AU2019101288A4

AU2019101288A4 - Self-illuminous polymer compositions and the article produced by said composition

Info

Publication number: AU2019101288A4
Application number: AU2019101288A
Authority: AU
Inventors: Chutinan Boonyapatipa; Apisit KOSITCHAIYONG; Ruksapong KUNANURUKSAPONG; Wattanachai Luankaew; Nuchanart Onchoy; Bunthita SUPPAIBULSUK
Original assignee: PTT Global Chemical PCL
Current assignee: PTT Global Chemical PCL
Priority date: 2018-12-27
Filing date: 2019-10-24
Publication date: 2019-11-28
Anticipated expiration: 2027-10-24

Abstract

C:\Interwoven\NRPortbl\DCC\RBR1 9421449 _.doex-10/24/2019 Abstract This invention relates to luminous polymer compositions and the article produced by said composition having self-luminous property in the dark, wherein said compositions comprising: 5 a) 80 - 95.0 % by weight of polyolefins; b) 4.0 - 15.0 % by weight of phosphorescent materials based on MA 204:X, when M is alkaline earth element and X is lanthanide element selected from lanthanum (La), neodymium (Nd), europium (Eu), and dysprosium (Dy); c) 0.01 - 0.10 % by weight of red pigment; and 10 d) 0.1 - 3.0 % by weight of polymer additives.

Description

Field of the Invention

Polymer science relates to self-illuminous polymer compositions and the article produced by said composition.

Background of the Invention

Article made from the luminescent plastic article aims mainly in the application for safety application and increasing the value of the products to be predominant to normal products. Normally, the phosphorescent materials, which are glow-in-the-dark materials, are applied into the compositions of several inventions which gain more interest such as golf ball, sole of the shoes, toys, safety tape for bicycle, direction indicator and signal, light for liquid crystal watch, safety helmet, etc.

However, it is difficult to produce article from plastic having a long term luminous property in dark color or opaque plastic especially the red luminous pigment because the limitation of available luminous compositions at present. Therefore, the luminous performance is not enough for uses.

At present, the phosphorescent materials used extensively are luminous phosphorous in sulfite group such as CaSrS:Bi (which emits blue light) or ZnS:Cu (which emits green light) and metal oxide aluminates group based on MAkCUX having M selected from magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or co-metals thereof, and X selected from lanthanum (La), neodymium (Nd), europium (Eu), dysprosium (Dy), or co-metals thereof, wherein the selection of the luminous materials can be one or more than one luminous materials in which said luminous materials absorb and release their lights at different wavelength such as CaAkCUEu (which emits blue light), SrAkCL; Eu (which emits green light), and BaAkCL: Eu (which emits green light) according to the chemical compositions of said above luminous materials.

US6375864B1 discloses the luminous plastic compositions for molding comprising transparent or translucent thermoplastic resin mixed with non-radioactive luminous materials or comprising sulfide product and heat resistant polymers that are solvent

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-2soluble. The plastics produced from compositions according to said invention are bright during daytime and suitable for the production of variety of products.

US6599444B2 discloses the luminous polymer compositions comprising thermosetting unsaturated polyester, filler, and phosphorescent materials for molding and gel coating application, wherein the unsaturated thermosetting of said polyester was prepared by the condensation of the ethylenically unsaturated derivative, aromatic dicarboxylic acids, anhydrides with dihydric alcohols, and polymerizable vinylidene monomer.

Thai petty patent no. 12179 discloses the luminous plastic compound compositions for the production of luminous safety helmet to be used in the dark focused in the white hue products employing titanium dioxide as the non-aromatic structured inorganic pigment and using SrALCffiEu as the luminescent material. Said luminous safety helmet was capable as luminescence according to the DIN 67510-1 standard.

From all reasons above, this invention aims to overcome the problems of luminescence in dark color articles by disclosing the luminous polymer compositions which can be luminescent in low light source are and can be molded into specimen in many industries by the injection molding process or blow molding process in order to provide luminescent property to coloring products. This invention can increase the luminescent property and suitable for demands in variety of uses.

Summary of Invention

This invention relates to luminous polymer compositions and article produced by said composition having self-luminous property in dark, wherein said compositions comprising:

a) 80 - 95.0 % by weight of polyolefins;

b) 4.0 - 15.0 % by weight of phosphorescent materials based on MAkCffiX, when

M is alkaline earth element and X is lanthanide element selected from lanthanum (La), neodymium (Nd), europium (Eu), and dysprosium (Dy);

c) 0.01 - 0.10 % by weight of red pigment; and

d) 0.1 - 3.0 % by weight of polymer additives.

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-3Description of the Invention

This invention discloses the luminous polymer compositions and the article produced by said composition comprising polyolefins, phosphorescent materials, red pigment, and polymer additives.

Any aspect shown here is meant to include the application of other aspects of this invention unless stated otherwise.

Technical terms or scientific terms used here have definitions as by a person skilled in the art unless stated otherwise.

The term “luminous” means light shedding, light emission, or light shining in dark 10 environment that can be seen with bare eyes and also including light shedding, light emission, or light shining in normal light environment or during daytime.

Any tools, equipment, methods, or chemicals named here mean tools, equipment, methods, or chemicals being used commonly by a person skilled in the art unless stated otherwise that they are tools, equipment, methods, or chemicals specific only in this invention.

Use of singular noun or singular pronoun with “comprising” in claims or specification means “one” and including “one or more”, “at least one”, and “one or more than one”.

All compositions and/or methods disclosed and claims in this application aim to 20 cover embodiments from any action, performance, modification, or adjustment without any experiment that significantly different from this invention, and obtain with object with utility and resulted as same as the present embodiment according to a person ordinary skilled in the art although without specifically stated in claims. Therefore, substitutable or similar object to the present embodiment, including any little modification or adjustment that clearly seen by a person skilled in the art should be construed as remains in spirit, scope, and concept of invention as appeared in appended claims.

Throughout this application, term “about” means any number that appeared or showed herein that could be varied or deviated from any error of equipment, method, or personal using said equipment or method.

Hereafter, invention embodiments are shown without any purpose to limit any scope of the invention.

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-4The following example is only for demonstrating the embodiments of this invention, not for limiting the scope of this invention in any way.

Luminous polymer compositions, characterized in that said compositions comprising:

a) 80 - 95.0 % by weight of polyolefins;

b) 4.0 - 15.0 % by weight of phosphorescent materials based on MAhCUX, when M is alkaline earth element and X is lanthanide element selected from lanthanum (La), neodymium (Nd), europium (Eu), and dysprosium (Dy);

c) 0.01 - 0.10 % by weight of red pigment; and

d) 0.1 - 3.0 % by weight of polymer additives.

In one embodiment, the polyolefins in a) can be selected from polyethylene, polypropylene, ethylene-polypropylene copolymers, or mixture thereof.

In one embodiment, the luminous polymer compositions in b) comprising 88.0 92.0 % by weight of polyethylene, polypropylene, ethylene-polypropylene copolymers.

In one embodiment, the phosphorescent materials based on MAhCUX are selected from, but not limited to, SrAhCULa, SrAhCUEu, SrAhCUDy, CaAhCUNd, CaAhCUEu, BaAhCUEu, BaAhCUDy, MgAhCUEu, or mixture thereof.

In one embodiment, the phosphorescent material in b) is SrAhCUEu.

In one embodiment, the red pigment in c) is selected from diketo-pyrrolo-pyrrole or anthraquinone, or mixture thereof.

In one embodiment, the polymer additives in d) are selected from processing aid, mold release, optical brightener, antioxidant, coupling agents, reinforcing agents, or mixture thereof.

In one embodiment, to obtain good red luminous polymer compositions, the 25 inventors have developed the mixture of two phosphorescent materials.

In one embodiment, the luminous polymer compositions, characterized in that said compositions comprising:

a) 80 - 95.0 % by weight of polyolefins;

b) 4.0 - 15.0 % by weight of the mixture of phosphorescent materials based on 30 MAkCUX, when M is alkaline earth element and X is lanthanide element selected from lanthanum (La), neodymium (Nd), europium (Eu), and dysprosium (Dy); and

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-5c) 0.1 - 3.0 % by weight of polymer additives.

In one embodiment, the polyolefins in a) are selected from polyethylene, polypropylene, ethylene-polypropylene copolymers, or mixture thereof.

In one embodiment, the mixture of phosphorescent materials in b) are mixture of 5 SrAkCUEu and CaS:Eu or SrS:Eu at the ratio of 1:2 - 2:1.

In one embodiment, the luminous polymer compositions may further comprising the red pigment selected from diketo-pyrrolo-pyrrole or anthraquinone or mixture thereof.

In one embodiment, the polymer additives in c) are selected from processing aid, mold release, optical brightener, antioxidant, coupling agents, reinforcing agents, or mixture thereof.

In one embodiment, the luminous polymer compositions have the following properties:

i) density of in a range of 0.95 - 1.20 g/cm³;

ii) melt flow index at the weight load of 2.16 kg of in a range of 3.0 - 4.6 g/10 min;

and iii) averaged molecular weight (Mw) of in a range of 66,500 - 103,100, wherein the molecular weight distribution is in a range of 8.20 - 9.80.

In one embodiment, the luminous polymer compositions are polymer compounds for producing the plastic product, including but not limited to, injection molding process and blow molding process.

In one embodiment, the luminous polymer compositions can be molded into articles, including but not limited to, plastic injection, clock & watch dials, traffic signs, outdoor path marking, exit sign boards, writing & printing, military applications, textile printing, fishing equipment, and vehicle parts.

The following examples are for demonstrating the embodiments of this invention, not the limitation of this invention in any way.

Preparation of comparative sample 1-2

The preparation of comparative sample started from grinding high density polyethylene. Then, it was mixed with CaS:Eu luminescent material (Manufactured by

New Prismatic Enterprise) and additives according to table 1 with high speed blender equipped with blade for about 3 min. Then, the obtained mixture was melted and mixed

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-6with screw extruder in order to obtain the resin compound pellets. Mixing temperature was set to in a range of 180 - 200 °C.

The obtained resin compound pellets were formed into specimen. The instrument employed was plastic injection molding machine. The forming temperature was in a range of 180 - 220 °C. The obtained specimen was about 3 mm thick, 5 cm wide and 10 cm long. Preparation of luminous sample according to the invention 1-2 The compositions according to the invention could be prepared by the preparation method for comparative sample as described above using SrAkCUEu as the phosphorescent materials. The amount of additives and pigments added in to the compositions according to this invention are shown in table 1.

Preparation of luminous sample according to the invention 3-4

The compositions according to the invention could be prepared as the descripted in the preparation method for comparative sample using SrAkCUEu as the phosphorescent materials and diketo-pyrrolo-pyrrole 2 or anthraquinone as red pigment. The amount of additives and pigments added to the compositions according to this invention are shown in table 1.

Preparation of luminous sample according to the invention 5-6

The compositions according to the invention could be prepared as the descripted in the preparation method for comparative sample using 2 types of phosphorescent materials, which were SrAkCUEu and Cas:Eu mixed at the ratio of 1:1 together with other compositions. The amount of additives and pigments added in to the compositions according to this invention are shown in table 1.

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Testing for luminous performance

The luminous performance could be acquired from the luminous time until the luminescent intensity reached 0.32 mcd/m² according to DIN 67510-1 standard. The specimen was kept without any exposure to the light source for at least 48 hours prior to the test. Then, it was exposed to the 150 watts xenon lamp through the D65 filter at 1,000 lux for 5 mins. The light was radiated perpendicular to the specimen. Then, the luminescent intensity emitted from the specimen was measured by luminance detector of Hanger model ERP-105. The luminescent intensity changed across time was recorded. Therefore, the data recording would continue until the luminescent intensity was substantially stable or until there was not light emitted from the sample. The relationship between luminescent intensity emitted from the sample across times was plotted into graph with fit curve equation. Moreover, the luminous performance was shown as “decay time” which could be calculated from the extrapolation calculation by assigning luminescent intensity variant to 0.32 mcd/m² and recording time or calculating from the graph obtained from the decay time of the specimen.

Results of luminous property testing

Table 2 shows the result of luminous property testing from the comparison of the luminous property of the comparative polymer specimen and the polymer according to the invention. It was found that the CaS:Eu which was the only red luminous compound (comparative sample 1) was difficult to be observed its luminous with naked eyes. When the amount of red luminous compound was increased (comparative sample 2), it was not increase the luminous observation significantly. Moreover, according to the nature of the red luminous compound, in order to increase its luminous performance and duration, the green luminous SrAkCUEu (sample according to the invention 1 and 2) were applied as the luminous compounds. From the test, it was found that the specimen could be well observed with naked eyes in the dark area and provided longer deterioration time than the red luminous compound.

However, in order to obtain good red luminous performance, it could be done by mixing both luminous compounds together at the suitable ratio (sample according to the invention 5 and 6). The luminous performance of the specimen would be higher and able to control red tone as demanded by the adjustment of both luminous compounds and

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-9increasing the durability of the specimen comparing to the use of only one red luminous compound.

Result of the effect of the quantity and ratio of the luminous mixture to the luminescent intensity at different times

From table 2, when comparing the luminescent performance of the comparative samples and the samples according to the invention using the luminous compound for 8 and 10 % at 1, 5, and 10 minutes, it was found that the sample containing 10 % of luminous compound had luminescent intensity at 1 minute higher than samples containing 8 % of luminous compound significantly. However, at 10 minutes, the luminescent intensity of samples containing 8 and 10 % of luminous compounds were quite similar.

Result of the type of red luminous compound that can improve the luminescent performance

When comparing the luminescent performance of the luminous compound of the samples according to the invention using 3 red pigments according to table 2 (sample according to the invention 1, 3, and 4), it was found that the luminescent performances were different although employing same luminous compound. Also, the different red pigment affected the overall luminescent performance. The use of anthraquinone as the red pigment provided higher luminescent performance than the use of diketo-pyrrolo-pyrrole as the red pigment. Moreover, diketo-pyrrolo-pyrrole having different specific area affected a lot on the starting luminescent performance. The diketo-pyrrolo-pyrrole 2 having higher specific area than the diketo-pyrrolo-pyrrole 1 provided higher luminescent performance at the beginning, but said luminescent performance was similar after 10 minutes.

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Sample	Sample according to the invention 6	{Q o C π — $ d o	Red- Yellow- Green light
Sample according to the invention 5	7, d d	Red- Yellow- Green light
Sample according to the invention 4	co OO d 2J -	Yellow- Green light
Sample according to the invention 3	2 so ON OO ’ C\	Yellow- Green light
Sample according to the invention 2	OO _o ά d — d _ ^r8 22 o	Yellow- Green light
Sample according to the invention 1	ON ON g d d	Yellow- Green light
Comparative sample 2	2j IT) IT) . on © d o	Red light
Comparative sample 1	£ 3 § s d d	Red light
	Luminescent intensity, mcd/m² - After 1 min - After 5 min - After 10 min	Glow-in-the- Dark Color

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- 11 From above-mentioned, the use of phosphorescent materials affected a lot on the luminescent performance of the dark color articles. Moreover, different pigments affected a lot on the luminescent performance. The pigment having high specific area had higher luminescent performance at the beginning than the pigment having low specific area significantly. Moreover, to obtain red luminous specimen, the mixing of phosphorescent materials having good luminescent property to the red pigment having lower luminescent property could provide better red luminescent property. The said method can be applied to the industrial that required a good luminescent performance and various color.

Brief Description of the Drawings

Best Mode of the Invention

Best mode of the invention is as provided in the description of the invention.

The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word comprise, and variations such as comprises and comprising, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

Claims

Claims

1. Luminous polymer compositions, characterized in that said compositions comprising:

a) 80 - 95.0 % by weight of polyolefins;

5 b) 4.0 - 15.0 % by weight of phosphorescent materials based on MAkCUX, when

M is alkaline earth element and X is lanthanide element selected from lanthanum (La), neodymium (Nd), europium (Eu), and dysprosium (Dy);

c) 0.01 - 0.10 % by weight of red pigment; and

d) 0.1 - 3.0 % by weight of polymer additives.

10
2. The luminous polymer compositions according to claim 1, wherein the polyolefins in a) are selected from polyethylene, polypropylene, ethylene-polypropylene copolymers, or mixture thereof.
3. The luminous polymer compositions according to claim 1, wherein the phosphorescent material in b) is SrAkCUEu.

15
4. The luminous polymer compositions according to claim 1, wherein the red pigment in c) is selected from diketo-pyrrolo-pyrrole or anthraquinone, or mixture thereof.
5. The luminous polymer compositions according to claim 1, wherein the polymer additives in d) are selected from processing aid, mold release, optical brightener, antioxidant, coupling agents, reinforcing agents, or mixture thereof.

20
6. The luminous polymer compositions, characterized in that said compositions comprising:

a) 80 - 95.0 % by weight of polyolefins;

b) 4.0 - 15.0 % by weight of the mixture of phosphorescent materials based on MAkCUX, when M is alkaline earth element and X is lanthanide element selected from

25 lanthanum (La), neodymium (Nd), europium (Eu), and dysprosium (Dy); and

c) 0.1 - 3.0 % by weight of polymer additives.
7. The luminous polymer compositions according to claim 6, wherein the polyolefins in a) are selected from polyethylene, polypropylene, ethylene-polypropylene copolymers, or mixture thereof.

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- 13
8. The luminous polymer compositions according to claim 6, wherein the mixture of phosphorescent materials in b) are mixture of SrAkCUiEu and CaS:Eu or SrS:Eu at the ratio of 1:2 - 2:1.
9. The luminous polymer compositions according to claim 6, further comprising the 5 red pigment selected from diketo-pyrrolo-pyrrole or anthraquinone or mixture thereof.
10. The luminous polymer compositions according to claim 6, wherein the polymer additives in c) are selected from processing aid, mold release, optical brightener, antioxidant, coupling agents, reinforcing agents, or mixture thereof.