CA1206312A - Composite structures and method of making same - Google Patents
Composite structures and method of making sameInfo
- Publication number
- CA1206312A CA1206312A CA000408418A CA408418A CA1206312A CA 1206312 A CA1206312 A CA 1206312A CA 000408418 A CA000408418 A CA 000408418A CA 408418 A CA408418 A CA 408418A CA 1206312 A CA1206312 A CA 1206312A
- Authority
- CA
- Canada
- Prior art keywords
- composite structure
- polypropylene
- ethylene
- copolymers
- diene
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J121/00—Adhesives based on unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- 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
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
COMPOSITE STRUCTURES AND METHOD OF MAKING SAME
ABSTRACT
Disclosed is a method of making a composite structure comprising polypropylene, a polar substrate and an adhesive blend in intimate contact therebetween comprising applying in contact with the polypropylene and the substrate an adhes-ive blend free of polypropylene, the blend consisting essential-ly of (a) a graft copolymer of about 70-99.999 wt. % of a poly-ethylene backbone grafted with about 30-0.001 wt. % of at least one compound containing at least one unsaturated carboxylic acid or acid anhydride or both blended with both, (b) at least 30 wt. % of the blend of at least one elastomer selected from the group consisting of copolymers of ethylene and an .alpha.-olefin, terpolymers of ethylene, an .alpha.-olefin and a diene, homopolymers of chloroprene, copolymers of isobutylene, homopolymers of isobutylene, copolymers of a diene and a vinyl aromatic compound, copolymers of a hydrogenated diene and a vinyl aromatic compound, homo-polymers of butadiene, copolymers of an ethylenically unsaturated nitrile and a diene, or a mixture of these, and (c) at least one non-elastomeric polyolefin resin that is either a homopolymer of ethylene, a copolymer of ethylene and .alpha.-olefin, or a mixture of these.
ABSTRACT
Disclosed is a method of making a composite structure comprising polypropylene, a polar substrate and an adhesive blend in intimate contact therebetween comprising applying in contact with the polypropylene and the substrate an adhes-ive blend free of polypropylene, the blend consisting essential-ly of (a) a graft copolymer of about 70-99.999 wt. % of a poly-ethylene backbone grafted with about 30-0.001 wt. % of at least one compound containing at least one unsaturated carboxylic acid or acid anhydride or both blended with both, (b) at least 30 wt. % of the blend of at least one elastomer selected from the group consisting of copolymers of ethylene and an .alpha.-olefin, terpolymers of ethylene, an .alpha.-olefin and a diene, homopolymers of chloroprene, copolymers of isobutylene, homopolymers of isobutylene, copolymers of a diene and a vinyl aromatic compound, copolymers of a hydrogenated diene and a vinyl aromatic compound, homo-polymers of butadiene, copolymers of an ethylenically unsaturated nitrile and a diene, or a mixture of these, and (c) at least one non-elastomeric polyolefin resin that is either a homopolymer of ethylene, a copolymer of ethylene and .alpha.-olefin, or a mixture of these.
Description
Composite Structures and Method of Making Same Backqround of the Invention Usually, polypropylene is adhered to polar pol-ymers, like nylon, ethylene-vinyl alcohol copolymers (EVOH) and polyvinyl alcohol polymers and to metals like aluminum, steel, copper, tin, brass, etc., by interposing a blend of polypropylene grafted with an unsaturated car-boxylic acid or acid derivative and polypropylene. This material is used directly as an adhesive layer between the polypropylene and the polar substrate.
It would sometimes be preEerable to use poly-ethylene gra~ted with unsaturated carboxylic acid or acid derivatives because it can be prepared very easily in a melt reaction system. If one blends the polyethylene graft copolymers with polypropylene, however, relatively poor adhesion is obtained to polar polymers and other ; polar substrates. In some instances, no adhesion at all is obtained between the graft copolymer blend with poly-~~ ~ propylene and the polar substrate. The methods and re-sulting structures of this invention avoid these diffi-culties.
Summary of the Invention By grafting suitable unsaturated carboxylic acids or acid derivatives, for example anhydrides, to 2S polyethylene and blending the resulting graft copolymer with a mixture of polyethylene and an elastomer we have obtained adllesives with-excellent adhesive strength to both polypropylene and to various substrates including polar polymers like nylon, ethylene vinyl alcohol copolymers, polyvinyl alcohol polymers and copolymers, metals, glass, paper, wood and the like. The elastomer aids the blend in adhering to polypropylene since wi-thout its presence, poor adhesion is obtained to polypropylene.
This result could not have been predicted by those skilled in the art, and is, therefore, surprising.
IL~
~ la -The invention in one aspect comprehends the method of making a composite structure comprising polypropylene, a polar substrate and an adhesive blend in intimate contact therebetween comprising applying in contact with the polypropy-lene a~d the substrate an adhesive blend free of polypropylene,the blend consisting essentially of (a~ a graft copolymer of about 70-99.999 wt. % of a polyethylene baokbone grafted with about 30-0.001 wt. % of at least one compound containing at least one unsaturated carboxylic acid or acid anhydride, or both blended with both, (b~ at least 30 wt. % of the blend of at least one elastomer selected from the group consisting of copolymers of ethylene and an ~-olefi.n, ter-polymers of ethylene, an a-olefin and a diene, homopolymers of chloroprene, copolymers of isobutylene, homopolyers of isobutylene, copolymers of a diene and a vinyl aromatic compound, copolymers of a hydrogenated diene and a vinyl aromatic compound, homopolymers of butadiene, copolymers of an ethylenically unsaturated nitrile and a diene, or mixtures of these, and (c) at least one non-elastomeric poly-olefin resin that is either a homopolymer of ethylene, a co-polymer of ethylene and an ~-olefin, or a mixture of these.
The invention also comprehends the composite structure of components comprising polypropylene, a solid substrAte and adhered therebetween the blend as recited above.
120631Z~
..~ ,~ . .. ....
I
Description of the Preferred Embodiments The term polyethylene used herein for the grafting backbone includes homopolymers of ethylene and copolymers of ethylene with propylene, butene-l and other unsaturated aliphatic hydrocarbons. Preferably, the eth-ylene polymer is linear. Also, it is preferable sometimes to graft blends of two or more of these homopolymers and copolymers.
The term polyethylene polymers used herein as a blending resin includes ethylene homopolymers and copol-ymers of ethylene with other unsaturated hydrocarbons with higher olefins such as propylene, butene-l andhexene-1. It is ~ometimes preferable to use blends of two or more of the above homopolymers or copolymers in the blending resin.
The polyethylene homopolymers or copolymers may be prepared by any known process using transition metal catalysts with low or medium pressure or radical initi-ators with high pressure. Hence, the polymers may be low density polyethylenes, linear low density polyethylenes, medium density polyethylenes or high density polyethyl-enes.
By elastomer is meant copolymers of ethylene and an ~-olefin, terpolymers of ethylene, an ~-olefin and a diene, homopolymers of isobutylene, copolymers of iso-butylene, homopolymers of chloroprene, copolymers of a diene and a vinyl aromatic compound~ block copolymers of a diene and vinyl aromatic compound~ copolymers of hydro-genated diene and vinyl aromatic compound, hydrogenated block copolymers of a diene and vinyl aromatic compound, homopolymers of butadiene, and copolymers of an ethylen-ically unsaturated nitrile and a diene.
Some examples of these elastomers are copoly-mers of ethylene and propylene, terpolymers of ethylene, propylene and a diene, copolymers of isobutylene with isoprene, chlorinated copolymers of isobutylene and ~:Z(;)63~
isoprene, copolymers of butadiene and styrene, copolymers of butadiene and vinyl toluene, block copolymers of buta-diene and styrene, block copolymers of butadiene and vinyl toluene, block copolymers of isoprene and s~yrene, block ; 5 copolymers of isoprene and vinyl toluene, hydrogenated copolymers of butadiene and styrene, hydrogenated block copolymers of butadiene and styrene, hydrogenated block copolymers o~ isoprene and styrene, styrene-ethylene bu~
tylene styrene block copolymers, copolymers of acrylo-nitrile and butadiene, copolymers of methacrylonitrile and butadiene, copolymers of acrylonitrile and isoprene, and copolymers of methacrylonitrile and isoprene.
It i5 preferred in the invention to use ethylene-propylene copolymers, ethylene-propylene-diene terpoly-lS mers, homopolymers of isobutylene, chlorinated copolymersof isobut~lene and isoprene, homopolymers of chloroprene, hydrogenated block copolymers of styrene and butadiene, and styrene-ethylene-butylene-styrene block copolymers.
he unsaturated carboxylic acids o~ acia deriva-tives used as the grafting monomers include compounds such as acrylic acid, fumaric acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, citroconic anhydride, itaconic anhydride, 4-methyl cyclohex-4-ene-1,2-dicarboxylic acid 25 anhydride, bicyclo(2.2.2)oct-S-ene-2,3-dicarboxylic acid anhydride, l,2,3,4,5,8,9,10-octahydronaphthalene-
It would sometimes be preEerable to use poly-ethylene gra~ted with unsaturated carboxylic acid or acid derivatives because it can be prepared very easily in a melt reaction system. If one blends the polyethylene graft copolymers with polypropylene, however, relatively poor adhesion is obtained to polar polymers and other ; polar substrates. In some instances, no adhesion at all is obtained between the graft copolymer blend with poly-~~ ~ propylene and the polar substrate. The methods and re-sulting structures of this invention avoid these diffi-culties.
Summary of the Invention By grafting suitable unsaturated carboxylic acids or acid derivatives, for example anhydrides, to 2S polyethylene and blending the resulting graft copolymer with a mixture of polyethylene and an elastomer we have obtained adllesives with-excellent adhesive strength to both polypropylene and to various substrates including polar polymers like nylon, ethylene vinyl alcohol copolymers, polyvinyl alcohol polymers and copolymers, metals, glass, paper, wood and the like. The elastomer aids the blend in adhering to polypropylene since wi-thout its presence, poor adhesion is obtained to polypropylene.
This result could not have been predicted by those skilled in the art, and is, therefore, surprising.
IL~
~ la -The invention in one aspect comprehends the method of making a composite structure comprising polypropylene, a polar substrate and an adhesive blend in intimate contact therebetween comprising applying in contact with the polypropy-lene a~d the substrate an adhesive blend free of polypropylene,the blend consisting essentially of (a~ a graft copolymer of about 70-99.999 wt. % of a polyethylene baokbone grafted with about 30-0.001 wt. % of at least one compound containing at least one unsaturated carboxylic acid or acid anhydride, or both blended with both, (b~ at least 30 wt. % of the blend of at least one elastomer selected from the group consisting of copolymers of ethylene and an ~-olefi.n, ter-polymers of ethylene, an a-olefin and a diene, homopolymers of chloroprene, copolymers of isobutylene, homopolyers of isobutylene, copolymers of a diene and a vinyl aromatic compound, copolymers of a hydrogenated diene and a vinyl aromatic compound, homopolymers of butadiene, copolymers of an ethylenically unsaturated nitrile and a diene, or mixtures of these, and (c) at least one non-elastomeric poly-olefin resin that is either a homopolymer of ethylene, a co-polymer of ethylene and an ~-olefin, or a mixture of these.
The invention also comprehends the composite structure of components comprising polypropylene, a solid substrAte and adhered therebetween the blend as recited above.
120631Z~
..~ ,~ . .. ....
I
Description of the Preferred Embodiments The term polyethylene used herein for the grafting backbone includes homopolymers of ethylene and copolymers of ethylene with propylene, butene-l and other unsaturated aliphatic hydrocarbons. Preferably, the eth-ylene polymer is linear. Also, it is preferable sometimes to graft blends of two or more of these homopolymers and copolymers.
The term polyethylene polymers used herein as a blending resin includes ethylene homopolymers and copol-ymers of ethylene with other unsaturated hydrocarbons with higher olefins such as propylene, butene-l andhexene-1. It is ~ometimes preferable to use blends of two or more of the above homopolymers or copolymers in the blending resin.
The polyethylene homopolymers or copolymers may be prepared by any known process using transition metal catalysts with low or medium pressure or radical initi-ators with high pressure. Hence, the polymers may be low density polyethylenes, linear low density polyethylenes, medium density polyethylenes or high density polyethyl-enes.
By elastomer is meant copolymers of ethylene and an ~-olefin, terpolymers of ethylene, an ~-olefin and a diene, homopolymers of isobutylene, copolymers of iso-butylene, homopolymers of chloroprene, copolymers of a diene and a vinyl aromatic compound~ block copolymers of a diene and vinyl aromatic compound~ copolymers of hydro-genated diene and vinyl aromatic compound, hydrogenated block copolymers of a diene and vinyl aromatic compound, homopolymers of butadiene, and copolymers of an ethylen-ically unsaturated nitrile and a diene.
Some examples of these elastomers are copoly-mers of ethylene and propylene, terpolymers of ethylene, propylene and a diene, copolymers of isobutylene with isoprene, chlorinated copolymers of isobutylene and ~:Z(;)63~
isoprene, copolymers of butadiene and styrene, copolymers of butadiene and vinyl toluene, block copolymers of buta-diene and styrene, block copolymers of butadiene and vinyl toluene, block copolymers of isoprene and s~yrene, block ; 5 copolymers of isoprene and vinyl toluene, hydrogenated copolymers of butadiene and styrene, hydrogenated block copolymers of butadiene and styrene, hydrogenated block copolymers o~ isoprene and styrene, styrene-ethylene bu~
tylene styrene block copolymers, copolymers of acrylo-nitrile and butadiene, copolymers of methacrylonitrile and butadiene, copolymers of acrylonitrile and isoprene, and copolymers of methacrylonitrile and isoprene.
It i5 preferred in the invention to use ethylene-propylene copolymers, ethylene-propylene-diene terpoly-lS mers, homopolymers of isobutylene, chlorinated copolymersof isobut~lene and isoprene, homopolymers of chloroprene, hydrogenated block copolymers of styrene and butadiene, and styrene-ethylene-butylene-styrene block copolymers.
he unsaturated carboxylic acids o~ acia deriva-tives used as the grafting monomers include compounds such as acrylic acid, fumaric acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, citroconic anhydride, itaconic anhydride, 4-methyl cyclohex-4-ene-1,2-dicarboxylic acid 25 anhydride, bicyclo(2.2.2)oct-S-ene-2,3-dicarboxylic acid anhydride, l,2,3,4,5,8,9,10-octahydronaphthalene-
2,2-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro(4,4)non-7-ene, bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic anhydride, maleo-pim~ric acid, tetrahydrophthalic anhydride,x-methylnorborn~5-ene-2,3-dicarboxylic acid anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, Nadic anhydride, methyl Nadic anhydride, Himic anhydride, methyl Himic anhydride and other fused ring monomers described in U.S. patents 35 3,873,643 and 3,882,194, both assigned to the present assignee. Cograft copolymers as described in this U.S.
patent 3,882,194 are also useful in this invention. The methods of preparation of the graf~ copolymers are described in the above U.S. patent~.
Since these blends do not contain polypropY1-ene, the discovery that the blends of this inventionadhere to polypropylene is surprising. Examples of the Gomposites of this invention are polypropylene/adhesive blends of this invention/nylon, polypropylene/-adhesive/ethylene-vinyl alcohol copolymer, polypro-10 pylene/adhesive/alumlnum, polypropylene/adhesive/steel,polypropylene/adhesive/glass, polypropylene/adhesive/-wood, polypropylene/adhesive/leather, polypropylene-/adhesive/nylon/adhesive,~polypropylene r polypropylene/-adhesive/EVOH/adhesive/polypropylene~ and polypropyl-eneJadhesive/aluminum/adhesive/polypropylene. Othermetals ~uch as copper, steel, brass, etc., can be used~
Tt is ob~rious that many more combinations can be made by one skilled in the art using the principles and blends disclosed~
In preparing the three component blends of this invention from the above graft copolymers, elastomers and non~elastomeric ethy~ene homopolymers and copolymers, any blending equipment or technique may be used. As an example, only, blends can be prepared in an electrically heated Brabender PlasticorderTM mixing head using a scroll type mixer under the following conditions: temp rature - 400~, rotor speed - 120 rpm and mixing time lO min. after flux.
The resultant blends were comp~ession mo~ded into films approximately 0.005~0.007 inches thick. The films were then heat sealed to the substrate under eval-uation at an appropriate temperature and time. These conditions are:
patent 3,882,194 are also useful in this invention. The methods of preparation of the graf~ copolymers are described in the above U.S. patent~.
Since these blends do not contain polypropY1-ene, the discovery that the blends of this inventionadhere to polypropylene is surprising. Examples of the Gomposites of this invention are polypropylene/adhesive blends of this invention/nylon, polypropylene/-adhesive/ethylene-vinyl alcohol copolymer, polypro-10 pylene/adhesive/alumlnum, polypropylene/adhesive/steel,polypropylene/adhesive/glass, polypropylene/adhesive/-wood, polypropylene/adhesive/leather, polypropylene-/adhesive/nylon/adhesive,~polypropylene r polypropylene/-adhesive/EVOH/adhesive/polypropylene~ and polypropyl-eneJadhesive/aluminum/adhesive/polypropylene. Othermetals ~uch as copper, steel, brass, etc., can be used~
Tt is ob~rious that many more combinations can be made by one skilled in the art using the principles and blends disclosed~
In preparing the three component blends of this invention from the above graft copolymers, elastomers and non~elastomeric ethy~ene homopolymers and copolymers, any blending equipment or technique may be used. As an example, only, blends can be prepared in an electrically heated Brabender PlasticorderTM mixing head using a scroll type mixer under the following conditions: temp rature - 400~, rotor speed - 120 rpm and mixing time lO min. after flux.
The resultant blends were comp~ession mo~ded into films approximately 0.005~0.007 inches thick. The films were then heat sealed to the substrate under eval-uation at an appropriate temperature and time. These conditions are:
3~L~
1. Nylon 6 - 430F, 2 sc.
2. Ethylene-vinyl alcohol copolymer (EVOH) - ~30C, 5 sec.
3. Polypropylene - 500C, 5 sec.
1. Nylon 6 - 430F, 2 sc.
2. Ethylene-vinyl alcohol copolymer (EVOH) - ~30C, 5 sec.
3. Polypropylene - 500C, 5 sec.
4. Aluminum - 430F, 2 ~ec.
The resultant composi~es were tested by cut-ting into strips one inch wide. Adhesion is then tested by the T-peel test similar to that described in ASTM D
187-72.
Comparative Example 1 X-methyl bicyclot2.2.1)hept-5-ene-2,3-dicar-boxylic anhydride (XMNA) is ~e~ted with a high density polyethylene homopolymer resin in a twin screw extruder to give a graft copolymer resin wi~h 1.5 wt.% XMNA incor-poration and a melt index of 1.5 g/10 min. The graftcopolymer is blended in varying amounts with a random polypropyl~ne-ethylene copolymer having a melt 10w rate (MFR) of 2. These blends were heat sealed to nylon 6 for 2 sec~ at 430F. T-peel adhesion resul~s are summarized below.
Graft CopolymerAdhesion to in Blend Nylon 6 (W`t:.Q ~ (lbsJin) 25 5 0.3 7 0.6 0.
Com~arative Example 2 ~sing the same graft copolymer as described in Example 1, blends were prepared with a propylene-ethylene bloc~ copolymer having an MFR of 2.
Graft CopolymerAdhesion to in Blend Nylon 6 twt.%) (lbs/in) 3510 0.0 lS 003 0.0 ~9 Comparative Example 3 The same blends used in comparative Example 2 were heat sealed for 5 sec. at 430F to an ethylene-vinyl alcohol copolymer (EVOH). All these blends give extremely poor adhesion to EVOH. The samples could not be tested because they fell apart.
Comparative Example 4 Ninety percent of a propylene-ethylene block copolymer containing 7.8% ethylene was blended with 10 wt.% of the same graft copolymers as described in Example 1. This blend was heat sealed to EVOH-and gave a heat seal adhesion of 0.5 lb/in.
Comparative Example 5 When 90% of a polypropylene homopolymer having an MFR of 4 blended with 10~ of the same graft copolymer as described in Example 1, was heat sealed to EVOH, the resultant heat seal adhesion is 0Ol lb/in. If this same blend is heat sealed to a random polypropylene copolymer as described in Comparative Example 1, its adhesion is greater than 10 lbs/in~
The above examples show that i~ a polyethylene graft copolymer is blended with a polypropylene homopol-ymer or a random or a block copolymer containing ethylene, the adhesion is not satisfactory to polar polymers.
Invention Examples 1-7 Blends were prepared using a low density poly-ethylene (LDPE) with a melt index of 1.8 gram per 10 minutes, an ethylene-propylene-diene monomer terpolymer tEPDM) elastomer and the graf~ copolymer described in Comparative Example 1. These blends were tes-ted for adhesion to an ethylene-vinyl alcohol copolymer (EVOH), a random polypropylene copolymer, aluminum and nylon 6.
The results are shown in Table I below:
TABLE I
Composition Adhesion To LDPEEPDM Gra~t EVOH PP Nylon 6Aluminum ~ - Copolymer Random - Copolymer % % lb/inlb/~n lb/in lb/in Example 1 90 -- 10 ~7.1 0 4.4 54 2 65 25 lO >7.6 0.5 3 60 30 lO ~8.0 2.8 >6.1 4.1 ~ 50 40 lO >7~ ~6.3 >5.3 5.9 ~i >7~7~6.5 ~9.~ 5.3 6 35 55 lO >6.5~6.5 ---7 25 65 10 7.4>6.8 >8.1 ;3~
These results show that if the blend contains at least 30% EPDM, adhesion is excellent not only to eth ylene-vinyl alcohol copolymer, nylon 6 and aluminum, but also to polypropylene.
s Inven~ion Examples 8-12 Blends were prepared using the same low density polyethylene as described in Examples 1-7; the same graft copolymer described in Comparative Example landa styrene-ethylene-butylene-styrene block copolymer (a styrene-hy-dxogenated diene-styrene copolymer known as Kraton G 1650 ~SEBS)). The results on adhesion are shown below in Table II.
TABLE II
~omposition Adhesion To LDPE- SEBS Graft EVOH~ PP Nylon 6Aluminum Copolymer 'Random ~ Copolymer~
% ~ % lb/inlb/in lb/in lb/in Example 8 65 25 10 6G 7 1~1 >6.3 ---9 60 30 10 6.8 5.5 >6.5 7.7
The resultant composi~es were tested by cut-ting into strips one inch wide. Adhesion is then tested by the T-peel test similar to that described in ASTM D
187-72.
Comparative Example 1 X-methyl bicyclot2.2.1)hept-5-ene-2,3-dicar-boxylic anhydride (XMNA) is ~e~ted with a high density polyethylene homopolymer resin in a twin screw extruder to give a graft copolymer resin wi~h 1.5 wt.% XMNA incor-poration and a melt index of 1.5 g/10 min. The graftcopolymer is blended in varying amounts with a random polypropyl~ne-ethylene copolymer having a melt 10w rate (MFR) of 2. These blends were heat sealed to nylon 6 for 2 sec~ at 430F. T-peel adhesion resul~s are summarized below.
Graft CopolymerAdhesion to in Blend Nylon 6 (W`t:.Q ~ (lbsJin) 25 5 0.3 7 0.6 0.
Com~arative Example 2 ~sing the same graft copolymer as described in Example 1, blends were prepared with a propylene-ethylene bloc~ copolymer having an MFR of 2.
Graft CopolymerAdhesion to in Blend Nylon 6 twt.%) (lbs/in) 3510 0.0 lS 003 0.0 ~9 Comparative Example 3 The same blends used in comparative Example 2 were heat sealed for 5 sec. at 430F to an ethylene-vinyl alcohol copolymer (EVOH). All these blends give extremely poor adhesion to EVOH. The samples could not be tested because they fell apart.
Comparative Example 4 Ninety percent of a propylene-ethylene block copolymer containing 7.8% ethylene was blended with 10 wt.% of the same graft copolymers as described in Example 1. This blend was heat sealed to EVOH-and gave a heat seal adhesion of 0.5 lb/in.
Comparative Example 5 When 90% of a polypropylene homopolymer having an MFR of 4 blended with 10~ of the same graft copolymer as described in Example 1, was heat sealed to EVOH, the resultant heat seal adhesion is 0Ol lb/in. If this same blend is heat sealed to a random polypropylene copolymer as described in Comparative Example 1, its adhesion is greater than 10 lbs/in~
The above examples show that i~ a polyethylene graft copolymer is blended with a polypropylene homopol-ymer or a random or a block copolymer containing ethylene, the adhesion is not satisfactory to polar polymers.
Invention Examples 1-7 Blends were prepared using a low density poly-ethylene (LDPE) with a melt index of 1.8 gram per 10 minutes, an ethylene-propylene-diene monomer terpolymer tEPDM) elastomer and the graf~ copolymer described in Comparative Example 1. These blends were tes-ted for adhesion to an ethylene-vinyl alcohol copolymer (EVOH), a random polypropylene copolymer, aluminum and nylon 6.
The results are shown in Table I below:
TABLE I
Composition Adhesion To LDPEEPDM Gra~t EVOH PP Nylon 6Aluminum ~ - Copolymer Random - Copolymer % % lb/inlb/~n lb/in lb/in Example 1 90 -- 10 ~7.1 0 4.4 54 2 65 25 lO >7.6 0.5 3 60 30 lO ~8.0 2.8 >6.1 4.1 ~ 50 40 lO >7~ ~6.3 >5.3 5.9 ~i >7~7~6.5 ~9.~ 5.3 6 35 55 lO >6.5~6.5 ---7 25 65 10 7.4>6.8 >8.1 ;3~
These results show that if the blend contains at least 30% EPDM, adhesion is excellent not only to eth ylene-vinyl alcohol copolymer, nylon 6 and aluminum, but also to polypropylene.
s Inven~ion Examples 8-12 Blends were prepared using the same low density polyethylene as described in Examples 1-7; the same graft copolymer described in Comparative Example landa styrene-ethylene-butylene-styrene block copolymer (a styrene-hy-dxogenated diene-styrene copolymer known as Kraton G 1650 ~SEBS)). The results on adhesion are shown below in Table II.
TABLE II
~omposition Adhesion To LDPE- SEBS Graft EVOH~ PP Nylon 6Aluminum Copolymer 'Random ~ Copolymer~
% ~ % lb/inlb/in lb/in lb/in Example 8 65 25 10 6G 7 1~1 >6.3 ---9 60 30 10 6.8 5.5 >6.5 7.7
5 . 7 >9 . 9 3 . 7 3 . 7 1 ~, 11 35 SS 10 5.6>lO.Q >5.8 12 25 6~ ~ 0~ 7.~~1 0.0 >6 .2 ~.
.
.
, :
; .
~ j .
Here again, the use of at least 30% of the elas-tomer enables these blends to adhere to polypropylene in addition to adhering to ethylene-vinyl alcohol copolymer, nylon 6 and aluminum.
Invention Examples 13-15 Blends were prepared with a high density poly-ethylene having an MI of 0.8 and a density o~ 0.96+ with the same graft modified ~DPE described in Comparative Example 1 and several elastomers: EPDM as described in Invention Examples 1-7, a styrene~ethylene-butylene-styrene block copolymer as described in Examples 8-12 and a polyisobutylene (PIB) (Vistanex ~80)TM The results in Table III show that blends containing 45% of the high density polyethylene, 45% of the elastomer and 10% o the modified high density graft copolymer give good ~o excellen~ adhesion to all four substrates.
. , .;
TABLE III
Composition Adhesion to HDPE EPDM PIBSEBSGraft Aluminum EVOH PP Nylon 6 Copolymer ~, Random ., Copolymer % % % % % lb/in lb/in lb/in lb/in ~xample 1345 45 10 >6.8 6.2 2.Q >8.7 ~ :-14 45 -- 45 . 10 3.8 8.3 3.5 >7.3 ~3 -- -- 45 10 3.7 3.4 7.5 4.1 16 90 -- -- -- 10 --- 2.2 0.2 1.9 3~;3:L~
Since adhesion can be obtained to polypropylene and to polar polymers, various composites, laminates and co-extrusions can be prepared using these materials. Com-posites containing polypropylene, adhesive blend and ny-lon, aluminum or ethylene-vinyl alcohol can be prepared both by lamination and by co-extrusion.
In preparing composites one can use any means for joining two or more layers known to one skilled in the art. Preferably methods are blown film co-extrusion, cast film and sheet co-extrusion, blow molding co-extru-sion, lamination, co-extrusion coatlng. Other methods are powder coating, rotomolding, profile co-extrusion, wire coating co-extrusion, etc.
Glossary o~ Terms EVOH ~ ethylene-vinyl asetate copolymers ;15 XMNA - X-methyl bicyclo(~.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride MFR - melt flow rate HDPE - high density polyethylene LDPE ~ low density polyethylene 20 EPDM - ethylene-propylene diene monomer terpolymer SEBS - styrene-ethylene-butylene-styrene copolymer known as Krato~ G 1650 PIB - polyisobutylene
.
.
, :
; .
~ j .
Here again, the use of at least 30% of the elas-tomer enables these blends to adhere to polypropylene in addition to adhering to ethylene-vinyl alcohol copolymer, nylon 6 and aluminum.
Invention Examples 13-15 Blends were prepared with a high density poly-ethylene having an MI of 0.8 and a density o~ 0.96+ with the same graft modified ~DPE described in Comparative Example 1 and several elastomers: EPDM as described in Invention Examples 1-7, a styrene~ethylene-butylene-styrene block copolymer as described in Examples 8-12 and a polyisobutylene (PIB) (Vistanex ~80)TM The results in Table III show that blends containing 45% of the high density polyethylene, 45% of the elastomer and 10% o the modified high density graft copolymer give good ~o excellen~ adhesion to all four substrates.
. , .;
TABLE III
Composition Adhesion to HDPE EPDM PIBSEBSGraft Aluminum EVOH PP Nylon 6 Copolymer ~, Random ., Copolymer % % % % % lb/in lb/in lb/in lb/in ~xample 1345 45 10 >6.8 6.2 2.Q >8.7 ~ :-14 45 -- 45 . 10 3.8 8.3 3.5 >7.3 ~3 -- -- 45 10 3.7 3.4 7.5 4.1 16 90 -- -- -- 10 --- 2.2 0.2 1.9 3~;3:L~
Since adhesion can be obtained to polypropylene and to polar polymers, various composites, laminates and co-extrusions can be prepared using these materials. Com-posites containing polypropylene, adhesive blend and ny-lon, aluminum or ethylene-vinyl alcohol can be prepared both by lamination and by co-extrusion.
In preparing composites one can use any means for joining two or more layers known to one skilled in the art. Preferably methods are blown film co-extrusion, cast film and sheet co-extrusion, blow molding co-extru-sion, lamination, co-extrusion coatlng. Other methods are powder coating, rotomolding, profile co-extrusion, wire coating co-extrusion, etc.
Glossary o~ Terms EVOH ~ ethylene-vinyl asetate copolymers ;15 XMNA - X-methyl bicyclo(~.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride MFR - melt flow rate HDPE - high density polyethylene LDPE ~ low density polyethylene 20 EPDM - ethylene-propylene diene monomer terpolymer SEBS - styrene-ethylene-butylene-styrene copolymer known as Krato~ G 1650 PIB - polyisobutylene
Claims (40)
1. The method of making a composite structure comprising polypropylene, a polar substrate and an adhesive blend in intimate contact therebetween comprising applying in contact with said polypropylene and said substrate an adhesive blend free of polypropylene, said blend consisting essentially of :
(a) a graft copolymer of about 70-99.999 wt. %
of a polyethylene backbone grafted with about 30-0.001 wt.
% of at least one compound containing at least one unsaturated carboxylic acid or acid anhydride or both blended with both, (b) at least 30 wt. % of said blend of at least one elastomer selected from the group consisting of co-polymers of ethylene and an .alpha.-olefin, terpolymers of ethylene, an .alpha.-olefin and a diene, homopolymers of chloroprene, copolymers of isobutylene, homopolymers of isobutylene, copolymers of a diene and a vinyl aromatic compound, copolymers of a hydrogenated diene and a vinyl aromatic compound, homopolymers of butadiene, copolymers of an ethylenically unsaturated nitrile and a diene, and mixtures of these, and (c) at least one non-elastomeric polyolefin resin that is either a homopolymer of ethylene, a copolymer of ethylene and an .alpha.-olfin, or a mixture of these.
(a) a graft copolymer of about 70-99.999 wt. %
of a polyethylene backbone grafted with about 30-0.001 wt.
% of at least one compound containing at least one unsaturated carboxylic acid or acid anhydride or both blended with both, (b) at least 30 wt. % of said blend of at least one elastomer selected from the group consisting of co-polymers of ethylene and an .alpha.-olefin, terpolymers of ethylene, an .alpha.-olefin and a diene, homopolymers of chloroprene, copolymers of isobutylene, homopolymers of isobutylene, copolymers of a diene and a vinyl aromatic compound, copolymers of a hydrogenated diene and a vinyl aromatic compound, homopolymers of butadiene, copolymers of an ethylenically unsaturated nitrile and a diene, and mixtures of these, and (c) at least one non-elastomeric polyolefin resin that is either a homopolymer of ethylene, a copolymer of ethylene and an .alpha.-olfin, or a mixture of these.
2. The method of Claim 1 wherein said applying comprises pressure laminating.
3. The method of Claim 1 wherein said applying comprises co-extrusion.
4. The method of Claim 1 wherein said applying comprises co-extrusion laminating.
5. The method of claim 1 wherein said (c) resin comprises an ethylene homopolymer.
6. The method of claim 1 wherein said (c) resin comprises a copolymer of ethylene an an .alpha.-olefin.
7. The method of claim 1 wherein said (c) resin comprises polyethylene of a density of from about 0.910-0.965.
8. The method of claim 1 wherein said (c) resin comprises a linear copolymer of an .alpha.-olefin containing 3-8 carbon atoms for a total of 100 wt.%.
9. The method of claim 1 wherein said (c) resin comprises a mixture of ethylene polymers and ethylene-.alpha.-olefin copolymers.
10. The method of claim 1 wherein said graft copolymer of (a) comprises a high density polyethylene polymer and x-methylbicyclo(2.2.l)hept-5-ene-2,3-dicar boxylic acid anhydride.
11. The method of claim 10 wherein said (b) comprises polyisobutylene and (c) comprises high density polyethylene.
12. The method of claim 10 wherein said (c) comprises polyethylene and (b) comprises chlorinated butyl rubber.
13. The method of claim 10 wherein said (c) comprises polyethylene and (b) comprises neoprene.
14. The method of Claim 10 wherein said (c) comprises polyethylene and (b) comprises a styrene-ethylene-butylene-styrene block copolymer.
15. The method of Claim 1 wherein said backbone of (a) comprises HDPE with a density of about 0.930-0.970.
16. The method of Claim 15 wherein said backbone of (a) has a density of about 0.940-0.970.
17. The method of Claim 1 wherein said graft copolymer of (a) comprises a high density polyethylene polymer and 4-methylcyclohex-4-ene-1, 2-dicarboxylic acid anhydride.
18. The method of Claim 1 wherein said graft copolymer of (a) comprises a high density polyethylene polymer and at least one monomer comprising tetrahydrophthalic anhydride.
19. The method of Claim 1 wherein said carboxylic acid anhydride of (a) consists essentially of x-methyl-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride.
20. The method of Claim 1 wherein said elastomer of (b) is selected from the group consisting of block copolymers of a diene and a vinyl aromatic compound, and hydrogenated block copolymers of a diene and a vinyl aromatic compound.
21. A composite structure of components com-prising:
(a) polypropylene;
(b) a solid substrate, and adhered therebetween (c) an adhesive blend as recited in claim 1.
(a) polypropylene;
(b) a solid substrate, and adhered therebetween (c) an adhesive blend as recited in claim 1.
22. The composite structure of claim 21 wherein said substrate comprises a member of the class consisting of polar polymers, solid metals, glass, paper, wood and Cellophane TM.
23. The composite structure of claim 21 wherein said substrate comprises nylon.
24. The composite structure of claim 21 wherein said substrate is polar.
25. The composite structure of claim 21 wherein the total of said components is greater than three.
26. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhe-sive blends of this invention/nylon.
27. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhe-sive/ethylene-vinyl alcohol copolymer.
28. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhe-sive/aluminum.
29. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhe-sive/steel.
30. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhesive/
glass.
glass.
31. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhesive/
wood.
wood.
32. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhe-sive/leather.
33. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhe-sive/nylon/adhesive/polypropylene.
34. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhe-sive/EVOH/adhesive/polypropylene.
35. The composite structure of claim 21 wherein said composite structure comprises polypropylene/adhe-sive/aluminum/adhesive/polypropylene.
36. The method of claim 1 wherein said graft copolymer of (a) comprises a high density polyethylene and maleic anhydride.
37. The method of claim 1 wherein said graft copolymer of (a) comprises a high density polyethylene and fumaric acid.
38. The method of claim 1 wherein said graft copolymer of (a) comprises a high density polyethylene and bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhy-dride.
39. The method of claim 1 wherein said graft copolymer of (a) comprises a high density polyethylene and acrylic acid.
40. The method of Claim 20 wherein said elastomer is a block copolymer of a hydrogenated diene and a vinyl aromatic compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30956181A | 1981-10-08 | 1981-10-08 | |
| US309,561 | 1989-02-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1206312A true CA1206312A (en) | 1986-06-24 |
Family
ID=23198717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000408418A Expired CA1206312A (en) | 1981-10-08 | 1982-07-29 | Composite structures and method of making same |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5871972A (en) |
| CA (1) | CA1206312A (en) |
| DE (1) | DE3230715C2 (en) |
| FR (1) | FR2514362B1 (en) |
| GB (1) | GB2107325B (en) |
| IT (1) | IT1149087B (en) |
| NL (1) | NL184909C (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4452942A (en) * | 1982-02-19 | 1984-06-05 | Chemplex Company | Adhesive blends containing anacid or anhydride grafted LLDPE |
| US4460745A (en) * | 1982-04-26 | 1984-07-17 | Chemplex Company | Adhesive three-component blends containing grafted HDPE |
| JPS6114272A (en) * | 1984-06-29 | 1986-01-22 | Ube Ind Ltd | Bondable polyethylene composition and metal laminate thereof |
| JPS63130649A (en) * | 1986-11-20 | 1988-06-02 | Idemitsu Petrochem Co Ltd | Modified polyethylene resin composition |
| US4868057A (en) * | 1987-12-21 | 1989-09-19 | Shell Oil Company | Laminated structure comprising a plurality of polymeric layers adhered with an adhesive composition |
| JPH0751343B2 (en) * | 1988-10-17 | 1995-06-05 | 日本石油化学株式会社 | Hollow container |
| US4921910A (en) * | 1989-04-19 | 1990-05-01 | Polysar Limited | Toughened thermoplastics |
| US5250349A (en) * | 1989-08-07 | 1993-10-05 | Mitsui Petrochemical Industries, Ltd. | Retortable packaging laminate structure with adhesive layer |
| US5225482A (en) * | 1989-08-07 | 1993-07-06 | Mitsui Petrochemical Industries Co., Ltd. | Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereof |
| KR930011760B1 (en) * | 1989-08-07 | 1993-12-20 | 미쓰이 세끼유 가가꾸 고오교오 가부시끼가이샤 | Adhesive resin composition laminate comprising this composition as adhesive layer |
| JP2760595B2 (en) * | 1989-09-19 | 1998-06-04 | 三井化学株式会社 | Laminate |
| US5045401A (en) * | 1989-12-21 | 1991-09-03 | The Dow Chemical Company | Non-isothermal crystallizable adhesive compositions for multilayer laminated structures |
| JPH03277501A (en) * | 1990-03-09 | 1991-12-09 | Tatsuta Electric Wire & Cable Co Ltd | Plywood |
| JPH03278903A (en) * | 1990-03-28 | 1991-12-10 | Tatsuta Electric Wire & Cable Co Ltd | Adhesive sheet for plywood |
| JPH04113803A (en) * | 1990-09-04 | 1992-04-15 | Tatsuta Electric Wire & Cable Co Ltd | Plywood |
| JPH04113807A (en) * | 1990-09-04 | 1992-04-15 | Tatsuta Electric Wire & Cable Co Ltd | Plywood |
| ES2107315T3 (en) * | 1994-03-29 | 1997-11-16 | Advanced Elastomer Systems | THERMOPLASTIC ELASTOMERS THAT HAVE IMPROVED SURFACE PROPERTIES. |
| US5709953A (en) * | 1996-02-21 | 1998-01-20 | Morton International, Inc. | Extrudable resin for polystyrene and laminate |
| US6004024A (en) * | 1997-11-14 | 1999-12-21 | Calgon Corporation | Emulsion feed assembly |
| US6855432B1 (en) * | 1999-09-03 | 2005-02-15 | E. I. Du Pont De Nemours And Company | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| CA2383728A1 (en) * | 1999-09-03 | 2001-03-15 | E.I. Du Pont De Nemours And Company | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| US8071220B2 (en) | 2006-07-21 | 2011-12-06 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizates having improved adhesion to polar substrates |
| US8012539B2 (en) | 2008-05-09 | 2011-09-06 | Kraton Polymers U.S. Llc | Method for making sulfonated block copolymers, method for making membranes from such block copolymers and membrane structures |
| JP4924664B2 (en) * | 2009-06-10 | 2012-04-25 | ウシオ電機株式会社 | High pressure discharge lamp |
| US8263713B2 (en) | 2009-10-13 | 2012-09-11 | Kraton Polymers U.S. Llc | Amine neutralized sulfonated block copolymers and method for making same |
| US8445631B2 (en) | 2009-10-13 | 2013-05-21 | Kraton Polymers U.S. Llc | Metal-neutralized sulfonated block copolymers, process for making them and their use |
| US9394414B2 (en) | 2010-09-29 | 2016-07-19 | Kraton Polymers U.S. Llc | Elastic, moisture-vapor permeable films, their preparation and their use |
| US9429366B2 (en) | 2010-09-29 | 2016-08-30 | Kraton Polymers U.S. Llc | Energy recovery ventilation sulfonated block copolymer laminate membrane |
| EP2630167B1 (en) | 2010-10-18 | 2018-05-30 | Kraton Polymers U.S. LLC | Method for producing a sulfonated block copolymer composition |
| US9861941B2 (en) | 2011-07-12 | 2018-01-09 | Kraton Polymers U.S. Llc | Modified sulfonated block copolymers and the preparation thereof |
| US9365711B2 (en) | 2011-09-23 | 2016-06-14 | Dow Global Technologies Llc | Olefin-based polymer compositions and articles prepared therefrom |
| TW201829574A (en) * | 2016-11-16 | 2018-08-16 | 美商陶氏全球科技有限責任公司 | Tie layer compositions and multilayer films incorporating same |
| JP7073918B2 (en) * | 2018-05-31 | 2022-05-24 | Ｍｃｐｐイノベーション合同会社 | Adhesive resin composition and laminate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3868433A (en) * | 1972-04-03 | 1975-02-25 | Exxon Research Engineering Co | Thermoplastic adhesive compositions |
| JPS5280334A (en) * | 1975-12-27 | 1977-07-06 | Mitsui Petrochem Ind Ltd | Method of adhering polyolefin and polar substrate |
| JPS5340387A (en) * | 1976-09-21 | 1978-04-12 | Asahi Breweries Ltd | Shrinkage cap with collar |
| US4298712A (en) * | 1977-08-01 | 1981-11-03 | Chemplex Company | Adhesive blends of elastomer, polyolefin, and graft of polyethylene with unsaturated fused ring anhydrides |
| JPS582825B2 (en) * | 1977-11-17 | 1983-01-18 | 日本クラウンコルク株式会社 | Olefin resin-metal adhesive structure and its manufacturing method |
| JPS5516904U (en) * | 1978-07-20 | 1980-02-02 |
-
1982
- 1982-07-29 CA CA000408418A patent/CA1206312A/en not_active Expired
- 1982-08-13 NL NLAANVRAGE8203182,A patent/NL184909C/en not_active IP Right Cessation
- 1982-08-18 DE DE3230715A patent/DE3230715C2/en not_active Expired - Fee Related
- 1982-08-24 GB GB08224302A patent/GB2107325B/en not_active Expired
- 1982-09-22 IT IT49154/82A patent/IT1149087B/en active
- 1982-10-05 JP JP57174092A patent/JPS5871972A/en active Granted
- 1982-10-07 FR FR8216811A patent/FR2514362B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL8203182A (en) | 1983-05-02 |
| JPH0259187B2 (en) | 1990-12-11 |
| IT8249154A0 (en) | 1982-09-22 |
| IT1149087B (en) | 1986-12-03 |
| FR2514362B1 (en) | 1986-04-18 |
| DE3230715A1 (en) | 1983-04-21 |
| NL184909B (en) | 1989-07-03 |
| FR2514362A1 (en) | 1983-04-15 |
| GB2107325A (en) | 1983-04-27 |
| DE3230715C2 (en) | 1993-11-18 |
| GB2107325B (en) | 1985-04-11 |
| JPS5871972A (en) | 1983-04-28 |
| NL184909C (en) | 1989-12-01 |
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