US5064699A — Semi-rigid heat-sealable laminates with permanent…

Claim 1

Independent Claim 382 words

A semi-rigid heat-sealable, laminate with permanent antistatic characteristics comprising a semi-rigid deformable substrate having a surface with a surface portion for supporting an item to be packaged, and a heat-sealable, permanently antistatic layer extending over and bonded to said surface, said layer including a modified acid copolymer selected from: (I) a mixture of (A) a polymer containing carboxyic acid moieties and (B) an antistatically effective amount of a quaternary amine; or from (II) an acid/base reaction product of (A) a polymer containing carboxylic acid moieties and (C) an antistatically effective amount of an organic base wherein (A), (B), and (C) are defined as follows: (A) the polymer containing carboxylic acid moieties is a copolymer of (i) an alpha-olefin of the formula RCH═CH 2 wherein R is H or C 1 to C 20 alkyl, C 1 to C 20 alkoxy, or C 6 aryl, and (ii) an alpha,beta-ethylenically unsaturated carboxylic acid, and (B) the quaternary amine is of the formula [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N|.sup.+ [X|.sup.- wherein R 1 is selected from H, aryl, or C 1 to C 50 alkyl optionally having one or more non-contiguous C═O or NHC═O or --S-- or --O-- in the carbon chain, or the same as R 2 ; each of R 2 , R 3 , and R 4 is the same or different and selected from H, C 1 to C 18 alkyl optionally substituted with one or more OH or from --(R 5 --O) a --H where a is an integer from 1 to 10 and R 5 is ethylene or propylene; and X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C 1 to C 20 alkyl phosphate, sulfate, C 1 to C 20 alkyl sulfate, formate, C 1 to C 20 alkyl or C 6 to C 24 alkaryl or aryl sulfonate, acetate, trifluoroacetate, citrate, propionate, or tartrate, and (C) the organic base is of the formula M + Y - , wherein M + is [R 6 R 7 R 8 R 9 N] + , where R 6 , R 7 , R 8 , and R 9 are independently selected from a C 1 to C 4 alkyl, benzyl, 2-hydroxyethyl, or hydroxypropyl, and Y| - is selected from hydroxide, C 1 to C 4 alkoxide, bicarbonate, or carbonate.

Claim 2

Dependent Claim 382 words

A semi-rigid heat-sealable, laminate with permanent antistatic characteristics comprising a semi-rigid deformable substrate having a surface with a surface portion for supporting an item to be packaged, and a heat-sealable, permanently antistatic layer extending over and bonded to said surface, said layer including a modified acid copolymer selected from: (I) a mixture of (A) a polymer containing carboxyic acid moieties and (B) an antistatically effective amount of a quaternary amine; or from (II) an acid/base reaction product of (A) a polymer containing carboxylic acid moieties and (C) an antistatically effective amount of an organic base wherein (A), (B), and (C) are defined as follows: (A) the polymer containing carboxylic acid moieties is a copolymer of (i) an alpha-olefin of the formula RCH═CH 2 wherein R is H or C 1 to C 20 alkyl, C 1 to C 20 alkoxy, or C 6 aryl, and (ii) an alpha,beta-ethylenically unsaturated carboxylic acid, and (B) the quaternary amine is of the formula [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N|.sup.+ [X|.sup.- wherein R 1 is selected from H, aryl, or C 1 to C 50 alkyl optionally having one or more non-contiguous C═O or NHC═O or --S-- or --O-- in the carbon chain, or the same as R 2 ; each of R 2 , R 3 , and R 4 is the same or different and selected from H, C 1 to C 18 alkyl optionally substituted with one or more OH or from --(R 5 --O) a --H where a is an integer from 1 to 10 and R 5 is ethylene or propylene; and X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C 1 to C 20 alkyl phosphate, sulfate, C 1 to C 20 alkyl sulfate, formate, C 1 to C 20 alkyl or C 6 to C 24 alkaryl or aryl sulfonate, acetate, trifluoroacetate, citrate, propionate, or tartrate, and (C) the organic base is of the formula M + Y - , wherein M + is [R 6 R 7 R 8 R 9 N] + , where R 6 , R 7 , R 8 , and R 9 are independently selected from a C 1 to C 4 alkyl, benzyl, 2-hydroxyethyl, or hydroxypropyl, and Y| - is selected from hydroxide, C 1 to C 4 alkoxide, bicarbonate, or carbonate.

Claim 3

Dependent Claim 79 words

The laminate of claim 1 wherein the polymer containing carboxylic acid moieties is ethylene-acrylic acid or ethylene-methacrylic acid and the quaternary amine is of the formula wherein: R 1 is C 4 to C 30 alkyl, straight or branched optionally including one or more ether linkages and each of R 2 , R 3 and R 4 is the same or different and selected from methyl or ethyl, and X is chloride, methyl sulfate, ethyl sulfate, methanesulfonate, or toluenesulfonate.

Claim 4

Dependent Claim 51 words

The laminate of claim 1 wherein the polymer containing carboxylic acid moieties is ethylene-acrylic acid or ethylene methacrylic acid and wherein R 6 , R 7 , R 8 and R 9 are selected from methyl, ethyl, or C 2 H 4 OH, and Y| - is hydroxide, methoxide, or ethoxide.

Claim 5

Dependent Claim 40 words

The laminate of claim 1 wherein the antistatic layer will exhibit polycarbonate compatibility and be free of causing crazing of polycarbonate at a stress condition of at least about 2500 psi (176 kg/cm 2 ) and 120° F. (48.9° C.).

Claim 6

Dependent Claim 142 words

The laminate of claim 1 wherein said laminate has the form of an X with a center including said surface portion, opposing first and second arms, each of said first and second arms foldable over said center or over the other arm of said first and second arms when said other arm is folded over said center, a third arm with a slotted opening, said third arm foldable over said center and said first and second arms when said first and second arms are folded, a fourth arm opposing said third arm and foldable over said third arm when said third arm is folded over said center and said first and second arms, and a tabl on said fourth arm for being received into said slotted opening to releasably close said package when said fourth arm is folded over said third arm.

Claim 7

Dependent Claim 80 words

A package constructed from the laminate of claim 1 wherein said surface includes a continuous border portion surrounding said surface portion, and when a static-sensitive item is placed on said surface portion to be packaged, said package further includes a sheet of flexible, heat-sealable, antistatic film vacuum formed over said surface portion and bonded to the portion of said anti-static layer extending over said border portion to form an enclosure over said surface portion, which contains the static sensitive item.

Claim 8

Dependent Claim 25 words

The laminate of claim 1 wherein the polymer containing carboxylic acid moieties is an ionomer containing carboxylic acid moieties partially neutralized by a metal salt.

Claim 9

Dependent Claim 42 words

The laminate of claim 1 wherein the antistatic layer will dissipate an applied charge of ±5000 Vdc in a static decay time less than about 3000 milliseconds and will have a surface resistivity from about 10 5 to about 10 12 ohms/square.

Claim 10

Dependent Claim 36 words

The laminate of claim 8 wherein the static decay time is less than about 3000 milliseconds and the surface resistivity is from about 10 5 to about 10 12 ohms/square, after a 24 hour water shower.

Claim 11

Dependent Claim 41 words

The laminate of claim 8 wherein the static decay time of less than about 3000 milliseconds and the surface resistivity is from about 10 5 to about 10 12 ohms/square, after 12 days in a hot oven of about 70° C.

Claim 12

Dependent Claim 15 words

The laminate of claim 1 wherein a triboelectric enhancer is present in the antistatic layer.

Claim 13

Dependent Claim 28 words

The laminate of claim 11, wherein said triboelectric enhancer is comprised of ethoxylated sorbitan ester, ethoxylated glycerol ester, coco amphopropionate, oleoamphopropyl sulfonate, or ethylene oxide propylene oxide copolymer.

Claim 14

Dependent Claim 365 words

A semi-rigid heat-sealable laminate with permanent anti-static characteristics comprising a semi-rigid deformable substrate having a surface with a surface portion for supporting an item to be packaged, and a heat-sealable, permanently antistatic layer extending over and bonded to said surface, said layer being resultant from mixing with heat, optionally with solvent, (A) a polymer containing carboxylic acid moieties and an antistatically effective amount of a modifier selected from either (B) a quaternary amine or (C) an organic base wherein (A), (B), and (C) are defined as follows: (A) the polymer containing carboxylic acid moieties is a copolymer of (i) an alpha-olefin of the formula RCH═CH 2 wherein R is H or C 1 to C 20 alkyl, C 1 to C 20 alkoxy, or C 6 aryl and (ii) an alpha,beta-ethylenically unsaturated carboxylic acid, and (B) the quaternary amine is of the formula (R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N|.sup.+ X|.sup.- wherein R 1 is selected from H, aryl, or C 1 to C 50 alkyl optionally having one or more non-contiguous C═O or NHC═O or --S-- or --O-- in the carbon chain, or the same as R 2 ; each of R 2 , R 3 , and R 4 is the same or different and selected from H, C 1 to C 18 alkyl optionally substituted with one or more OH or from --R 5 --O) a --H where a is an integer from 1 to 10 and R 5 is ethylene or propylene; and X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C 1 to C 8 alkyl phosphate, sulfate, C 1 to C 8 alkyl sulfate, formate, C 1 to C 8 alkyl or C 6 to C 24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, or tartrate, and (C) the organic base is of the formula M + Y| - , wherein M| + is [R 6 R 7 R 8 R 9 N] + , where R 6 , R 7 , R 8 , and R 9 are independently selected from a C 1 to C 4 alkyl, benzyl, 2-hydroxyethyl, or hydroxypropyl, and Y - is selected from hydroxide, C 1 to C 4 alkoxide, bicarbonate, or carbonate.

Claim 15

Dependent Claim 365 words

A semi-rigid heat-sealable laminate with permanent anti-static characteristics comprising a semi-rigid deformable substrate having a surface with a surface portion for supporting an item to be packaged, and a heat-sealable, permanently antistatic layer extending over and bonded to said surface, said layer being resultant from mixing with heat, optionally with solvent, (A) a polymer containing carboxylic acid moieties and an antistatically effective amount of a modifier selected from either (B) a quaternary amine or (C) an organic base wherein (A), (B), and (C) are defined as follows: (A) the polymer containing carboxylic acid moieties is a copolymer of (i) an alpha-olefin of the formula RCH═CH 2 wherein R is H or C 1 to C 20 alkyl, C 1 to C 20 alkoxy, or C 6 aryl and (ii) an alpha,beta-ethylenically unsaturated carboxylic acid, and (B) the quaternary amine is of the formula (R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N|.sup.+ X|.sup.- wherein R 1 is selected from H, aryl, or C 1 to C 50 alkyl optionally having one or more non-contiguous C═O or NHC═O or --S-- or --O-- in the carbon chain, or the same as R 2 ; each of R 2 , R 3 , and R 4 is the same or different and selected from H, C 1 to C 18 alkyl optionally substituted with one or more OH or from --R 5 --O) a --H where a is an integer from 1 to 10 and R 5 is ethylene or propylene; and X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C 1 to C 8 alkyl phosphate, sulfate, C 1 to C 8 alkyl sulfate, formate, C 1 to C 8 alkyl or C 6 to C 24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, or tartrate, and (C) the organic base is of the formula M + Y| - , wherein M| + is [R 6 R 7 R 8 R 9 N] + , where R 6 , R 7 , R 8 , and R 9 are independently selected from a C 1 to C 4 alkyl, benzyl, 2-hydroxyethyl, or hydroxypropyl, and Y - is selected from hydroxide, C 1 to C 4 alkoxide, bicarbonate, or carbonate.

Claim 16

Dependent Claim 130 words

A semi-rigid, heat-sealable laminate with permanently anti-static characteristics comprising a planar, semi-rigid deformable substrate having a surface with a surface portion for supporting an item to be packaged, and a heat-sealable, permanently antistatic layer extending over and bonded to said surface, said layer obtained from mixing with heat, optionally with solvent, ethylene-acrylic acid or ethylenemethacrylic acid and a quaternary amine of the formula [(R 1 )(R 2 )(R 3 )(R 4 )N + [X - where R 1 is a C 4 to C 30 straight or branched alkyl optionally including one or more ether linkages, each of R 2 and R 3 and R 4 is the same or different and selected from methyl or ethyl, and X is chloride, methyl sulfate, ethyl sulfate, methane sulfonate, or toluene sulfonate.

Claim 17

Dependent Claim 130 words

A semi-rigid, heat-sealable laminate with permanently anti-static characteristics comprising a planar, semi-rigid deformable substrate having a surface with a surface portion for supporting an item to be packaged, and a heat-sealable, permanently antistatic layer extending over and bonded to said surface, said layer obtained from mixing with heat, optionally with solvent, ethylene-acrylic acid or ethylenemethacrylic acid and a quaternary amine of the formula [(R 1 )(R 2 )(R 3 )(R 4 )N + [X - where R 1 is a C 4 to C 30 straight or branched alkyl optionally including one or more ether linkages, each of R 2 and R 3 and R 4 is the same or different and selected from methyl or ethyl, and X is chloride, methyl sulfate, ethyl sulfate, methane sulfonate, or toluene sulfonate.

Claim 18

Dependent Claim 52 words

A package according to claim 14, wherein the permanently antistatic layer will, after a 24 hour water shower, after 12 day oven aging at 70° C., or after both, dissipate an applied charge of ±5000 Vdc in less than about 3000 ms without having being subjected to irradiation from an electron beam.

Claim 19

Dependent Claim 113 words

A semi-rigid, heat-sealable laminate with permanently antistatic characteristics comprising a planar, semi-rigid deformable substrate having a surface with a surface portion for supporting an item to be packaged, and a heat-sealable, permanently antistatic layer extending over and bonded to said surface, said layer obtained from mixing with heat, optionally with solvent, ethylene-acrylic acid or ethylenemethacrylic acid and an organic base of the formula M| + Y| - where M + is R 6 R 7 R 8 R 9 N + wherein R 6 , R 7 , R 8 , and R 9 are selected from methyl, ethyl, or C 2 H 4 OH, and Y - is hydroxide, methoxide, or ethoxide.

Claim 20

Dependent Claim 113 words

A semi-rigid, heat-sealable laminate with permanently antistatic characteristics comprising a planar, semi-rigid deformable substrate having a surface with a surface portion for supporting an item to be packaged, and a heat-sealable, permanently antistatic layer extending over and bonded to said surface, said layer obtained from mixing with heat, optionally with solvent, ethylene-acrylic acid or ethylenemethacrylic acid and an organic base of the formula M| + Y| - where M + is R 6 R 7 R 8 R 9 N + wherein R 6 , R 7 , R 8 , and R 9 are selected from methyl, ethyl, or C 2 H 4 OH, and Y - is hydroxide, methoxide, or ethoxide.

Claim 21

Dependent Claim 42 words

A package according to claim 16, wherein the permanently antistatic layer will, after a 24 hour water shower, after 12 day oven aging at 70° C. or after both, dissipate an applied charge of ±5000 Vdc in less than about 3000 ms.

Claim 22

Independent Claim 359 words

A method for making a semi-rigid, antistatic, heat-sealable laminate with permanent antistatic characteristics comprising (1) modifying an acid copolymer by mixing with heat, optionally with solvent, (A) a polymer containing carboxylic acid moieties and an antistatically effective amount of a modifier selected from either (B) a quaternary amine or (C) an organic base wherein (A), (B), and (C) are defined as follows: (A) the polymer containing carboxylic acid moieties is a copolymer of (i) an alpha-olefin of the formula RCH═CH 2 wherein R is H or C 1 to C 20 alkyl, C 1 to C 20 alkoxy, or C 6 aryl, and (ii) an alpha,beta-ethylenically unsaturated carboxylic acid, and (B) the quaternary amine is of the formula [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N .sup.+ [X .sup.- wherein R 1 is selected from H, aryl, or C 1 to C 50 alkyl optionally having one or more non-contiguous C═O or NHC═O or --S-- or --O-- in the carbon chain, or the same as R 2 ; each of R 2 , R 3 and R 4 is the same or different and selected from H, C 1 to C 18 alkyl optionally substituted with one or more OH or from --(R 5 --O) a --H where a is an integer from 1 to 10 and R 5 is ethylene or propylene; and X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C 1 to C 8 alkyl phosphate, sulfate, C 1 to C 8 alkyl sulfate, formate, C 1 to C 8 alkyl or C y to C 24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, or tartrate, and (C) the organic base is of the formula M + Y - , wherein M + is [R 6 R 7 R 8 R 9 N] + , where R 6 , R 7 , R 8 , and R 9 are independently selected from a C 1 to C 4 alkyl, benzyl, 2-hydroxyethyl, or hydroxypropyl, and Y - is selected from hydroxide, C 1 to C 4 alkoxide, bicarbonate, or carbonate, and (2) applying a layer of said modified acid copolymer/quaternary amine mixture to a sheet of semi-rigid substrate.

Claim 23

Independent Claim 359 words

A method for making a semi-rigid, antistatic, heat-sealable laminate with permanent antistatic characteristics comprising (1) modifying an acid copolymer by mixing with heat, optionally with solvent, (A) a polymer containing carboxylic acid moieties and an antistatically effective amount of a modifier selected from either (B) a quaternary amine or (C) an organic base wherein (A), (B), and (C) are defined as follows: (A) the polymer containing carboxylic acid moieties is a copolymer of (i) an alpha-olefin of the formula RCH═CH 2 wherein R is H or C 1 to C 20 alkyl, C 1 to C 20 alkoxy, or C 6 aryl, and (ii) an alpha,beta-ethylenically unsaturated carboxylic acid, and (B) the quaternary amine is of the formula [(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N .sup.+ [X .sup.- wherein R 1 is selected from H, aryl, or C 1 to C 50 alkyl optionally having one or more non-contiguous C═O or NHC═O or --S-- or --O-- in the carbon chain, or the same as R 2 ; each of R 2 , R 3 and R 4 is the same or different and selected from H, C 1 to C 18 alkyl optionally substituted with one or more OH or from --(R 5 --O) a --H where a is an integer from 1 to 10 and R 5 is ethylene or propylene; and X is an anion selected from chloride, bromide, iodide, fluoride, nitrate, fluoborate, phosphate, C 1 to C 8 alkyl phosphate, sulfate, C 1 to C 8 alkyl sulfate, formate, C 1 to C 8 alkyl or C y to C 24 alkaryl or aryl sulfonate, acetate, citrate, trifluoroacetate, propionate, or tartrate, and (C) the organic base is of the formula M + Y - , wherein M + is [R 6 R 7 R 8 R 9 N] + , where R 6 , R 7 , R 8 , and R 9 are independently selected from a C 1 to C 4 alkyl, benzyl, 2-hydroxyethyl, or hydroxypropyl, and Y - is selected from hydroxide, C 1 to C 4 alkoxide, bicarbonate, or carbonate, and (2) applying a layer of said modified acid copolymer/quaternary amine mixture to a sheet of semi-rigid substrate.

Claim 24

Dependent Claim 44 words

The method of claim 18, wherein said layer is a permanently antistatic film which will, after a 24-hour water shower, after a 12 day oven at 70° C., or after both, dissipate an applied charge of ±5000 Vdc in less than about 3000 milliseconds.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1994-11-11	1995-05-13	1995-11-12	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1998-11-11	1999-05-13	1999-11-12	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2002-11-11	2003-05-13	2003-11-12	$7700.00	Window Closed / Lapsed

Semi-rigid heat-sealable laminates with permanent antistatic characteristics

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