Tear resistant gels, composites, and articles

• US 7,105,607 B2
• Filed: 04/21/2003
• Issued: 09/12/2006
• Est. Priority Date: 04/19/1994
• Status: Expired due to Fees

• Current Assignee: Applied Elastomerics Incorporated
• Original Assignee: Applied Elastomerics Incorporated
• Inventors: Chen, John Y.
• Primary Examiner(s): Harlan, Robert D.
• Application Number:
  US10/420,490
• Publication Number:
  US 20040068040A1
• Time in Patent Office: 1,240 Days
• Field of Search: 525/240, 525/241, 524/366, 524/379
• US Class Current: 525/240
• CPC Class Codes: A61F 2/7843 Inflatable bladders
• CPC Class Codes: C08K 3/013 Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 5/01 Hydrocarbons C08K5/0091 takes precedence
• CPC Class Codes: C08L 53/02 of vinyl-aromatic monomers and conjugated dienes
• CPC Class Codes: C08L 53/025 modified

Abstract

Novel gelatinous compositions, composites, and articles are formed from an intimate melt blend admixture of one or more of a high viscosity poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene)_n, poly(styrene-ethylene)_n triblock and branched copolymers and the like, in combination with high levels or one or more selected plasticizing oil(s) to achieve improvements of compression set resistance and low gel tack.

Claims

1. A composite gel article comprising a gelatinous elastomer composition, G, in contact with one or more of a selected substrate material, M, said gelatinous elastomer composition comprising:

(i) 100 parts by weight of one or more of a hydrogenated styrene isoprene/butadiene block copolymer(s) having one or more selected Brookfield Viscosity value(s) (cps) at 5 weight percent solids solution in toluene at 30°

C.;

(a.) from about 20 to about 35,

(b.) from about 25 to about 150,

(c.) from about 60 to about 150,

(d.) from about 200 to about 400, and

(e.) about 90 cps and higher, which corresponds to a viscosity at 10 weight percent of about 5800 cps and higher which corresponds to a viscosity at 20 weight percent solids solution in toluene at 25°

C. of at about 80,000 cps and higher; and

from

(ii) about 300 to about 1,600 parts by weight of one or more of a selected plasticizer(s) being in sufficient amounts to achieve a gel rigidity of from about 20 gram Bloom to about 1,800 gram Bloom; and

in combination with or without

(iii) a selected amount of one or more polymers or copolymers of poly(styrene-butadiene-styrene), poly(styrene-butadiene)_n, poly(styrene-isoprene-styrene)_n, poly(styrene-isoprene)_n, poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_n, poly(styrene-ethylene-butylene)_n, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, or polyethylene, wherein said selected copolymer is a linear, radial, star-shaped, branched or multiarm copolymer, wherein n is greater than one; and

wherein said composite formed from the combination G_nM_n, G_nM_nM_nG_n, G_nG_nM_nM_n, G_nM_nG_nM_nM_n, G_nM_nG_n, M_nG_nM_n, G_nG_nM_n, M_nM_nM_nG_n, M_nM_nM_nG_nM_n, M_nG_nG_nM_n, G_nM_nG_nG_n, G_nM_nM_nG_n, G_nG_nM_nM_n, G_nG_nM_nG_nM_n, G_nM_nG_nM_nM_n, M_nG_nM_nG_nM_nG_n, G_nG_nM_nM_nG_n, G_nG_nM_nG_nM_nG_n, a sequential addition or a permutation of one or more of said G_n with M_n;

wherein when n is a subscript of M, n is the same or different selected from the group consisting of foam, plastic, fabric, metal, concrete, wood, glass, ceramics, synthetic resin, synthetic fibers or refractory materials; and

wherein when n is a subscript of G, n denotes the same or a different gel rigidity.

6. A gel article of claim 1, 3, 4, or 5, wherein said hydrogenated styrene block copolymer is one or more of a block copolymer of poly(styrene-ethylene-ethylene-propylene-styrene).

7. A gel article of claim 1 or 4, wherein said hydrogenated poly(styrene-isoprene/butadiene-styrene) block polymer is a poly(styrene-ethylene-ethylene-propylene-styrene) block copolymer;

said (iii) polymers and copolymers having sufficient styrene content and in effective minor amounts for said gelatinous elastomer composition to exhibit a greater non-tacky feel to the hand;

wherein one or more of said (ii) plasticizer(s) having a cSt viscosity value at 40°

C. of from about 3 to about 10 in combination with or without one or more plasticizer(s) having a viscosity of at least about 20 cSt being in effective amounts for said gelatinous compositions to have a lower compression set than a conventional plastisol polyvinyl chloride composition of corresponding rigidity.

8. A gel article of claim 1, 3, 4, or 5, wherein one or more of said (i) block copolymer(s) is poly(styrene-ethylene-ethylene-propylene-styrene) having a weight percent of styrene content greater than about 30, and wherein one or more of said component (ii) having a cst viscosity value at 40°

C. selected from;

(k.) about 30 to about 500 and greater,

(l). about 10 to about 30, and

(m.) about 3 to about 10;

wherein said (iii) block copolymer comprises one or more selected poly(ethylene-styrene) interpolymer(s), poly(styrene-ethylene-propylene-styrene), and poly(styrene-butadiene-styrene) copolymer of having a weight percent of styrene content of about 35 and greater and in effective minor amounts for said gelatinous elastomer composition to exhibit a lower non-tack feel to the touch;

one or more of said (k.) and (l.) in effective amounts for said gelatinous compositions to have a lower compression set than a conventional plastisol polyvinyl chloride composition of corresponding rigidity.

12. A gel article according to claim 1, 4, 2 or 11 wherein said gel article is a gel liner for lower limb or above the knee amputee prosthesis formed by injection molding, extruding, spinning, casting, or dipping of said gel;

said gel liner is of the type selected from;

(b.1) L5664 (lower extremity socket insert, above knee),

(b.2) L5665 (socket insert, multi-durometer, below knee),

(b.3) L5666 (below knee, cuff suspension interface), or

(b.4)L5667 (below knee, above knee, socket insert, suction suspension with locking mechanism) devices as described by the American Orthotic &

Prosthetic Association (AOPA) codes.

2. A composite gel article comprising a gelatinous elastomer composition, G, in contact with one or more of a selected substrate material, M, said gelatinous elastomer composition comprising:

(i) 100 parts by weight of a block copolymer of one or a mixture of two or more poly(styrene-ethylene-ethylene-propylene-styrene block copolymers having one or more selected Brookfield Viscosity value(s) (cps) at 5 weight percent solids solution in toluene at 30°

C.;

(a.) from about 20 to about 35,

(b.) from about 25 to about 150,

(c) from about 60 to about 150,

(d.) from about 200 to about 400, and

(e.) about 90 cps and higher, which corresponds to a viscosity at 10 weight percent of about 5800 cps and higher which corresponds to a viscosity at 20 weight percent solids solution in toluene at 25°

C. of at about 80,000 cps and higher; and

(ii) from about 300 to about 1,600 parts by weight of one or more of a plasticizer(s);

wherein said composite formed from the combination G_nM_n, G_nM_nG_n, M_nG_nM_n, M_nG_nG_n, M_nM_nM_nG_n, M_nM_nM_nG_nM_n, M_nG_nG_nM_n, G_nM_nG_nG_n, G_nM_nM_nG_n, G_n G_nM_nG_nM_n, G_nM_nG_nM_nM_n, M_nG_nM_nG_nM_nG_n, G_nG_nM_nM_nG_n, G_nG_nM_nG_nM_nG_n, a sequential addition or a permutation of one or more of said G_n with M_n;

wherein when n is a subscript of M, n is the same or different selected from the group consisting of foam, plastic, fabric, metal, concrete, wood, glass, ceramics, synthetic resin, synthetic fibers or refractory materials; and

wherein when n is a subscript of G, n denotes the same or a different gel rigidity.

9. A gel article of claim 3, 4, or 2 wherein said gelatinous elastomer composition is a dielectric encapsulant formed in combination with one or more of an electrical, or an electronic component(s).

3. A gel article comprising a non-tacky gelatinous elastomer composition formed from:

(i) 100 parts by weight of one or a mixture of two or more of a hydrogenated styrene isoprene/butadiene block copolymer(s) having one or more selected Brookfield Viscosity value(s) (cps) at 5 weight percent solids solution in toluene at 30°

C.;

(a.) from about 20 to about 35,

(b.) from about 25 to about 150,

(c.) from about 60 to about 150,

(d.) from about 200 to about 400, and

(e.) about 90 cps and higher, which corresponds to a viscosity at 10 weight percent of about 5800 cps and higher which corresponds to a viscosity at 20 weight percent solids solution in toluene at 25C of at about 80,000 cps and higher; and

(ii) about 300 to about 1,600 parts by weight of one or more of a selected plasticizer(s) being in sufficient amounts to achieve a gel rigidity of from about 20 gram Bloom to about 1,800 gram Bloom; and

in combination with or without

(iii) a selected amount of one or more polymer or copolymer of poly(styrene-butadiene-styrene), poly(styrene-butadiene)_r, poly(ethylene-styrene), poly(styrene-isoprene-styrene), poly(styrene-isoprene)_n, poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_n, poly(styrene-ethylene-butylene)_n, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, or polyethylene, in effective amounts for said gelatinous compositions to have a greater temperature compression heat set than a conventional plastisol polyvinyl chloride composition of corresponding rigidity, wherein said selected copolymer is a linear, radial, branched, star-shaped, or multiarm copolymer, and n is an integer greater than one; and

wherein at least one said selected plasticizer(s) having a viscosity below about 6 cST at 40°

C.

4. A composite gel article comprising a non-tacky gelatinous elastomer composition:

(i) 100 parts by weight of one or more of a hydrogenated styrene block copolymer(s) with 2-methyl-1,3-butadiene and 1,3-butadiene having one or more selected Brookfield Viscosity value(s) (cps) at 5 weight percent solids solution in toluene at 30°

C.;

(a.) from about 20 to about 35,

(b.) from about 25 to about 150,

(c.) from about 60 to about 150,

(d.) from about 200 to about 400, and

(e.) about 90 cps and higher, which corresponds to a viscosity at 10 weight percent of about 5800 cps and higher which corresponds to a viscosity at 20 weight percent solids solution in toluene at 25°

C. of at about 80,000 cps and higher; and

(ii) about 300 to about 1,600 parts by weight of one or more of a selected plasticizer(s) being in sufficient amounts to achieve a gel rigidity of from about 20 gram Bloom to about 1,800 gram Bloom; and

in combination with or without

(iii) a selected amount of one or more selected polymer or copolymer selected from the group consisting of poly(styrene-butadiene-styrene), poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-isoprene), poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene- butylene), poly(styrene-ethylene-propylene)_n, poly(styrene-ethylene-butylene)_n, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, or polyethylene, wherein said selected copolymer is a linear, radial, branched, star-shaped, or multiarm copolymer; and

n is an integer greater than one, wherein said gelatinous elastomer compositions characterized by a gel rigidity of from about 20 to about 800 gram Bloom;

wherein said composite formed from the combination G_nG_nM_n, M_nM_nM_nG_n, M_nM_nM_nG_nM_n, M_nG_nG_nM_n, G_nM_nG_nG_n, G_nM_nM_nG_n, G_nG_nM_n, G_nG_nM_n, M_nM_nM_nG_n, M_nM_nM_nG_nM_n, M_nG_nG_nM_n, G_nM_nG_nG_n, G_nM_nG_nG_n, G_nM_nM_nG_n, G_nG_nM_nM_n, G_nG_nM_nG_nM_n, G_nM_nG_nM_nM_n, M_nG_nM_nG_nM_nG_n, G_nG_nM_nM_nG_n, G_nG_nM_nG_nM_nG_n a sequential addition or a permutation of one or more of said G_n with M_n;

wherein when n is a subscript of M, n is the same or different selected from the group consisting of foam, plastic, fabric, metal, concrete, wood, glass, ceramics, synthetic resin, synthetic fibers or refractory materials; and

wherein when n is a subscript of G, n denotes the same or a different gel rigidity.

5. A gel article comprising a non-tacky gelatinous elastomer composition formed from components:

(i) 100 parts by weight of one or more of a hydrogenated styrene isoprene/butadiene block copolymer(s) having one or more selected Brookfield Viscosity value(s) (cps) at 5 weight percent solids solution in toluene at 30°

C.;

(a.) from about 20 to about 35,

(b.) from about 25 to about 150,

(c.) from about 60 to about 150,

(d.) from about 200 to about 400, and

(e.) about 90 cps and higher, which corresponds to a viscosity at 10 weight percent of about 5800 cps and higher which corresponds to a viscosity at 20 weight percent solids solution in toluene at 25°

C. of at about 80,000 cps and higher, and

(ii) about 300 to about 1,600 parts by weight of one or more selected plasticizer(s) being in sufficient amounts to achieve a gel rigidity of from about 20 gram Bloom to about 1,800 gram Bloom; and

in combination with or without

(iii) a selected amount of one or more polymers or copolymers of poly(styrene-butadiene-styrene), poly(styrene-butadiene), poly(ethylene-styrene), poly(styrene-isoprene-styrene), poly(styrene-isoprene), poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_n, poly(styrene-ethylene-butylene)_n, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, or polyethylene, wherein said selected copolymer is a linear, branched, radial, star-shaped, or multiarm, copolymer;

wherein one or more of said component (i) having a weight percent of styrene content selected from;

(f.) about 29 and greater,

(g.) about 30 and greater,

(h.) about 35 and greater, and

(j.) about 37 and greater;

 

wherein one or more of said component (ii) having a cSt viscosity value at 40°

C. selected from;

(k.) about 30 to about 500 and greater,

(l). about 10 to about 30,

(m.) about 3 to about 10;

 

wherein said copolymers of one or more of said component (iii) having a styrene to midblock ratio selected from;

(n.) about 20;

80, 21;

79, 22;

78, 23;

77, 24;

76, 25;

75, 26;

74, 27;

73, 28;

72, 29;

71, 30;

70, 31;

69, 32;

68, 33;

67, and greater,

(o.) about 34;

66, 35;

65, 36;

64 and greater,

(p.) About 37;

63, 38;

62, 39;

61, 40;

60, 41;

59, 42;

58, 43;

57, 44;

65, 45;

55, 46;

54, 47;

53, 48;

52, 49;

51 and greater,

(q.) 50;

50, 51;

49, 52;

48, 53;

47, 54;

46, 55;

45, 56;

44, 57;

43, 58;

42, 59;

41, 60;

40, 61;

39, 62;

38, 63;

37, 64;

36, 65;

35, 66;

34, 6;

33, 68;

32, and greater;

one or more of said (h.), (j.), (m.), (o.), and (p.) being selected in effective amounts to impart to said gelatinous composition a greater non-tacky feel to the hand;

one or more of said (h.), (j.), (k.), (o.), (p.), and (q.) in effective amounts to impart to said gelatinous composition an improved lower compression set;

one or more of said (a.)-(e.) in combination with one or more said (m.) in effective amounts to impart to said gelatinous composition a greater non-tacky feel to the hand;

one or more of said (h.), (j.), (k.), and (p.) in combination with one or more said (m.) in effective amounts to impart to said gelatinous composition an improved lower compression set.

10. A gel article comprising a gelatinous elastomer composition, G, in contact with one or more of a selected substrate material, M, said gelatinous elastomer composition comprising:

(i) 100 parts by weight of one or more poly(styrene-ethylene-ethylene-propylene-styrene) block copolymers having one or more selected Brookfield Viscosity value(s) (cps) at 5 weight percent solids solution in toluene at 30°

C.;

(a.) from about 20 to about 35,

(b.) from about 25 to about 150,

(c.) from about 60 to about 150,

(d.) from about 200 to about 400, and

(e.) about 90 cps and higher, which corresponds to a viscosity at 10 weight percent of about 5800 cps and higher which corresponds to a viscosity at 20 weight percent solids solution in toluene at 25°

C. of at about 80,000 cps and higher; and

(ii) about 300 to about 1,600 parts by weight of one or more of a selected plasticizer(s) being in sufficient amounts to achieve a gel rigidity of from about 20 gram Bloom to about 1,800 gram Bloom; and

in combination with or without

(iii) a selected amount of one or more polymers or copolymers of poly(styrene-butadiene-styrene), poly(styrene-butadiene)_n, poly(styrene-isoprene-styrene)_n, poly(styrene-isoprene)_n, poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_n, poly(styrene-ethylene-butylene)_n, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, or polyethylene, wherein said selected copolymer is a linear, radial, star-shaped, branched or multiarm copolymer, wherein n is greater than one;

wherein said composite formed from the combination G_nM_n, G_nM_nG_n, M_nG_nM_n, G_nG_nM_n, G_nG_n, G_nG_nG_nG_n, G_nG_nM_nG_nG_n, M_nM_nM_nG_nM_nM_nM_n, G_nG_nM_n, M_nM_nM_nG_n, M_nM_nM_nG_nM_n, M_nG_nG_nM_n, G_nM_nG_nG_n, G_nM_nM_nG_n, G_nG_nM_nM_n, G_nG_nM_nG_nM_n, G_nM_nG_nM_nM_n, M_nG_nM_nG_nM_nG_n, G_nG_nM_nM_nG_n, G_nG_nM_nG_nM_nG_n, a sequential addition or a permutation of one or more of said G_n with M_n;

wherein when n is a subscript of M, n is the same or different selected from the group consisting of foam, plastic, fabric, metal, metal flakes, concrete, wood, glass, ceramics, synthetic resin, synthetic fibers or refractory materials; and

wherein when n is a subscript of G, n denotes the same or a different gel rigidity;

said composite gel article is formed into a gel hand exercising grip, a gel shape floss suitable for use as a dental floss, a gel crutch cushion, a gel cervical pillow, a gel bed wedge pillow, a gel leg rest, a gel neck cushion, a gel mattress, a gel bed pad, a gel elbow pad, a gel dermal pad, a gel wheelchair cushion, a gel helmet liner, a gel cold and hot pack, a gel exercise weight belt, a gel traction pad or belt, a gel cushion for splints, a gel sling, a gel brace for the hand, wrist, finger, forearm, knee, leg, clavicle, shoulder, foot, ankle, neck, back, rib, a gel sole for orthopedic shoe, a gel shaped toy article, a gel optical cladding for cushioning optical fibers from bending stresses, a gel swab tip, a gel fishing bait, a gel seal against pressure, a gel thread, a gel strip, a gel yarn, a gel tape, a weave gel cloth, a gel fabrics, a gel balloon, a gel air bag, for valvuloplasty of the mitral valve, a gel trointestinal balloon dilator, a gel esophageal balloon dilator, a gel dilating balloon catheter use in coronary angiogram, a gel condom, a gel toy balloon, a gel surgical and examination glove, a self sealing enclosures for splicing electrical and telephone cables and wires, a gel film, a gel liner, a mask, a pad, a blood bags, a tubing, a male and female tubing connectors, and a needle protector sheath, said gel article made by injection molding, extruding, spinning, casting, or dipping of said gel.

11. A composite gel article comprising a gelatinous elastomer composition, G, in contact with one or more of a selected substrate material, M, said gelatinous elastomer composition comprising:

(i) 100 parts by weight of one or a mixture of two or more poly(styrene-ethylene-ethylene-propylene-styrene) block copolymers having one or more selected Brookfield Viscosity value(s) (cps) at 5 weight percent solids solution in toluene at 30°

C.;

(a.) from about 20 to about 35,

(b.) from about 25 to about 150,

(c.) from about 60 to about 150,

(d.) from about 200 to about 400, and

(e.) about 90 cps and higher, which corresponds to a viscosity at 10 weight percent of about 5800 cps and higher which corresponds to a viscosity at 20 weight percent solids solution in toluene at 25°

C. of at about 80,000 cps and higher;

wherein one or more of said component (i) having a weight percent of styrene content selected from;

(f.) about 30 and greater,

(g.) about 35 and greater, and

(h.) about 37 and greater, and

(ii) from about 300 to about 1,600 parts by weight of one or more of a plasticizer(s) and in combination with or without

(iii) a selected amount of one or more polymers or copolymers of poly(styrene-butadiene-styrene), poly(styrene-butadiene)_n, poly(styrene-isoprene-styrene)_n, poly(styrene-isoprene)_n, poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_n, poly(styrene-ethylene-butylene)_n, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, or polyethylene, wherein said selected copolymer is a linear, radial, star-shaped, branched or multiarm copolymer, wherein n is greater than one;

wherein said gelatinous elastomer composition characterized by a gel rigidity of from about 20 to about 800 gram Bloom;

wherein said composite formed from the combination G_nM_n, G_nM_nG_n, M_nG_nM_n, M_nG_nG_n, M_nM_nM_nG_n, M_nM_nM_nG_nM_n, M_nG_nG_nM_n, G_nM_nG_nG_n, G_nM_nM_nG_n, G_nG_nM_nM_n, G_nG_nM_nG_nM_n, G_nM_nG_nM_nM_n, M_nG_nM_nG_nM_nG_n, G_nG_nM_nM_nG_n, G_nG_nM_nG_nM_nG_n, a sequential addition or a permutation of one or more of said G_n with M_n;

wherein when n is a subscript of M, n is the same or different selected from the group consisting of foam, plastic, fabric, metal, concrete, wood, glass, ceramics, synthetic resin, synthetic fibers or refractory materials; and

wherein when n is a subscript of G, n denotes the same or a different gel rigidity.