the modifier is pyrophosphate titanate in an amount of 10 wt % of the weight of the light-storing powder (Table 1, Formula No. A4).

[0048] 2. According to raw material formula of Table 2, 79.5 wt % PET polyester resin, 20 wt % of modified light-storing powder A4, and 0.5 wt % of antioxidant RCPEP36 are taken as a raw material, and melt granulated by a twin-screw extruder so as to obtain the light-storing masterbatch.

[0049] The pressure rise value of the light-storing masterbatch prepared is tested, and the results are shown in Table 2. After the light-storing masterbatch is spun and woven, the test luminance is shown in Tables 3 and 4. After the garter has been washed for 50 times, the luminance test results are as shown in Table 5. The light-storing effect is maintained at the initial level, and the luminance of the yarn before and after washing has not been affected.

COMPARATIVE EXAMPLE

[0050] 1. light-storing powder is not modified (Table 1, Formula No. A5)

[0051] 2. According to raw material formula of Table 2, 79.5 wt % PET polyester resin, 20 wt % of modified light-storing powder A5, and 0.5 wt % of antioxidant RCPEP36 are taken as a raw material, and melt granulated by a twin-screw extruder so as to obtain the light-storing masterbatch.

[0052] The pressure rise value of the light-storing masterbatch prepared is tested, and the results are shown in Table 2. After the light-storing masterbatch is spun and woven, the test luminance is shown in Tables 3 and 4. After the garter has been washed for 50 times, the luminance test results are as shown in Table 5. The light-storing effect is maintained at the initial level, and the luminance of the yarn before and after washing has not been affected.

Conclusion

[0053] 1. The light-storing powder of embodiments1-3 is treated with the modifier 3-acryloxypropyltrimethoxydecane and the light-storing powder of embodiment4 is treated with the modifier pyrophosphate titanate, and then the resin and a dispersing agent are mixed and granulated, respectively. After the light-storing masterbatch is dried, the pressure rise value is evaluated by a filter tester, and the test value (as shown Table 2) is less than or equal to 0.5 bar/g. Therefore the light-storing powder is excellently dispersed in the polyester resin.

[0054] 2. The light-storing powder of Comparative Example 1 is not modified, and is directly mixed with resin and dispersant. After the light-storing masterbatch is dried, the pressure rise is evaluated by a filter=tester. The test value (as shown Table 2) is 1.2 bar/g, greater than 0 5 bar/g. Therefore the light-storing powder is not well dispersed in the polyester resin.

[0055] 3. The above two conclusions confirm that the light-storing powder treated by the modifier can effectively help the light-storing powder to be dispersed in the polyester resin, reduce the phenomenon of powder agglomeration, and improve the pressure rise, which helps the spinning process of the light-storing fiber to proceed smoothly.

[0056] 4. Regarding the light-storing masterbatch produced by embodiments 1-4, after drying and removing water, fiber structure of the light-storing fiber can be formed by composite spinning to form a core-sheath structure, the core is a light-storing masterbatch, and the sheath is a polyester. After being coiled, the light-storing masterbatch is processed into drawn textured yarn, and the garter is evaluated. After the surface of the light-storing powder is modified, the yarn is spun and the luminance of the yarn is higher than that of the unmodified powder surface, as shown in Table 3. Under low light source, there is also the same result, as shown in Table 4.

[0057] 5. After the spinning of embodiments 1-4 and comparative example 1, there is no change of the luminance of the yarn before and after the yarn being washed, since the yarn is made by composite spinning, and the light-storing powder is wrapped in the fiber center, so that the luminance of the yarn before and after being washed would not be affected, as shown in Table 5.

TABLE-US-00001 TABLE 1 modified light-storing powder formula Modified powder formula number Item Raw material (wt %) A1 A2 A3 A4 A5 modified light- SrAl.sub.2O.sub.4Eu.sub.0.001Dy.sub.0.003 99 95 90 99 100 light- storing storing powder powder Modifier 3-propenyloxypropyl- 1 5 10 trimethoxysilane Pyrophosphate titanate 1

TABLE-US-00002 TABLE 2 light-storing masterbatch formula (wt %) and pressure rise com- parative Raw Embodi- Embodi- Embodi- Embodi- example Item material ment 1 ment 2 ment 3 ment 4 1 Polyester PET(IV = 79.5 79.5 79.5 79.5 79.5 modified 1.2) light- A1 20 storing A2 20 powder A3 20 A4 20 A5 20 Anti- RC PEP 0.5 0.5 0.5 0.5 0.5 oxidant 36.sup.* 1 Pressure 0.4 0.1 0.002 0.5 1.2 rise (bar/g) Note 1: RC PEP 36 represents bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

TABLE-US-00003 TABLE 3 light-storing fiber and luminance (D65 at 200LUX irradiation for 20 min) com- Time Embodi- Embodi- Embodi- Embodi- parative Item (min) ment 1 ment 2 ment 3 ment 4 example1 Fiber 75D/72F 75D/72F 75D/72F 75D/72F 75D/72F specification luminance 2 156 158 157 156 110 (mcd/m.sup.2) 10 66 68 67 66 56 20 52 53 55 54 32 30 32 33 34 33 13 60 15 16 15 15 5 Residual 2.fwdarw.60 9.6 10.1 9.5 9.6 4.5 luminance %

TABLE-US-00004 TABLE 4 light-storing fiber and luminance (D65 at 25LUX irradiation for 15 min) com- Time Embodi- Embodi- Embodi- Embodi- parative Item (min) ment1 ment2 ment3 ment4 example1 Fiber 75D/72F 75D/72F 75D/72F 75D/72F 75D/72F specification luminance 2 52 53 52 53 36 (mcd/m.sup.2) 10 22 23 22 21 56 20 17 18 18 17 19 30 10 11 11 12 4 60 6 6 6 6 2 Residual 2.fwdarw.60 11.5 11.3 11.5 11.3 5.5 luminance %

TABLE-US-00005 TABLE 5 light-storing fiber before and after washed com- Embodi- Embodi- Embodi- Embodi- parative Item Unit ment1 ment2 ment3 ment4 example1 Fiber (D/F) 75D/72F 75D/72F 75D/72F 75D/72F 75D/72F specification Initial 2 min mcd/m.sup.2 156 158 157 156 110 luminance before washed Initial 2 min mcd/m.sup.2 156 158 157 156 110 luminance after washed

[0058] The foregoing description of the exemplary embodiments of the disclosure has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the disclosure to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching.

[0059] The embodiments were chosen and described in order to explain the principles of the disclosure and their practical application so as to enable others skilled in the art to utilize the disclosure and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the present disclosure pertains without departing from its spirit and scope.