CA1106270A - Thermoformable printed laminate including a clear polyvinyl chloride overlay - Google Patents
Thermoformable printed laminate including a clear polyvinyl chloride overlayInfo
- Publication number
- CA1106270A CA1106270A CA292,191A CA292191A CA1106270A CA 1106270 A CA1106270 A CA 1106270A CA 292191 A CA292191 A CA 292191A CA 1106270 A CA1106270 A CA 1106270A
- Authority
- CA
- Canada
- Prior art keywords
- polyvinyl chloride
- acrylonitrile
- butadiene
- thermoformable
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
- B44C3/02—Superimposing layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2327/00—Polyvinylhalogenides
- B32B2327/06—PVC, i.e. polyvinylchloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2355/00—Specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of index codes B32B2323/00 - B32B2333/00
- B32B2355/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2375/00—Polyureas; Polyurethanes
Landscapes
- Laminated Bodies (AREA)
- Purses, Travelling Bags, Baskets, Or Suitcases (AREA)
Abstract
A THERMOFORMABLE PRINTED LAMINATE
INCLUDING A CLEAR POLYVINYL CHLORIDE OVERLAY
Abstract of the Disclosure A laminated sheet is comprised of a rigid thermo-plastic base layer, an intermediate layer having a design printed thereon and a clear cover sheet of unplasticized polyvinyl chloride. The laminate is thermoformable into luggage components which are resistant to abrasion, resis-tant to crazing upon impact by sharp objects and resistant to whitening when thermoformed.
INCLUDING A CLEAR POLYVINYL CHLORIDE OVERLAY
Abstract of the Disclosure A laminated sheet is comprised of a rigid thermo-plastic base layer, an intermediate layer having a design printed thereon and a clear cover sheet of unplasticized polyvinyl chloride. The laminate is thermoformable into luggage components which are resistant to abrasion, resis-tant to crazing upon impact by sharp objects and resistant to whitening when thermoformed.
Description
f~~6~70 BAC~GROUND GF THE INVENTION
This invention relates to a laminate having a rigid base sheet, an intermediate layer having a design printed on one side thereof and a clear unplasticized polyvinyl chloride cover sheet which protects the printed design from abrasion.
Historically, rigid thermoformable acrylonitrile-butadiene-styrene copolymer or polyvinyl chloride sheets have been produced in solid colors and the aesthetics of the finished thermoformed part was primarily achieved by the use cf various gralns and e~ossing patterns on the embossing ; rolls of the take-off equipment. The lnablllty to produce mar and scratch resistant decorative sheets severely limited its use in some areas, such as luggage. In thls area, the use of lntricate multicolor prlnts has been restricted to the soft-sided plastic or fabric luggage.
In order to produce decorative rigid thermoplastic sheeting,cap sheets of compatible materials (.25 to .5mm) were prlnted and comblned at the extruder to produce a decorative rigid thermoplastic laminate for luggage and other applications. Unfortunately, these constructions ex-hibited poor scratch and mar resistance, especially with dark print pattern on a light base sheet. Applications of various top finishes did not eliminate this problem. The use of plasticized polyvinyl chloride as cover sheet results in mi-gration of the plasticizer into the acrylonitrile-butadiene-styrene substrate resulting in embrittlement. The plasti-cizer also prevents rework of sheeting, because the incor-poration of plasticizer into acrylonitrile-butadiene-styrene 3C copolymer again causes embrittlement.
This invention relates to a laminate having a rigid base sheet, an intermediate layer having a design printed on one side thereof and a clear unplasticized polyvinyl chloride cover sheet which protects the printed design from abrasion.
Historically, rigid thermoformable acrylonitrile-butadiene-styrene copolymer or polyvinyl chloride sheets have been produced in solid colors and the aesthetics of the finished thermoformed part was primarily achieved by the use cf various gralns and e~ossing patterns on the embossing ; rolls of the take-off equipment. The lnablllty to produce mar and scratch resistant decorative sheets severely limited its use in some areas, such as luggage. In thls area, the use of lntricate multicolor prlnts has been restricted to the soft-sided plastic or fabric luggage.
In order to produce decorative rigid thermoplastic sheeting,cap sheets of compatible materials (.25 to .5mm) were prlnted and comblned at the extruder to produce a decorative rigid thermoplastic laminate for luggage and other applications. Unfortunately, these constructions ex-hibited poor scratch and mar resistance, especially with dark print pattern on a light base sheet. Applications of various top finishes did not eliminate this problem. The use of plasticized polyvinyl chloride as cover sheet results in mi-gration of the plasticizer into the acrylonitrile-butadiene-styrene substrate resulting in embrittlement. The plasti-cizer also prevents rework of sheeting, because the incor-poration of plasticizer into acrylonitrile-butadiene-styrene 3C copolymer again causes embrittlement.
- 2 -~1~6z~o SUMMARY OF TIIE INVENTION
It has been found that laminated scratch and mar resistant printed decorative thermoformable sheets can be produced by laminating an extruded thermoplastic base layer, a printed thermoplastic intermediate cap layer, and a thinJ clear, rigid polyvinyl chloride overlay film. This clear, rigid poly-vinyl chloride film protects the printed thermoplastic cap layer and imparts scratch and mar resistance to the print on the layer. Furthermore, it pro-vides ultra-violet stability which maintains color stability and maintains the physical properties of the combination.
Thus, in a recyclable laminate of layers of rigid plastic, formed by hot calendering which laminate is thermoformable without significant stress whitening and which will sustain point impact without significant crazing having: (a) a base layer of a rigid thermoformable sheet of acrylonitrile-butadiene-styrene copolymer having a thickness of from 1 to 5 mms. (b) a decorative intermediate layer of thermoformable acrylonitrile-butadiene-styrene copolymer having a thickness of .1 to .4 mm, having a design printed on one side thereof; this invention provides for the improvement which comprises:
(c) a protective cover sheet consisting essentially of a rigid polyvinyl chloride having a thickness of from 0.025 to 0.25 mm.
The laminates of the present invention do not stress whiten when thermoformed and are resistant to crazing when subjected to a point impact. -~
An additional advantage of the laminates of the present invention is that scrap laminates can be reprocessed to form new base sheets for the manu-facture of subsequent laminates of the present invention. This is important because the trim from the luggage manufacturers is repurchased and recycled saving energy and preventing pollution.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawing shows the extrusion of the base layer and the lamination of the base layer with the printed intermediate layer and the rigid, clear overlay between two heated rolls. The heat of the extruded acrylonitrile-butadiene-styrene causes the laminating. The heated rolls are ... ..
,. . . ...
actually at a lower temperature than the acrylonitrile-butadiene-styrene and they provide the pressure for the lamination process, and an embossing pattern, if desired.
The laminate then continues between the second and third rolls to begin the cooling of the laminate.
DESCP;IPTION OF THE PREFERRED EM~ODIMENTS
The preferred base layer is an acrylonitrile-butadiene-styrene copolymer. The base layer has a thick-ness of from 1 to 5 mm and preferably from 2 to 4 ~m.
The thickness of the base layer is not critical and is deter~mined by practical considerations. These materials are old and well-known in the art and will not be described in detail here. They are commercially available from B Uniroyal as Kralastic SRS acrylonitrile-butadiene-styrene pellets, from Marbon as Cycolac pellets and from Goodrich as Abson pellets.
The acrylonitrile-butadiene-styrene copolymers are manufactured by "graft" polymerization techniques.
The process begins with manufacture of rubber by the polymerization of butadiene, after which styrene and acrylonitrile monomers are added and polymerized (grafted) onto the rubber. The resultant product is either sold as-is or compounded with lubricants, stabilizers, color-ants or other polymers to provide specific levels of per-formance required by the end use.
The acrylonitrile-butadiene-styrene copolymer made by this process contain three ma~or components:
(1) a styrene acrylonitrile copolymer, (2) a styrene a~/e f~ S
11~6~70 acrylonitrile ~opolymer grafted on a polybutadiene rubber and (3) polybutadiene rubber. These components provide a polymer syste~. with two phases - a continuous phase and a dispersed phase - and a boundary layer.
The continuous phase is the styrene acrylonitrile copolymer. It provides processability, rigidity, strength and chemical resistance. Strength, rigidity and process-ability are primarily dependent on molecular weight of the copolymer when the acrylonitrile content is within the normal commercial ranges.
While increased molecular weight improves strength and rigidity, it hampers processabllity through increased melt vlscosity, hence a molecular weight is selected for balanced strength and processability. The chemical resis-tance of the commercial grade styrene acrylonitrile co-polymer is affected by the acrylonitrile content and improves with increased acrylonitrile levels.
The polybutadiene based rubber is the dispersed phase in the acrylonitrile-butadiene-styrene. This phase contributes toughness and impact resistance, both of which depend on many factors. These include the concen-tration of rubber, generally 10 to 30%, and size and dis-tribution of rubber particles, preferably the butadiene content of the copolymer (including polybutadiene) is 15% to 20%.
The second or intermediate layer of the laminate is again preferably an acrylonitrile-butadiene-styrene copolymer. This material is preferred because it is readily printable and will not interfere with the reworking 1.1¢1 6~70 of scrap sheet; to produce new base layers. The acrylo-nitrile-butadiene-styrer.e ir.termediate layer is well-known in the art because it is the composition presently used by various manufacturers in the manufacture of the cap layer of luggage. Various materlals are blended into the inter-mediate layer such as phosphite chelating agents, lubricants, and pigments.
The overlay film is rigid polyvinyl chloride having a thickness of from 0.025 to 0.25 mm and preferably from 0.05 to 0~15 ~. While scrap laminated sheets are reproces-sable from polyvinyl chloride cover sheets, it is preferred that the amount of polyvinyl chloride in the laminated sheet be processed to be as low as possible. In addition, it is necessary that the polyvinyl chloride cover sheet be thick -~
enough to resist tearing durlng the lamination operation.
A compromise of the above two considerations results in the cover sheet having a thickness of fr~m 0.025 to 0.25 mm and preferably from 0.05 to 0.15 mm.
The preferred polyvinyl chloride is a rigid poly-vinyl chloride-polyvinyl acetate copolymer containing from 6 to 12% of polyvinyl acetate. Copolymers of vinyl chloride and propylene are also operable in the practice of the pre-sent invention. Less preferred is polyvinyl chloride made ;
entirely fro~ vinyl chloride monomer. By the term "poly-vinyl chloride" is meant polymers and copolymers of polyvinyl chloride wherein the polyvinyl chloride content of the polymer is at least 50%. By "rigid" polyvinyl chloride it is meant that the polyvinyl chloride not be plasticized.
6 2~ 0 The rolyvinyl chloride can also contain various additives such as impact modifiers. Some examples are methyl methacrylate-butadiene-styrene. The common organotin heat stabilizer can also be present. Lubricants such as stearic acid which are commonly used in polyvinyl chloride can also be present. The polyvinyl chloride can be tinted with colors to mask any yellow color which might be formed during processing or after storage.
A cover sheet which can be used to replace the poly-vinyl chloride cover sheet which is also operable but not pre-ferred in the practice of the present invention is a clear polyurethane sheet having a thickness of from 0.025 to 0.2 mm and preferably from .05 to .15 mm. The poly-urethane, however, is not preferred in part, due to the high cost of this material and the tear problem encountered during lamination.
The following is a speciflc example of the prac-tice of the present invention.
Cycolac pellets obtained from Marbon, a divlsion of Borg Warner, are fed lnto a heated extruder. The ex-truder has a 4-1/2" dlameter barrel and the ratlon of length to dlameter of the extruder barrel is 24 to 1*. -The Cycolac pellets used are an unpigmented acrylonitrile butadiene-styrene copolymer. To the pellets are added -5% based upon the weight of the pellet, of a brown color con-centrate in an acrylonitrile-butadiene-styrene base copoly-mer.
*Preferably the ratio would be 36 to 1.
iz70 The pigmented ~ycolac is extruded at 210C forming a base layer 3.2 m~. thick and 1.13 meters wide. The ex-truder is shown generally as 1 in the drawir.g. The base layer shown as 3 in the drawing passes from the extruder to the nip 16 between rolls 4 and 5. The nip is a space between rollers of 3.2 mm. Roll 4 is heated at 95C, and roll 6 is heated to a temperature of 165C. Simul-taneously, a printed and embossed acrylonitrile-butadiene-styrene intermediate layer 8 having a thickness of 0.3 mm and a rigid polyvinyl chloride overlay 12 having a thick-ness of .12 mm are fed into the nip 16. Layer 8 feeds from roll 10 and overlay 12 feeds from roll 14. In the nip 16 the three layers are combined by the heat of the base sheet and the pressure of rolls 4 and 6 to form a laminate having a thickness of about 3.2 mm. The thick-ness of layer 8 after lamination is estimated at about 0.15 mm. The thickness of overlay 12 after lamination is estimated to be about 0.05 mm.
The laminate 18 which is formed then continues around heated roll 6 and between the spacing 20 formed by the rolls 6 and 22 which is larger than nip 16. Roll 22 has a temperature of 95C and aids in cooling and flattening the laminated sheet. The laminated sheet which is formed is then cooled and cut into appropriate sizes by a mechanism not shown. The intermediate layer 8 previous to its being incorporated into the laminate is calendered and printed. The formulation of the inter-mediate layer 8 is as follows:
11~6~70 Component Amount (Kgs) Acrylonitrile-butadiene-styrene 68.o4 R copolymer (Blendex~qQl from Borg ~W Warner) Phosphite chelator (Ferrc 904 1.4 from Ferro Corp.) Calcium stearate (lubricant) 1.8 Grey pigment (titanium dioxide 1.8 and carbon black) The composition of the overlay is as follows:
Ccmponent Amount (Kg-s) Polyvinyl chloride-polyvinyl136.o8 acetate (6.6% polyvinyl acetate) r~ethyl methacrylate-butadiene 19.9 styrene (Blendex BTA-3-S from (Borg Warner) Organotin heat stabilizer 9.1 Stearic acid .9 Resoform violet tinting agents 0.02 The amounts of materials used in formulating the blends do not indicate the relative amounts of materials which go into each layer.
Attempts to rework the finished laminate by blending it with virgin acrylonitrile-butadiene-styrene and extruding the blend were successful.
It was surprising that polyvinyl chloride was successful as an overlay material because all of the other materials tried except the polyurethane resulted in laminates having one or more drawbacks. The biggest pro-blem encountered was that of stress whitening when ~ ~J¢~u~k 11~6270 atterr.pts were made to therrnoform the larr.inate. Other problems encountered included:
1) a reduction in the irr.pact strength of laminates containing reworked scrap;
r 2) crazing on point impact;
It has been found that laminated scratch and mar resistant printed decorative thermoformable sheets can be produced by laminating an extruded thermoplastic base layer, a printed thermoplastic intermediate cap layer, and a thinJ clear, rigid polyvinyl chloride overlay film. This clear, rigid poly-vinyl chloride film protects the printed thermoplastic cap layer and imparts scratch and mar resistance to the print on the layer. Furthermore, it pro-vides ultra-violet stability which maintains color stability and maintains the physical properties of the combination.
Thus, in a recyclable laminate of layers of rigid plastic, formed by hot calendering which laminate is thermoformable without significant stress whitening and which will sustain point impact without significant crazing having: (a) a base layer of a rigid thermoformable sheet of acrylonitrile-butadiene-styrene copolymer having a thickness of from 1 to 5 mms. (b) a decorative intermediate layer of thermoformable acrylonitrile-butadiene-styrene copolymer having a thickness of .1 to .4 mm, having a design printed on one side thereof; this invention provides for the improvement which comprises:
(c) a protective cover sheet consisting essentially of a rigid polyvinyl chloride having a thickness of from 0.025 to 0.25 mm.
The laminates of the present invention do not stress whiten when thermoformed and are resistant to crazing when subjected to a point impact. -~
An additional advantage of the laminates of the present invention is that scrap laminates can be reprocessed to form new base sheets for the manu-facture of subsequent laminates of the present invention. This is important because the trim from the luggage manufacturers is repurchased and recycled saving energy and preventing pollution.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawing shows the extrusion of the base layer and the lamination of the base layer with the printed intermediate layer and the rigid, clear overlay between two heated rolls. The heat of the extruded acrylonitrile-butadiene-styrene causes the laminating. The heated rolls are ... ..
,. . . ...
actually at a lower temperature than the acrylonitrile-butadiene-styrene and they provide the pressure for the lamination process, and an embossing pattern, if desired.
The laminate then continues between the second and third rolls to begin the cooling of the laminate.
DESCP;IPTION OF THE PREFERRED EM~ODIMENTS
The preferred base layer is an acrylonitrile-butadiene-styrene copolymer. The base layer has a thick-ness of from 1 to 5 mm and preferably from 2 to 4 ~m.
The thickness of the base layer is not critical and is deter~mined by practical considerations. These materials are old and well-known in the art and will not be described in detail here. They are commercially available from B Uniroyal as Kralastic SRS acrylonitrile-butadiene-styrene pellets, from Marbon as Cycolac pellets and from Goodrich as Abson pellets.
The acrylonitrile-butadiene-styrene copolymers are manufactured by "graft" polymerization techniques.
The process begins with manufacture of rubber by the polymerization of butadiene, after which styrene and acrylonitrile monomers are added and polymerized (grafted) onto the rubber. The resultant product is either sold as-is or compounded with lubricants, stabilizers, color-ants or other polymers to provide specific levels of per-formance required by the end use.
The acrylonitrile-butadiene-styrene copolymer made by this process contain three ma~or components:
(1) a styrene acrylonitrile copolymer, (2) a styrene a~/e f~ S
11~6~70 acrylonitrile ~opolymer grafted on a polybutadiene rubber and (3) polybutadiene rubber. These components provide a polymer syste~. with two phases - a continuous phase and a dispersed phase - and a boundary layer.
The continuous phase is the styrene acrylonitrile copolymer. It provides processability, rigidity, strength and chemical resistance. Strength, rigidity and process-ability are primarily dependent on molecular weight of the copolymer when the acrylonitrile content is within the normal commercial ranges.
While increased molecular weight improves strength and rigidity, it hampers processabllity through increased melt vlscosity, hence a molecular weight is selected for balanced strength and processability. The chemical resis-tance of the commercial grade styrene acrylonitrile co-polymer is affected by the acrylonitrile content and improves with increased acrylonitrile levels.
The polybutadiene based rubber is the dispersed phase in the acrylonitrile-butadiene-styrene. This phase contributes toughness and impact resistance, both of which depend on many factors. These include the concen-tration of rubber, generally 10 to 30%, and size and dis-tribution of rubber particles, preferably the butadiene content of the copolymer (including polybutadiene) is 15% to 20%.
The second or intermediate layer of the laminate is again preferably an acrylonitrile-butadiene-styrene copolymer. This material is preferred because it is readily printable and will not interfere with the reworking 1.1¢1 6~70 of scrap sheet; to produce new base layers. The acrylo-nitrile-butadiene-styrer.e ir.termediate layer is well-known in the art because it is the composition presently used by various manufacturers in the manufacture of the cap layer of luggage. Various materlals are blended into the inter-mediate layer such as phosphite chelating agents, lubricants, and pigments.
The overlay film is rigid polyvinyl chloride having a thickness of from 0.025 to 0.25 mm and preferably from 0.05 to 0~15 ~. While scrap laminated sheets are reproces-sable from polyvinyl chloride cover sheets, it is preferred that the amount of polyvinyl chloride in the laminated sheet be processed to be as low as possible. In addition, it is necessary that the polyvinyl chloride cover sheet be thick -~
enough to resist tearing durlng the lamination operation.
A compromise of the above two considerations results in the cover sheet having a thickness of fr~m 0.025 to 0.25 mm and preferably from 0.05 to 0.15 mm.
The preferred polyvinyl chloride is a rigid poly-vinyl chloride-polyvinyl acetate copolymer containing from 6 to 12% of polyvinyl acetate. Copolymers of vinyl chloride and propylene are also operable in the practice of the pre-sent invention. Less preferred is polyvinyl chloride made ;
entirely fro~ vinyl chloride monomer. By the term "poly-vinyl chloride" is meant polymers and copolymers of polyvinyl chloride wherein the polyvinyl chloride content of the polymer is at least 50%. By "rigid" polyvinyl chloride it is meant that the polyvinyl chloride not be plasticized.
6 2~ 0 The rolyvinyl chloride can also contain various additives such as impact modifiers. Some examples are methyl methacrylate-butadiene-styrene. The common organotin heat stabilizer can also be present. Lubricants such as stearic acid which are commonly used in polyvinyl chloride can also be present. The polyvinyl chloride can be tinted with colors to mask any yellow color which might be formed during processing or after storage.
A cover sheet which can be used to replace the poly-vinyl chloride cover sheet which is also operable but not pre-ferred in the practice of the present invention is a clear polyurethane sheet having a thickness of from 0.025 to 0.2 mm and preferably from .05 to .15 mm. The poly-urethane, however, is not preferred in part, due to the high cost of this material and the tear problem encountered during lamination.
The following is a speciflc example of the prac-tice of the present invention.
Cycolac pellets obtained from Marbon, a divlsion of Borg Warner, are fed lnto a heated extruder. The ex-truder has a 4-1/2" dlameter barrel and the ratlon of length to dlameter of the extruder barrel is 24 to 1*. -The Cycolac pellets used are an unpigmented acrylonitrile butadiene-styrene copolymer. To the pellets are added -5% based upon the weight of the pellet, of a brown color con-centrate in an acrylonitrile-butadiene-styrene base copoly-mer.
*Preferably the ratio would be 36 to 1.
iz70 The pigmented ~ycolac is extruded at 210C forming a base layer 3.2 m~. thick and 1.13 meters wide. The ex-truder is shown generally as 1 in the drawir.g. The base layer shown as 3 in the drawing passes from the extruder to the nip 16 between rolls 4 and 5. The nip is a space between rollers of 3.2 mm. Roll 4 is heated at 95C, and roll 6 is heated to a temperature of 165C. Simul-taneously, a printed and embossed acrylonitrile-butadiene-styrene intermediate layer 8 having a thickness of 0.3 mm and a rigid polyvinyl chloride overlay 12 having a thick-ness of .12 mm are fed into the nip 16. Layer 8 feeds from roll 10 and overlay 12 feeds from roll 14. In the nip 16 the three layers are combined by the heat of the base sheet and the pressure of rolls 4 and 6 to form a laminate having a thickness of about 3.2 mm. The thick-ness of layer 8 after lamination is estimated at about 0.15 mm. The thickness of overlay 12 after lamination is estimated to be about 0.05 mm.
The laminate 18 which is formed then continues around heated roll 6 and between the spacing 20 formed by the rolls 6 and 22 which is larger than nip 16. Roll 22 has a temperature of 95C and aids in cooling and flattening the laminated sheet. The laminated sheet which is formed is then cooled and cut into appropriate sizes by a mechanism not shown. The intermediate layer 8 previous to its being incorporated into the laminate is calendered and printed. The formulation of the inter-mediate layer 8 is as follows:
11~6~70 Component Amount (Kgs) Acrylonitrile-butadiene-styrene 68.o4 R copolymer (Blendex~qQl from Borg ~W Warner) Phosphite chelator (Ferrc 904 1.4 from Ferro Corp.) Calcium stearate (lubricant) 1.8 Grey pigment (titanium dioxide 1.8 and carbon black) The composition of the overlay is as follows:
Ccmponent Amount (Kg-s) Polyvinyl chloride-polyvinyl136.o8 acetate (6.6% polyvinyl acetate) r~ethyl methacrylate-butadiene 19.9 styrene (Blendex BTA-3-S from (Borg Warner) Organotin heat stabilizer 9.1 Stearic acid .9 Resoform violet tinting agents 0.02 The amounts of materials used in formulating the blends do not indicate the relative amounts of materials which go into each layer.
Attempts to rework the finished laminate by blending it with virgin acrylonitrile-butadiene-styrene and extruding the blend were successful.
It was surprising that polyvinyl chloride was successful as an overlay material because all of the other materials tried except the polyurethane resulted in laminates having one or more drawbacks. The biggest pro-blem encountered was that of stress whitening when ~ ~J¢~u~k 11~6270 atterr.pts were made to therrnoform the larr.inate. Other problems encountered included:
1) a reduction in the irr.pact strength of laminates containing reworked scrap;
r 2) crazing on point impact;
3) tended to tear during the larr.ination process;
4) poor adhesion resulting in delamination;
5) poGr scratch resistance, and
6) too much gloss The laminates of the present invention are pri-r.~arily useful in the manufacture of the main body of luggage. The lamlnates of the present invention, however, are also useful in thermoforming other articles con-taining an artlstic design and which require a good wear surface. These articles include carrying cases of all kinds, contoured seats, and the exterior shells of tele-phones.
As used in the claims and ln the specification, all parts and percentages are by weight unless otherwise 2Q indicated. The abbreviation "mm" indicates millimeter;
"mms" is the abbreviation for millimeters; and "Kgs" is the abbreviation for kilograms.
As used in the claims and ln the specification, all parts and percentages are by weight unless otherwise 2Q indicated. The abbreviation "mm" indicates millimeter;
"mms" is the abbreviation for millimeters; and "Kgs" is the abbreviation for kilograms.
Claims (2)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a recyclable laminate of layers of rigid plastic, formed by hot calendering which laminate is thermoformable with-out significant stress whitening and which will sustain point impact without significant crazing having:
(a) a base layer of a rigid thermoformable sheet of acrylonitrile-butadiene-styrene copolymer having a thickness of from 1 to 5 mms.
(b) a decorative intermediate layer of thermoformable acrylonitrile-butadiene-styrene copolymer having a thickness of .1 to .4 mm, Having a design printed on one side thereof; where-in the improvement comprises:
(c) a protective cover sheet consisting essentially of a rigid polyvinyl chloride having a thickness of from 0.025 to 0.25 mm.
(a) a base layer of a rigid thermoformable sheet of acrylonitrile-butadiene-styrene copolymer having a thickness of from 1 to 5 mms.
(b) a decorative intermediate layer of thermoformable acrylonitrile-butadiene-styrene copolymer having a thickness of .1 to .4 mm, Having a design printed on one side thereof; where-in the improvement comprises:
(c) a protective cover sheet consisting essentially of a rigid polyvinyl chloride having a thickness of from 0.025 to 0.25 mm.
2. In a recyclable laminate of claim 1 formed by hot calendering having:
(a) the base layer consisting essentially of a sheet of acrylonitrile-butadiene-styrene copolymer having a thickness of from 2 to 4 mm;
(b) the decorative intermediate layer consisting essentially of a sheet of acrylonitrile-butadiene-styrene co-polymer having a thickness of from 0.1 to 0.4 mm wherein the improvement comprises:
(c) a cover sheet consisting essentially of a rigid polyvinyl chloride having a thickness of from 0.05 to 0.15 mm.
(a) the base layer consisting essentially of a sheet of acrylonitrile-butadiene-styrene copolymer having a thickness of from 2 to 4 mm;
(b) the decorative intermediate layer consisting essentially of a sheet of acrylonitrile-butadiene-styrene co-polymer having a thickness of from 0.1 to 0.4 mm wherein the improvement comprises:
(c) a cover sheet consisting essentially of a rigid polyvinyl chloride having a thickness of from 0.05 to 0.15 mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76787177A | 1977-02-11 | 1977-02-11 | |
| US767,871 | 1977-02-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1106270A true CA1106270A (en) | 1981-08-04 |
Family
ID=25080825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,191A Expired CA1106270A (en) | 1977-02-11 | 1977-12-01 | Thermoformable printed laminate including a clear polyvinyl chloride overlay |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5399287A (en) |
| BE (1) | BE863878A (en) |
| CA (1) | CA1106270A (en) |
| DE (1) | DE2757153A1 (en) |
| FR (1) | FR2380132A1 (en) |
| GB (1) | GB1590769A (en) |
| IT (1) | IT1089789B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4935290A (en) * | 1986-08-29 | 1990-06-19 | Rancourt Hubert De | Heat-superstabilized semi-finished products containing thermoplastics resin |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5694328U (en) * | 1979-12-21 | 1981-07-27 | ||
| CA1162471A (en) * | 1980-06-25 | 1984-02-21 | Terence C. O'neill | Decorative laminate of thermoplastic material |
| JPS595334U (en) * | 1982-07-02 | 1984-01-13 | 住友ベークライト株式会社 | multilayer cylindrical container |
| GB2153744B (en) * | 1984-02-08 | 1987-07-29 | Pearce & Cutler Glass Limited | Laminated structure and method of manufacture |
| JP2634917B2 (en) * | 1988-04-28 | 1997-07-30 | イーストマン コダック カンパニー | Protective and decorative sheet material with transparent topcoat |
| US6080473A (en) * | 1999-03-17 | 2000-06-27 | Premark Rwp Holdings, Inc. | ABS substrate extrusion process |
| DE102005023337A1 (en) * | 2005-05-17 | 2006-11-23 | Wipak Walsrode Gmbh & Co.Kg | Thermoformable laminated film, used for packaging, including deep drawn packaging, especially for perishable food has internal printed image between outer carrier and sealing layers |
| BR202019023554U2 (en) * | 2019-11-08 | 2021-05-25 | Bws Conserto De Malas Eireli Me | constructive arrangement applied to travel bags, flasks, bags and similar objects for the purpose of customizing them and process for producing hulls for said pieces |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1482231A (en) * | 1965-05-10 | 1967-05-26 | American Cyanamid Co | Stabilization of polymeric materials including polyvinyl chloride sensitive to light |
| GB1219641A (en) * | 1967-01-10 | 1971-01-20 | Dow Chemical Co | Synthetic polymer laminate |
| FR2196894A1 (en) * | 1972-08-04 | 1974-03-22 | Ono | Polystyrene packaging material - laminated with ABS, MBS and PVC |
| JPS5148507B2 (en) * | 1972-12-22 | 1976-12-21 |
-
1977
- 1977-12-01 CA CA292,191A patent/CA1106270A/en not_active Expired
- 1977-12-20 IT IT30970/77A patent/IT1089789B/en active
- 1977-12-21 DE DE19772757153 patent/DE2757153A1/en not_active Ceased
- 1977-12-28 JP JP15753577A patent/JPS5399287A/en active Granted
-
1978
- 1978-01-12 FR FR7800790A patent/FR2380132A1/en active Granted
- 1978-01-18 GB GB2086/78A patent/GB1590769A/en not_active Expired
- 1978-02-10 BE BE185095A patent/BE863878A/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4935290A (en) * | 1986-08-29 | 1990-06-19 | Rancourt Hubert De | Heat-superstabilized semi-finished products containing thermoplastics resin |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2757153A1 (en) | 1978-08-17 |
| JPS5399287A (en) | 1978-08-30 |
| BE863878A (en) | 1978-05-29 |
| IT1089789B (en) | 1985-06-18 |
| FR2380132A1 (en) | 1978-09-08 |
| JPS5523745B2 (en) | 1980-06-25 |
| GB1590769A (en) | 1981-06-10 |
| FR2380132B1 (en) | 1982-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1274571B2 (en) | Multilayer, co-extruded, ionomeric decorative surfacing | |
| US5728476A (en) | Floor coverings | |
| US7488399B2 (en) | Multi-layer sheet having a weatherable surface layer | |
| AU2001253390A1 (en) | Multilayer, co-extruded, ionomeric decorative surfacing | |
| EP0881261B1 (en) | Acrylic film and moldings made using the same | |
| CA1106270A (en) | Thermoformable printed laminate including a clear polyvinyl chloride overlay | |
| US20020164490A1 (en) | Acrylic resin film and laminated film comprising the same | |
| JP3287255B2 (en) | Acrylic film and molded article using the same | |
| JP3287315B2 (en) | Acrylic film for simultaneous lamination of injection molding | |
| US6348117B1 (en) | Process of preparing textured fluoropolymer films | |
| US11660836B2 (en) | Decorative sheet | |
| EP1000978B1 (en) | Acrylic resin film and laminated film containing the same | |
| US11890845B2 (en) | Decorative sheet | |
| CN116265238A (en) | Synthetic resin skin material, method for producing same, and molded article | |
| JPH09226072A (en) | Decorative sheet and laminated molding | |
| JPH1016141A (en) | Molding skin material and laminate molded body | |
| JPH08309950A (en) | Laminated molding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |