Luminescent gel coats and moldable resins

• US 6,207,077 B1
• Filed: 10/13/1998
• Issued: 03/27/2001
• Est. Priority Date: 02/18/2000
• Status: Expired due to Fees

• Current Assignee: Ozewave Australia Pty Limited
• Original Assignee: Orion 21A.D. Pty., Ltd.
• Inventors: Burnell-Jones, Peter
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US09/170,432
• Time in Patent Office: 896 Days
• Field of Search: 252/301.36, 252/301.33, 252/301.4 K, 252/301.65, 523/514, 523/521, 523/526, 525/15, 525/12, 525/23, 524/403.468, 524/420, 524/423, 524/425, 524/427, 524/437, 524/442, 524/447, 524/786, 524/787, 524/783, 428/690
• US Class Current: 252/301.36
• CPC Class Codes: C08J 2367/06 Unsaturated polyesters
• CPC Class Codes: C08J 5/043 with glass fibres
• CPC Class Codes: C08J 5/244 using glass fibres
• CPC Class Codes: C08J 5/249 characterised by the additives used in the prepolymer mixture
• CPC Class Codes: C08K 3/013 Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 5/0008 Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08K 5/0041 Optical brightening agents, organic pigments
• CPC Class Codes: C08K 5/005 Stabilisers against oxidation, heat, light, ozone
• CPC Class Codes: C08L 2666/18 Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/06 Unsaturated polyesters
• CPC Class Codes: C09K 11/025 non-luminescent particle coatings or suspension media
• CPC Class Codes: C09K 11/584 with zinc or cadmium
• CPC Class Codes: H05K 1/0269 for visual or optical inspection
• CPC Class Codes: H05K 1/0373 containing additives, e.g. fillers H05K1/036 takes precedence

Abstract

Luminescent polymers are prepared from thermosetting unsaturated polyesters, suspending fillers and phosphorescent pigments and utilized to make gel coated articles and molded, cast and fiberglass reinforced plastic (FRP) articles. The luminescent polymers show bright and long-lasting photoluminescent afterglow, strong thermostimulation of afterglow by heat and electroluminescent properties. The preferred thermosetting unsaturated polyester resins are prepared by condensing mixtures of ethylenically unsaturated and aromatic dicarboxylic acids and anhydrides with dihydric alcohols and a polymerizable vinylidene monomer. Phthalic (orthophthalic) and isophthalic aromatic modified polyesters and their substituted derivatives are preferred, particularly those formed from maleate or fumarate unsaturated dicarboxylic acids and anhydrides and a glycol or mixtures of glycols. The preferred monomer is styrene. Preferred suspending fillers and thixotropic modifiers include silica, microspheres, glass fibers and other short fibers, nepheline syenite, feldspar, mica, pumice, magnesium sulfate, calcium carbonate, bentonite and the various clays and thixotropic modifiers and mixtures thereof. Preferred phosphorescent pigments include alkaline earth aluminate phosphors, zinc sulfide phosphors and mixtures of these phosphors. The luminescent resins may be rendered fire retardant and made flexible. As the heavy phosphorescent pigments remain in suspension, the raw luminescent resins are suitable for long-term storage and use.

Claims

1. A luminescent polymer comprising:

a) a thermosetting polyester;

b) a suspending filler;

c) a phosphorescent pigment;

d) a polymerization catalyst; and

e) a reinforcing material comprising a reinforcing fabric, wherein the reinforcing fabric is a fiberglass fabric.

2. A photoluminescent and thermoluminescent gel coated article prepared by adding a polymerization catalyst to a photoluminescent and thermoluminescent polymer and applying as a gel coat to a surface of an article wherein the photoluminescent and luminescent polymer comprises

a) a thermosetting polyester resin;

b) a suspending filler; and

c) photoluminescent and thermoluminescent phosphorescent particles.

3. Coated articles formed by adding a polymerization catalyst to a photoluminescent and thermoluminescent polymer comprising a thermosetting polyester resin, a suspending filler and photoluminescent and thermoluminescent phosphorescent particles wherein catalyzed photoluminescent and thermoluminescent polymer is utilized as a gel coat to form coated articles selected from the group consisting of laminated articles, cast articles and molded articles.

4. A photoluminescent and thermoluminescent article prepared by adding a polymerization catalyst to a photoluminescent and thermoluminescent polymer and applying to a preexisting article to form the photoluminescent and thermoluminescent article, wherein the photoluminescent and thermoluminescent polymer comprises a thermosetting polyester resin, a suspending filler and photoluminescent and thermoluminescent phosphorescent particles and the preexisting article is a fiber optic material.

5. A photoluminescent and thermoluminescent article prepared by adding a polymerization catalyst to a photoluminescent and thermoluminescent polymer and applying to a preexisting article to form the photoluminescent and thermoluminescent article, wherein the photoluminescent and thermoluminescent polymer comprises a thermosetting polyester resin, a suspending filler and photoluminescent and thermoluminescent phosphorescent particles and the preexisting article is a UV bulb.

6. A photoluminescent and thermoluminescent article prepared by adding a polymerization catalyst to a photoluminescent and thermoluminescent polymer and applying to a preexisting article to form the photoluminescent and thermoluminescent article, wherein the photoluminescent and thermoluminescent polymer comprises a thermosetting polyester resin, a suspending filler and photoluminescent and thermoluminescent phosphorescent particles, and wherein the photoluminescent and thermoluminescent polymer additionally comprises a flexible polyester component and is applied to fabrics to form photoluminescent and thermoluminescent fabrics and articles of clothing.

7. A photoluminescent and thermoluminescent article prepared by adding a polymerization catalyst to a photoluminescent and thermoluminescent polymer and applying to a preexisting article to form the photoluminescent and thermoluminescent article, wherein the photoluminescent and thermoluminescent polymer comprises a thermosetting polyester resin, a suspending filler and photoluminescent and thermoluminescent phosphorescent particles and wherein the photoluminescent and thermoluminescent polymer further comprises a fire retardant material selected from the group consisting of fire retardant resins and fire retardant additives.

8. The photoluminescent and thermoluminescent article of claim 7 wherein the fire retardant resins comprise reactive intermediates selected from the group consisting of chlorendic anhydride, tetrabromophthalic anhydride, dibromoneopentyl glycol, tetrachlorophthalic anhydride, decabromodiphenyl oxide (DBDPO) (ether), bromobisphenol-A and pentabromodiphenyl oxide.

9. The photoluminescent and thermoluminescent article of claim 7 wherein the fire retardant additives are selected from the group consisting of ionic bromines, phosphonium bromide, alumina trihydrate, magnesium hydroxide, phosphate esters, vinylphosphonates, bis(hydrocarbyl)vinylphosphonates and their condensation products, antimony oxide, zinc borates, barium metaborates, molybdenum compounds, magnesium carbonate and mixtures of these additives.

10. The photoluminescent and thermoluminescent article of claim 7 wherein the photoluminescent and thermoluminescent polymer is applied to a fabric and utilized to form fire retardant articles selected from the group consisting of clothing and hot air balloons.

11. A process of preparing a luminescent polymer comprising the steps of mixing:

a) a thermosetting polyester resin;

b) a vinylidene monomer;

c) a suspending filler;

d) a thixotropic modifier;

e) a Uv stabilizer; and

f) a phosphorescent pigment;

wherein the thermosetting polyester resin comprises;

i) an ethylenically unsaturated dicarboxylic acid or anhydride component selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, methacrylic acid, acrylic acid, itaconic acid and citraconic acid;

ii) an aromatic dicarboxylic acid or anhydride component selected from the group consisting of phthalic anhydride, isophthalic acid, phthalic acid, chlorendic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic acid and anhydride, adipic acid, succinic acid, suberic acid, sebacic acid, azelaic acid, terephthalic acid and mixtures thereof; and

iii) a dihydric alcohol selected from the group consisting of neopentyl glycol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, dibromoneopentyl glycol, bisphenol dipropoxy ether, 2,2,4-trimethylpentane-1,3-diol, tetrabromobisphenol dipropoxy ether, 1,4-butanediol, Bisphenol A adducts, hydrogenated Bisphenol A, DCPD hydroxyl adducts and mixtures thereof.

12. A process of preparing a luminescent polymer comprising the steps of mixing:

a) a thermosetting polyester resin;

b) a vinylidene monomer;

c) a suspending filler;

d) a thixotropic modifier;

e) a UV stabilizer; and

f) a phosphorescent pigment;

wherein the thermosetting polyester resin comprises;

i) an unsaturated component selected from the group consisting of maleic anhydride, fumaric acid, maleic acid and mixtures thereof;

ii) an aromatic component selected from the group consisting of phthalic anhydride, isophthalic acid and phthalic acid; and

iii) a glycol selected from the group consisting of neopentyl glycol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, dibromoneopentyl glycol, bisphenol dipropoxy ether, 2,2,4-trimethylpentane-1,3-diol, tetrabromobisphenol dipropoxy ether, 1,4-butanediol, Bisphenol A adducts, hydrogenated Bisphenol A, DCPD hydroxyl adducts and mixtures thereof.

13. The process of preparing a luminescent polymer coated surface comprising the steps of:

a) preparing a luminescent polymer resin by mixing a thermosetting polyester resin, a vinylidene monomer, a suspending filler, a thixotropic modifier, a UV stabilizer and a phosphorescent pigment;

b) adding a polymerization catalyst to form a catalyzed luminescent polymer resin; and

c) applying the catalyzed luminescent polymer resin to a surface.

14. A luminescent article comprising an article having at least a portion of a surface to which a luminescent polymer has been applied, wherein the luminescent polymer is prepared by a process comprising the steps of mixing a thermosetting polyester resin, a vinylidene monomer, a suspending filler, a thixotropic modifier, a UV stabilizer and a phosphorescent pigment and adding a polymerization catalyst.

15. The process of making a luminescent polymer comprising:

a) mixing a thermosetting polyester gel coat resin with a thermosetting moldable resin selected from the group consisting of thermosetting laminating resins, thermosetting casting resins and mixtures thereof to form a thermosetting polyester resin mixture;

b) adding a suspending filler to the thermosetting polyester resin mixture in amounts sufficient to suspend heavy phosphorescent pigments; and

c) adding a phosphorescent pigment to the thermosetting polyester resin mixture.

16. The process of making a luminescent polymer of claim 15 wherein the thermosetting polyester resin mixture is selected from the group consisting of orthophthalic polyester resins, isophthalic polyester resins, maleate polyester resins, fumarate polyester resins, glycol polyester resins and mixtures thereof.

17. The process of making the luminescent polymer of claim 15 wherein the process further comprises mixing a thermosetting fire retardant polyester resin into the resin mixture.

18. The process of making the luminescent polymer of claim 15 wherein the process further comprises mixing a thermosetting flexible polyester resin into the resin mixture.

19. The process of making a luminescent shaped article comprising:

a) mixing a thermosetting polyester gel coat resin with a thermosetting moldable resin selected from the group consisting of thermosetting laminating resins, thermosetting casting resins and mixtures thereof to form a thermosetting polyester resin mixture;

b) adding a suspending filler to the thermosetting polyester resin mixture in amounts sufficient to suspend heavy phosphorescent pigments;

c) adding a phosphorescent pigment to the thermosetting polyester resin mixture;

d) adding a catalyst to the thermosetting polyester resin mixture; and

e) forming the thermosetting polyester resin mixture into the luminescent shaped article.

21. The process of making the luminescent shaped article of claim 19 wherein the luminescent shaped article is reinforced with a fiberglass fabric.

20. A luminescent shaped article made by the process comprising:

a) mixing a thermosetting polyester gel coat resin with a thermosetting moldable resin selected from the group consisting of thermosetting laminating resins, thermosetting casting resins and mixtures thereof to form a thermosetting polyester resin mixture;

b) adding a suspending filler to the thermosetting polyester resin mixture in amounts sufficient to suspend heavy phosphorescent pigments;

c) adding a phosphorescent pigment to the thermosetting polyester resin mixture;

d) adding a catalyst to the thermosetting polyester resin mixture; and

e) forming the thermosetting polyester resin mixture into the luminescent shaped article.

22. The process of making a luminescent gel coated product comprising mixing a thermosetting polyester gel coat resin with a thermosetting moldable resin selected from the group consisting of thermosetting laminating resins, thermosetting casting resins and mixtures thereof to form a thermosetting polyester resin mixture, adding a suspending filler to the thermosetting polyester resin mixture in amounts sufficient to suspend heavy phosphorescent pigments, adding a phosphorescent pigment to the thermosetting polyester resin mixture to form a luminescent thermosetting polyester resin mixture, adding a polymerization initiator to the luminescent thermosetting resin mixture to form a catalyzed thermosetting luminescent resin mixture and applying the catalyzed thermosetting luminescent resin mixture as a gel coat to a surface of a product to make the luminescent gel coated product.

23. A luminescent gel coated product made by the process comprising mixing a thermosetting polyester gel coat resin with a thermosetting moldable resin selected from the group consisting of thermosetting laminating resins, thermosetting casting resins and mixtures thereof to form a thermosetting polyester resin mixture, adding a suspending filler to the thermosetting polyester resin mixture in amounts sufficient to suspend heavy phosphorescent pigments adding a phosphorescent pigment to the thermosetting polyester resin mixture to form a luminescent thermosetting polyester resin mixture, adding a polymerization initiator to the thermosetting resin mixture to form a catalyzed luminescent resin mixture and applying the catalyzed luminescent resin mixture as a gel coat to a surface of a product.