Fiber size, sized reinforcements, and articles reinforced with sized reinforcements

• US 20060083922A1
• Filed: 12/07/2005
• Published: 04/20/2006
• Est. Priority Date: 05/01/2001
• Status: Active Grant

• Current Assignee: Ocv Intellectual Capital, Llc (Owens Corning)
• Original Assignee: Ocv Intellectual Capital, Llc (Owens Corning)
• Inventors: Kashikar, Sanjay, Henrion, Jean-Marc, Campbell, Les E.
• Granted Patent: US 7,732,047 B2
• Time in Patent Office: Days
• US Class Current: 428/375
• CPC Class Codes: C03C 25/30 Polyolefins
• CPC Class Codes: C03C 25/40 Organo-silicon compounds
• CPC Class Codes: C03C 25/42 Coatings containing inorganic materials
• CPC Class Codes: C03C 3/087 containing calcium oxide, e.g. common sheet or container glass
• CPC Class Codes: C03C 3/112 containing fluorine
• CPC Class Codes: C08K 5/544 containing nitrogen
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 51/06 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• CPC Class Codes: C09D 151/06 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• CPC Class Codes: Y10T 428/249924 Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
• CPC Class Codes: Y10T 428/249948 Fiber is precoated
• CPC Class Codes: Y10T 428/2933 Coated or with bond, impregnation or core
• CPC Class Codes: Y10T 428/2938 Coating on discrete and individual rods, strands or filaments
• CPC Class Codes: Y10T 428/2958 Metal or metal compound in coating
• CPC Class Codes: Y10T 428/2962 Silane, silicone or siloxane in coating
• CPC Class Codes: Y10T 428/2964 Artificial fiber or filament
• CPC Class Codes: Y10T 428/2967 Synthetic resin or polymer

Abstract

A fiber size composition contains a modified polyolefin, a hydrophilic coupling agent, a boron-containing, fluorine-containing compound, a blend of at least two fatty acids and a compound selected from phosphorus(V) compounds and sulfur(VI) compounds, the fiber size composition being substantially free of conventional lower oxidation state antioxidants and optical brighteners. Composite materials produced from reinforcing fiber materials sized with a fiber size composition according to the invention exhibit improved properties such as, for example, increased strength and/or improved color stability.

Claims

1. A fiber size composition comprising:

1) a modified polyolefin;

2) a hydrophilic coupling agent; and

3) at least one size enhancing compound selected from the group of

a) fatty acids;

b) boron compounds;

c) fluorine compounds;

d) fluoro-boro compounds;

e) hydrophobic coupling agents;

f) phosphorus(V) compounds;

g) sulfur(VI) compounds; and

mixtures and combinations thereof;

wherein the fiber size composition is substantially free of P(III) and S(IV) compounds.

2. The fiber size composition according to claim 1, wherein:

the fiber size composition is an aqueous emulsion.

3. The fiber size composition according to claim 1, wherein:

the at least one size enhancing compound includes a fatty acid selected from the group of linear fatty acids, cyclic fatty acids and fatty dimer diacids.

4. The fiber size composition according to claim 1 wherein:

the modified polyolefin is a nonionic aqueous polymer emulsion, the modified polyolefin being modified by the addition of a substituent selected from a group consisting of maleic acid, acrylic acid, methacrylic acid, maleic anhydride, acrylic anhydride, methacrylic anhydride, and oxiranes such as glycidyl acrylates or methacrylates.

5. The fiber size composition according to claim 4 wherein:

the modified polyolefin is a maleic anhydride modified polypropylene having a molecular weight of at least about 10,000.

6. The fiber size composition according to claim 4 wherein:

the modified polyolefin is a maleic anhydride modified polypropylene having a molecular weight of at least about 80,000.

18. A fiber size composition according to claim 1, wherein:

the at least one size enhancing compound includes a fluorine compound selected from the group of fluoroborates, alkali-metal fluorides, alkaline-earth fluorides, fluoroaluminates, fluorozirconates and mixtures thereof.

19. A fiber size composition according to claim 18, wherein:

the fluorine compound is a tetrafluoroborate.

20. A fiber size composition according to claim 19, wherein:

the tetrafluoroborate is selected from the group of alkali metal tetrafluoroborates, alkaline earth tetrafluoroborates, ammonium tetrafluroborate and mixtures thereof.

21. A fiber size composition according to claim 20, wherein:

the tetrafluoroborate is selected from the group of sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium tertrafluoroborate and mixtures thereof.

22. A fiber size composition according to claim 21, wherein:

the tetrafluoroborate is sodium tetrafluoroborate.

23. A fiber size composition according to claim 21, wherein:

the tetrafluoroborate is ammonium tetrafluoroborate.

24. The fiber size composition of claim 1 wherein:

the at least one size enhancing compound includes a boron compound selected from a group consisting of borohydrides, boron halides, boron nitride, organoboron compounds, borazoles, perborates, borosilicates, borates, tetraborates, boric acid and mixtures thereof.

25. The fiber size composition of claim 24 wherein:

the boron compound includes boric acid.

26. The fiber size composition of claim 24 wherein:

the boron compound is a tetraborate selected from the group of alkali metal tetraborates, alkaline earth tetraborates, ammonium borates and mixtures thereof.

27. The fiber size composition of claim 26 wherein:

the tetraborate is selected from the group of disodium tetraborate, dipotassium tetraborate, diammonium tetraborate and mixtures thereof.

28. The fiber size composition of claim 27 wherein:

the tetraborate is disodium tetraborate.

29. The fiber size composition of claim 1, further comprising:

a polyurethane.

7. A fiber size composition comprising:

a modified polyolefin;

a hydrophilic coupling agent;

a compound selected from the group of boron compounds and fluorine compounds;

a blend of at least two fatty acids;

an additive selected from P(III) compounds, P(V) compounds, S(IV) compounds, S(VI) compounds and mixtures thereof.

8. The fiber size composition of claim 7, wherein:

the hydrophilic coupling agent includes one or more aminosilanes.

9. The fiber size composition of claim 7, wherein:

the blend of at least two fatty acids includes a saturated fatty acid having at least two fatty acid groups.

10. The fiber size composition of claim 9, wherein:

the fatty acids include a compound selected from a group consisting of C₈-C₄₀ alkyl chain fatty acids, lower alkyl acids and mixtures thereof.

11. The fiber size composition of claim 10, wherein:

the fatty acids include a lower alkyl acid selected from a group consisting of succinic acid, propionic acid and butyric acid.

12. A fiber size composition according to claim 7, wherein:

the hydrophilic coupling agent includes an aminosilane;

the additive includes both a P(III) compound and a P(V) compound, the P(III) and P(V) compounds being included at a molar ratio of from 1;

1 to 10;

1.

13. A fiber size composition according to claim 7, wherein:

the hydrophilic coupling agent includes an aminosilane;

the additive includes both a P(III) compound and a P(V) compound, the P(III) and P(V) compounds being included at a molar ratio of from 10;

1 to 100;

1.

14. A fiber size composition according to claim 7, wherein:

the hydrophilic coupling agent includes an aminosilane;

the additive consists essentially of a P(V) compound selected from the group of orthophosphoric acid, cyclopolyphosphoric acids, cyclopolyphosphates, orthophosphoric acid salts, phosphates, orthophosphates, NaH₂PO₄, Na₂HPO₄, (NH₄)H₂PO₄, (NH₄)₂HPO₄, phosphate salts formed with other alkali metals and alkaline earth metals, and mixtures thereof.

15. A fiber size composition according to claim 7, wherein:

the hydrophilic coupling agent includes an aminosilane;

the additive consists essentially of a P(V) compound, the P(V) compound being selected from a group consisting of aromatic alcohol phosphates, aromatic phosphoric acid esters and aromatic phosphoric acid ester salts, fatty alcohol phosphates and ethoxylated phosphates.

16. A fiber size composition according to claim 13, wherein:

the additive consists essentially of sodium-2,2′

-methylene-bis(4,6-di-t-butylphenyl)phosphate.

17. A fiber size composition according to claim 7, wherein:

the hydrophilic coupling agent includes an aminosilane;

the additive consists essentially of a S(VI) compound selected from a group consisting of sulfuric acid (H₂SO₄), ammonium salts, NaHSO₄, (NH₄)HSO₄, (NH₄)₂SO₄, salts formed with other alkali metals and alkaline earth metals and mixtures thereof.

30. A reinforcing fiber comprising:

a mineral fiber; and

a size composition layer formed on a majority of a surface area of the mineral fiber, wherein the size composition layer includes,

1) a modified polyolefin;

2) a hydrophilic coupling agent; and

3) at least one enhancer selected from the group of

a) fatty acids;

b) boron compounds;

c) fluorine compounds;

d) fluoro-boro compounds;

e) hydrophobic coupling agents;

f) phosphorus(V) compounds;

g) sulfur(VI) compounds; and

mixtures and combinations thereof;

wherein the fiber size composition is substantially free of P(III) and S(IV) compounds.

31. The reinforcing fiber according to claim 30, wherein:

the at least one enhancer includes a fatty acid selected from the group of straight chain fatty acids, branched chain fatty acids, cyclic fatty acids, fatty dimer diacids and mixtures thereof.

32. The reinforcing fiber according to claim 30, wherein:

the at least one enhancer includes at least one phosphorus(V) compound or sulfur(VI) compound.

33. The reinforcing fiber according to claim 30, wherein:

the at least one enhancer includes boric acid.

34. The reinforcing fiber according to claim 30, wherein:

the at least one enhancer includes a hydrophobic silane coupling agent.

35. The reinforcing fiber according to claim 34, wherein:

the hydrophobic silane coupling agent is selected from the group of alkylsilanes, vinylsilanes and mixtures thereof.

36. The reinforcing fiber according to claim 31, wherein:

the fatty acid includes at least one cyclic fatty acid or fatty dimer diacid.

37. A composite, fiber reinforced product comprising:

a polymer matrix; and

reinforcing fibers distributed throughout the polymer matrix, wherein the reinforcing fibers include a substantially complete layer of a size composition, and further wherein the size composition includes,

1) a modified polyolefin;

2) a hydrophilic coupling agent; and

3) at least one enhancer selected from the group of

a) fatty acids;

b) boron compounds;

c) fluorine compounds;

d) fluoro-boro compounds;

e) hydrophobic coupling agents;

f) phosphorus(V) compounds;

g) sulfur(VI) compounds; and

mixtures and combinations thereof;

wherein the fiber size composition is substantially free of P(III) and S(IV) compounds.

38. The composite, fiber reinforced product according to claim 37, wherein:

the at least one enhancer includes a fatty acid selected from the group of straight chain fatty acids, branched chain fatty acids, cyclic fatty acids and fatty dimer diacids.

39. The composite, fiber reinforced product according to claim 38, wherein:

the fatty acid includes at least one cyclic fatty acid or fatty dimer diacid.

40. The composite, fiber reinforced product according to claim 37, wherein:

the at least one enhancer includes boric acid.

41. The composite, fiber reinforced product according to claim 37, wherein:

the at least one enhancer includes a hydrophobic silane coupling agent.

42. The reinforcing fiber according to claim 41, wherein:

the hydrophobic silane coupling agent is selected from the group of alkylsilanes, vinylsilanes and mixtures thereof.