Fiber Size, Sized Reinforcements, and Articles Reinforced with Sized Reinforcements

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.

1 . A fiber size composition comprising:
 1) a modified polyolefin;   2) a hydrophilic coupling agent;   3) at least one size enhancing compound selected from
 a) one or more fatty acids selected from cyclic fatty acids and fatty dimer diacids; 
 b) boron compounds; 
 c) one or more fluorine compounds selected from alkali metal fluorides, alkali metal tetrafluoroaluminates, alkali metal hexafluorozirconates and hexafluorosilicates; 
 d) fluoro-boro compounds; and 
 e) hydrophobic coupling agents; and 
   4) a phosphorous(V) compound selected from
 a) phosphoric acid; 
 b) sodium dihydrogen phosphate; 
 c) disodium hydrogen phosphate; 
 d) ammonium phosphate; 
 e) aromatic alcohol phosphates; 
 f) fatty alcohol phosphates; 
 g) ethoxylated phosphates and 
 h) combinations thereof. 
   
     
     
         2 . The fiber size composition according to  claim 1 , wherein:
 the fiber size composition is an aqueous emulsion.   
     
     
         3 . (canceled) 
     
     
         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 maleic acid, acrylic acid, methacrylic acid, maleic anhydride, acrylic anhydride, methacrylic anhydride and oxiranes. 
 
     
     
         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. 
 
     
     
         7 . A fiber size composition comprising:
 a modified polyolefin;   a hydrophilic coupling agent;   a compound selected from boron compounds and fluorine compounds;   a blend of at least two fatty acids; and   a phosphorous(V) compound selected from
 a) phosphoric acid; 
 b) sodium dihydrogen phosphate; 
 c) disodium hydrogen phosphate; 
 d) ammonium phosphate; 
 e) aromatic alcohol phosphates; 
 f) fatty alcohol phosphates; 
 g) ethoxylated phosphates and 
 h) combinations 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 C 8 -C 40  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 succinic acid, propionic acid and butyric acid.   
     
     
         12 . A fiber size composition according to  claim 7 , further comprising a P(III) compound,
 wherein the hydrophilic coupling agent includes an aminosilane; and   wherein the P(III) and P(V) compounds are included at a molar ratio of from 1:1 to 10:1.   
     
     
         13 . A fiber size composition according to  claim 12 ,
 wherein the P(III) and P(V) compounds are included at a molar ratio of from 10:1 to 100:1.   
     
     
         14 .- 23 . (canceled) 
     
     
         24 . The fiber size composition of  claim 1  wherein:
 the at least one size enhancing compound includes a boron compound selected from 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 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 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.   
     
     
         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; 
 3) at least one enhancer selected from
 a) one or more fatty acids selected from cyclic fatty acids and fatty dimer diacids; 
 b) boron compounds; 
 c) one or more fluorine compounds selected from alkali metal fluorides, alkali metal tetrafluoroaluminates, alkali metal hexafluorozirconates and hexafluorosilicates; 
 d) fluoro-boro compounds; and 
 e) hydrophobic coupling agents; and 
 
 4) a phosphorous(V) compound selected from
 a) phosphoric acid; 
 b) sodium dihydrogen phosphate; 
 c) disodium hydrogen phosphate; 
 d) ammonium phosphate; 
 e) aromatic alcohol phosphates; 
 f) fatty alcohol phosphates; 
 g) ethoxylated phosphates and 
 h) combinations thereof. 
 
   
     
     
         31 .- 32 . (canceled) 
     
     
         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 alkylsilanes, vinylsilanes and mixtures thereof.   
     
     
         36 . (canceled) 
     
     
         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, said size composition including,
 1) a modified polyolefin; 
 2) a hydrophilic coupling agent; and 
 3) at least one enhancer selected from
 a) one or more fatty acids selected from cyclic fatty acids and fatty dimer diacids; 
 b) boron compounds; 
 c) one or more fluorine compounds selected from alkali metal fluorides, alkali metal tetrafluoroaluminates, alkali metal hexafluorozirconates and hexafluorosilicates; 
 d) fluoro-boro compounds; 
 e) hydrophobic coupling agents; and 
 
 4) a phosphorous(V) compound selected from
 a) phosphoric acid; 
 b) sodium dihydrogen phosphate; 
 c) disodium hydrogen phosphate; 
 d) ammonium phosphate; 
 e) aromatic alcohol phosphates; 
 f) fatty alcohol phosphates; 
 g) ethoxylated phosphates and 
 h) combinations thereof. 
 
   
     
     
         38 .- 39 . (canceled) 
     
     
         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 alkylsilanes, vinylsilanes and mixtures thereof.   
     
     
         43 . The fiber size composition of  claim 1 , wherein said P(V) compound is phosphoric acid. 
     
     
         44 . The fiber size composition of  claim 1 , wherein said fiber size composition is substantially free of P(III) and S(IV) compounds. 
     
     
         45 . The fiber size composition of  claim 7 , wherein said P(V) compound is phosphoric acid. 
     
     
         46 . The reinforcing fiber of  claim 30 , wherein said size composition is substantially free of P(III) and S(IV) compounds. 
     
     
         47 . The reinforcing fiber of  claim 30 , wherein said P(V) compound is phosphoric acid. 
     
     
         48 . The composite of  claim 37 , wherein said size composition is substantially free of P(III) and S(IV) compounds. 
     
     
         49 . The composite of  claim 37 , wherein said P(V) compound is phosphoric acid.