CN100354385C - Low activation temperature adhesive composition with high peel strength and cohesive failure - Google Patents

Low activation temperature adhesive composition with high peel strength and cohesive failure Download PDF

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Publication number
CN100354385C
CN100354385C CNB008141495A CN00814149A CN100354385C CN 100354385 C CN100354385 C CN 100354385C CN B008141495 A CNB008141495 A CN B008141495A CN 00814149 A CN00814149 A CN 00814149A CN 100354385 C CN100354385 C CN 100354385C
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resin combination
weight
ethylene
weight part
elastomerics
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CN1378579A (en
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S·霍亚布尔
S·R·坦尼
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/06—Polyethene
    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate

Abstract

The present invention provides a resin composition made from admixing starting materials comprising: (a) 0 to 90 parts by weight of a polyolefin; (b) 5 to 95 parts by weight of a functional polyolefin; (c) 5 to 40 parts by weight of a polystyrenic; and (d) 0 to 30 parts by weight of an elastomer, where the total amount of components of (a), (b), (c) and (d) in the resin composition is 100 parts by weight. In a further embodiment, component (a) is a non-olefin copolymer and component (c) is high impact polystyrene. The resin compositions are useful as adhesives for metal and polyolefin substrates.

Description

Binder composition with low activation temperature of high-peeling strength and cohesive failure
TECHNICAL FIELD OF THE INVENTION
The present invention relates to new resin and binder composition, relate in particular to can be used as self-supporting (self-supporting) film or can be on matrix by the binder composition of co-extrusion or extrusion coated low activation temperature.
The background technology of invention
Although known acid modification or anhydride modified polymkeric substance can be used as tackiness agent, be used for bonded metal and polyolefine the two, not only the two has high bond strength but also needs can activate bonding at a lower temperature to metal and polyolefine but still need tackiness agent.Traditional with present commercially available modified polyolefin or sacrifice to metal or to polyolefinic bond strength, perhaps do not activate at low temperatures when bonding with metal or polyolefine.In addition, the normally very soft and material that is clamminess of activatory binder composition at low temperatures, make to be difficult in heat lamination processing, handling these compositions, and handle these compositions and may require very expensive mold release film (release film) to prevent adhesion with free film (free film) form.And the passing in time after being delivered for use of most of present tackiness agents has the trend of losing bond strength significantly.This phenomenon is at industrial being called as " aging (age-down) ".
Many patents that open binder composition is arranged in the art, but the mentioned in this manual each side of these prior art patents not all is gratifying.The example of these prior art patent comprises United States Patent (USP) 551 6583,4861676,4861677,4552819 and 5965255.
An example of prior art is a United States Patent (USP) 5225842 of authorizing middle river (Nakagawa) etc. on June 6th, 1993, and it discloses a kind of binder composition that contains polyethylene, polystyrene elastomerics and the ethene-alpha-olefin copolymer of vinyl-vinyl acetate copolymer, styrenic polymer resins, graft modification.The wherein not open high-impact polystyrene that is used in combination with ethene/non-ethylene copolymer as styrene resin.
It is many to have found that binder combination composition formula of the present invention has solved, or all, these problems.Binder composition bonded metal of the present invention and polyolefine the two, activation at a lower temperature and as freely or the co-extrusion film handle easily, and do not require middle layer or release paper.In addition, have found that these binder compositions produce 100% cohesive failure in the stripping test process.Cohesive failure is required character because it is the index of high bond strength, its bond strength height so far so that bond strength is greater than the cohesive strength of tackiness agent.Cohesive failure also makes can be bonding suitably to guarantee the multilayered structure quilt with a kind of visual test easily when other test method is difficult for obtaining.At last, product has strong relational degree between the cohesive failure pattern of tackiness agent and the retention characteristic of bond strength after being delivered for use.
Therefore, the invention provides binder composition, it has good cementability to metal matrix with to many polymer materialss, thereby produces the bonding coat with high-peeling strength.The present invention also makes and can use relatively low activation temperature in the manufacturing of profiled sheeting.
Binder composition of the present invention can be used as adhesive resin or be used as adhesive films with the form of pellet.
Summary of the invention
Therefore, on the one hand, the invention provides a kind of binder composition of making by the parent material mixing that contains following component:
(a) 0-90 weight part polyolefine;
(b) 5-95 weight part functional polyalkylene alkene;
(c) 5-40 weight part polystyrene thing; With
(d) 0-30 weight part elastomerics,
Wherein component (a) and (b), (c) and total amount (d) are 100 weight parts in the resin combination.
Second aspect present invention provides a kind of and has been mixed and the binder composition of manufacturing by the parent material that contains following component:
(a) 0-90 weight part non-olefinic multipolymer;
(b) 5-95 weight part functional polyalkylene alkene;
(c) 5-40 weight part high-impact polystyrene; With
(d) 0-30 weight part elastomerics,
Wherein component (a) and (b), (c) and total amount (d) are 100 weight parts in the resin combination.
Brief description of drawings
The preferred embodiments of the invention will be described with reference to the drawings, and wherein identical Reference numeral is meant parts identical in different views, and wherein:
Fig. 1 a and 1b are to use an embodiment of binder composition of the present invention and five synoptic diagram of laminated structure layer by layer made.
Detailed description of preferred embodiments
To the present invention be described with reference to embodiment preferred.
Described preferred resin of the present invention of the application and binder composition are the fusion admixtures of many polymkeric substance.These tackiness agents can use in various application, and decide to have various performance on concrete application.A kind of application of these preferred adhesive is to be used for building industry to make metal sheet, and metal sheet wherein is a kind of composite structure form, and it contains and polyolefine core-as the metal matrix of polyethylene-bonding-as aluminium or steel.Preferred adhesive composition of the present invention is used for bonded metal matrix and polyethylene core.
In this application, importantly bonding coat provides good bonding effect to polyolefine and metal matrix.Equally, in application process, the cohesive failure of tackiness agent is required, and tackiness agent should more easily be prepared and use.Have found that binder composition of the present invention is to metal matrix, all provide good bonding to many polymer materialss.They produce 100% cohesive failure in the stripping test process.These binder compositions can be used as the self-supporting film, and it is handled and processing easily.
Compare with common employed tackiness agent in manufacturing template (building panel), preferred adhesive composition of the present invention activates at a lower temperature.For the preferred adhesive composition; activation temperature can be reduced to about 125 ℃; the activation temperature of this reduction causes sizable cost savings and safer operation concerning the manufacturing of sheet material, because can save the protective layer (needing the color spot of this protective layer to prevent to paint under comparatively high temps) that uses lacquer painting to use from manufacturing process.
On the one hand, resin combination of the present invention comprises:
(a) 0-90 weight part polyolefine;
(b) 5-95 weight part functional polyalkylene alkene;
(c) 5-40 weight part polystyrene thing; With
(d) 0-30 weight part elastomerics,
Wherein component (a) and (b), (c) and total amount (d) are 100 weight parts in the resin combination.
Second aspect, resin combination of the present invention comprises:
(a) 0-90 weight part non-olefinic multipolymer;
(b) 5-95 weight part functional polyalkylene alkene;
(c) 5-40 weight part high-impact polystyrene; With
(d) 0-30 weight part elastomerics,
Wherein component (a) and (b), (c) and total amount (d) are 100 weight parts in the resin combination.
In patent specification, term " polyolefine " is meant homopolymer and its polymers of alkene.More particularly, homopolymer comprises the polymkeric substance of being made up of single unsaturated olefin, contains the analogue of 2-20 carbon atom as polyethylene, polypropylene, polybutene or alkene wherein.The multipolymer of alkene comprises by one or more with 2-20 carbon atom plants the polymkeric substance that unsaturated hydrocarbons or many unsaturated hydrocarbons are formed.The example includes, but are not limited to ethylene/propene copolymer, ethylene/butylene copolymers, ethylene/hexene multipolymer, ethylene/octene, ethylene/styrene multipolymer, ethylene/butylene/octene copolymer, ethylene/propene/norbornadiene multipolymer and propene/but-1-ene copolymer.
In patent specification, term " non-olefinic multipolymer " is meant the multipolymer of alkene and non-olefinic.Can include, but are not limited to vinyl-acetic ester, acrylate with the non-olefinic of alkene-mainly be ethene-copolymerization or have the methacrylic ester, unsaturated acid anhydride of 1-20 carbon atom-as maleic anhydride or itaconic anhydride, unsaturated acid-as toxilic acid, fumaric acid, vinylformic acid, methacrylic acid or methylene-succinic acid.The example of the multipolymer of alkene and non-olefinic includes, but are not limited to Ethylene/vinyl acetate, ethylene/methyl acrylate, ethylene/butyl acrylate.Can comprise and use metallocene catalyst, Ziegler-Natta catalyst and other catalyzer that in " low pressure " polymerization process, uses to make these polymkeric substance by method known in the art.Perhaps, also can make these polymkeric substance under " high pressure " polymerization process of radical initiator for example using.Can use polyolefinic mixture or admixture.
In patent specification, term " functional polyalkylene alkene " is meant to have the polyolefine or the non-olefinic multipolymer that can react the particular functional group who forms covalent linkage or ionic linkage.Functional polyalkylene alkene comprises following defined graft polyolefin.
Term " graft polyolefin " is meant the mixture or the admixture of polyolefine, non-olefinic multipolymer or polyolefine and/or non-olefinic multipolymer, at least a monomer of grafting on the mixture of non-olefinic multipolymer or polyolefine and/or non-olefinic multipolymer or admixture, described monomer is selected from ethylenic unsaturated carboxylic acid and ethylenic unsaturated carboxylic acid anhydrides, also non-preferentially comprise the derivative that these are sour, and composition thereof.These acid and acid anhydrides can be monocarboxylic acid, di-carboxylic acid or polycarboxylic acid, example is the maleic anhydride of vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, Ba Dousuan, itaconic anhydride, maleic anhydride and replacement, as dimethyl maleic anhydride or crotonic anhydride (citrotonic anhydride), nadic anhydride, methyl nadic anhydride (nadic methyl anhydride) and tetrahydronaphthalic anhydride, wherein preferred especially maleic anhydride.The example of the derivative of unsaturated acid is its salt, acid amides, imide and ester, as toxilic acid list sodium and toxilic acid disodium, acrylamide, glycidyl methacrylate and dimethyl fumarate.Graft polyolefin is known in the art, can prepare described graft polyolefin by various method, is included in hot joining branch in forcing machine or other mixing equipment, grafting or grafting in fluidized-bed reactor in solution.Also can use the mixture or the admixture of graft polyolefin.
In patent specification, term " polystyrene thing " is meant the homopolymer of vinylbenzene or alpha-methyl styrene, or vinylbenzene and unsaturated monomer-for example, but be not limited to ethene, butylene, divinyl or isoprene-multipolymer.Concrete example includes, but are not limited to the random or segmented copolymer of ethylene/styrene, ethene/divinyl is random or segmented copolymer and hydrogenation and partially hydrogenated butadiene/styrene copolymers.Further modification also is useful with the polystyrene thing that increases erosion-resisting characteristics, and this class polystyrene thing typically refers to high-impact polystyrene or HIPS.Also can use the admixture and the mixture of polystyrene thing.Concrete example includes, but are not limited to the high-performance polystyrene thing (High PerformanceStyrenics) of Nova Chemicals sale and the name of Dow Chemicai sale is called Index TMThe ethylene/styrene multipolymer.
In patent specification, term " elastomerics " also refers to polyolefine or polystyrene thing, but is different from above-mentioned polyolefine or polystyrene thing, and difference is that its degree of crystallinity is low relatively, that is to say, and relatively be unbodied.Defined herein elastomerics has heat fusing character-under 10 ℃/minute, rate of heating less than 30 joules/g, measure according to differential scanning calorimeter (DSC).Polyolefin elastomer, for example can be ethene and alpha-olefin copolymer, comprise that name that ExxonMobil sells is called the metallocene ethylene/octene that the low density metallocene ethylene/butylene copolymers of " Extravt  " or name that DuPont Dow Elastomers sells are called " Engage  ", comprise that also the name of ExxonMobil sale is called the ethylene/propene copolymer of " Vistalon  ", the name that Mitsui sells is called ethylene/propene/norbornadiene multipolymer that the ethylene/alpha-olefin copolymer of " Tafmer  " or name that DuPont Dow Elastomers sells are called " Nordel  ", also comprises polybutene rubbers, polyisobutene.The elastomeric example of polystyrene thing includes, but are not limited to name that Shell for example sells and is called name that the diblock of " Kraton  " and triblock copolymer or Firestone sell and is called those of " Stereon  ".
Except above-mentioned component, preferred adhesive composition of the present invention can contain small quantities of usual and in adhesive field known other material.These materials comprise, for example primary and secondary (primary and seeondary) oxidation inhibitor, stablizer, slip additive, antiblocking additive-as silicon-dioxide or talcum, dyestuff, pigment and tackifying resin-as at Kirk Othmer Among the Encyclopedia of Chemical Technology disclosed those, prerequisite is the bond properties that the adding of these additives can not influence composition significantly unfriendly.
As known in the art, can do and mix binder composition of the present invention, melting mixing and granulation again in twin screw extruder subsequently.Subsequently, can transform and use these fused hybrid resins by various technology and technology.For example can pass through casting or blown film die head extruding technology, tackiness agent is changed film forming and this binder film can be laminated on the suitable matrix (as metal or polyolefine).Perhaps, this binder composition can carry out co-extrusion with other polyolefine as the top layer on this polyolefinic surface or two surfaces, prepare more economical binder film.
In addition, mix polar support resin-, use binder composition of the present invention and polar support material directly bonding, can produce the co-extrusion film as polymeric amide, ethylene-vinyl alcohol copolymer (EVOH) or polyester.Can pass through the heat-activatable adhesive film, these binder films are laminated on the various matrix.Can absorb infrared energy by the whole bag of tricks-include, but are not limited to directly contact with hot plate or roller, in baking oven direct heating or by RF frequently or microwave radiation activate-carry out thermal activation.
In the Another Application of binder composition of the present invention,, for example extrude lamination, extrusion coated, co-extrusion lamination, co-extrusion and be coated with-tackiness agent can be coated directly onto on the matrix with technology well known in the art-comprise.Can use the bonding polar support resin of binder composition of the present invention-as EVOH, polymeric amide or polyester.Also can use it to come bonding metal, as steel, aluminium, copper and brass and bonding polyolefine, as polyethylene, ethylene copolymer and polypropylene.
In an embodiment preferred of the present invention, provide a kind of resin combination of making by the parent material that contains following component:
(a) 0-90 weight part, more preferably 20-60 weight part linear low density of polyethylene (for example commercially available in ExxonMobil, name is called Extract  or is available commercially from Nova Chemicals, and name is called Sclair );
(b) 5-95 weight part, the more preferably polyethylene of 10-30 weight part maleic anhydride graft (for example, commercially available in DuPont, name is called Fusabond );
(c) 5-40 weight part, more preferably 10-35 weight part high-impact polystyrene (for example, commercially available in Nova Chemicals, name is called high-performance vinylbenzene); With
(d) 0-30 weight part, more preferably 10-25 parts by weight of ethylene-propylene diene rubber compound (for example, commercially available in DuPont-Dow Elastomers, name is called NordelIP );
Component (a) in the resin combination wherein, (b), (c) and total amount (d) be 100 weight parts.
Second embodiment of the present invention provides a kind of binder composition that contains following component:
(a) 0-90 weight part, more preferably 40-60 parts by weight of ethylene-vinyl acetate copolymer, preferably has 3-40 weight % vinyl-acetic ester, more preferably 5-30 weight % vinyl-acetic ester (for example the DuPont name of selling be called Elvax  be the suitable vinyl-vinyl acetate copolymer that is purchased);
(b) 5-95 weight part, the more preferably polyethylene of 10-30 weight part maleic anhydride graft (for example, be available commercially from DuPont, name is called Fusabond );
(c) 5-40 weight part, more preferably 10-35 weight part high-impact polystyrene (for example, be available commercially from Nova Chemicals, name is called high-performance polystyrene thing); With
(d) 0-30 weight part, more preferably 10-25 parts by weight of ethylene-propylene diene rubber compound (for example, be available commercially from DuPont-Dow Elastomers, name be called Nordel IP ),
Component (a) in the resin combination wherein, (b), (c) and total amount (d) be 100 weight parts.
In these two embodiment preferred of the present invention, can use polyisobutene to substitute ethylene-propylene diene elastomer compound.Equally, can use the polystyrene styrene butadiene elastomerics that contains different butadiene content with similar effect.
Each component in the binder composition of the present invention preferably provides certain characteristic to final tackiness agent.Low melting point polyolefin, low activation temperature performance as polyethylene or vinyl-vinyl acetate copolymer enhancing tackiness agent, graftomer is mainly to excellent bonding the working of binder composition and metal matrix, elastic component strengthens stripper-resistance and increases the toughness of final binder composition, and last polystyrene thing component provides excellent cohesive failure performance and higher astoundingly bond properties.
The melt flow rate (MFR) of preferred adhesive composition of the present invention-according to ASTM-1238E measure-can be between 0.1-100dg/min, more preferably 0.5-50dg/min and most preferably 0.8-25dg/min.Can between 55 ℃-140 ℃, decide according to the fusion peak value that DSC is measured on forming.
When the processed film forming of preferred adhesive composition of the present invention with when bonding at low temperatures, because it possesses high-peeling strength and low surface viscosity uniquely simultaneously, so they are useful in the manufacturing of the profiled sheeting of aluminium and steel.
Embodiment
Following embodiment demonstrates and uses polystyrene thing-as high-impact polystyrene (HIPS)), the wonderful advantage aspect the binder film that additional stripping strength, cohesive failure pattern is provided and is not clamminess.
Embodiment 1
Table 1 shows composition 1A, 1B and the 1C that contains 0 weight %, 10 weight % and 20 weight % high-impact polystyrene (" HIPS ") % respectively.At first, do and mix these compositions, be input in little synchronous rotation (co-rotating) twin screw extruder.Material to melt compounded carries out granulation, blows out the about 75 microns film of mean thickness then.Use this film as bonding coat subsequently, 5 layers of composite structure shown in shop drawings 1a and the 1b.Aluminium is handled by aludyne, and thickness is 0.38mm.Employed polyethylene core is the thick new LDPE (film grade) of 2mm (LDPE) sheet material.
In following electric heating press, implement the lamination (Fig. 1 a and 1b) of structure:
1-is at 100 ℃ of preheating five-layer structures, through 4.5 minutes,
2-applies 5kgf/cm at 135 ℃ 2Pressure through 20 seconds,
The 3-release of pressure, and matrix material was stopped 1.5 minutes again at 135 ℃,
4-air cooling sample is to room temperature.
The test compound structure is used Instron then TMInstrument is measured stripping strength (ASTM1876).In peeling strength test, use following condition:
I) right angle extruder rate (crosshead speed): 100mm/min,
Ii) separation mode: 180 degree
Last two hurdles of table 1 show that the consumption with component d (HIPS) is increased to 20 weight %, the result of stripping strength and failure mode from 0 weight %.Comparative composition 1A and composition 1B and 1C can find out owing to have polystyrene HIPS component, the wonderful effect of stripping strength enhanced.It also is highly required reaching cohesive failure (polyethylene and aluminium are respectively 50/50).Compare with the adhesion failure of other two kinds of compositions, sample 1C demonstrates 80% cohesive failure.
Table 1: the tackiness agent of individual layer ethane-acetic acid ethyenyl ester (EVA) base
Sequence number Component (a), weight % Component (b), weight % Component (c), weight % Component (d), weight % Component (e), weight % Stripping strength, kilogram force/25mm Failure mode
1A 49.9 30.0 20.0 0.0％ 0.1 16.4 Bonding with aluminium
1B 39.9 30.0 20.0 10.0 0.1 23.6 Bonding with aluminium
1C 29.9 30.0 20.0 20.0 0.1 29.8 80% adhesion
Component (a)=12%VA content and MI are ethane-acetic acid ethyenyl ester (EVA) multipolymer of 2.5dg/min
The linear low density of polyethylene (LLDPE) of component (b)=be 2.5dg/min with maleic anhydride graft and the MI of 0.9 weight %
Component (c)=Mooney (Moony) viscosity is ethylene/propene/norbornadiene multipolymer (EPDM) elastomerics of 20
Polystyrene (HIPS) elastomerics that component (d)=polyhutadiene is impact-resistant modified
Component (e)=hindered phenol antioxygen stablizer
Embodiment 2
Except the binder film (in order to reduce the cost of employed tackiness agent) of the coextrusion film blowing of making polyethylene/tackiness agent and instead of pure, to prepare sample with embodiment 1 described method.With composition 2A, 2B and 2C and linear low density of polyethylene (LLDPE) co-extrusion, preparation LLDPE-tackiness agent (thickness of each layer is 25 microns).The results are summarized in table 2.From the comparison of 1C and 2A (be respectively 29.8 and 16.5kgf/25mm), can find out that the co-extrusion film produces lower stripping strength usually, but still be functional.The high-impact polystyrene (2C) that adds 30 weight % content can reduce stripping strength.This back one composition remains functional, although be not optimum.
The tackiness agent of table 2:2 layer ethane-acetic acid ethyenyl ester (EVA)/polyvinyl
Sequence number Component (a), weight % Component (b), weight % Component (c), weight % Component (d), weight % Component (e), weight % Stripping strength, kilogram force/25mm Failure mode
2A 29.9 30.0 20.0 20.0 0.1 16.4 100% adhesion
2B 44.9 20.0 15.0 20.0 0.1 17.5 100% adhesion
2C 34.9 20.0 15.0 30.0 0.1 10.9 100% adhesion
Component (a)=density be 0.905 and MI be the metallocene ethylene-butene copolymer of 4.5dg/min
The high density polyethylene(HDPE) (HDPE) of component (b)=be 11dg/min with maleic anhydride graft and the MI of 1.0 weight %
Component (c)=Mooney (Moony) viscosity is ethylene/propene/norbornadiene multipolymer (EPDM) multipolymer of 20
Polystyrene (HIPS) elastomerics that component (d)=polyhutadiene is impact-resistant modified
Component (e)=hindered phenol antioxygen stablizer
Embodiment 3
In the present embodiment, use the metallocene linear low density of polyethylene to make composition as base resin.Table 3 has been summed up composition.To prepare sample 3A, 3B and 3C with embodiment 1 and 2 described methods.For commerical prod closer that is virtually reality like reality, prepare back two kinds of composition 3D and 3E with two-step approach.Initial with 3D and 3E tackiness agent under 149 ℃ temperature, use 8.5kgf/cm 2Pressure be laminated on the aluminium through 30 seconds.Then that these are pre-laminated aluminium flake uses 8.5kgf/cm under 132 ℃ 2Pressure compressed together through 10 seconds with the LDPE core of preheating.Opposite with the employed 180 degree angles of other embodiment, carry out the stripping test of an angle of 90 degrees.Composition 3D is the repetition of 3C, is used for more different laminations and the performance between the test method.Compare with 3C, the stripping strength that sample 3D representative is much lower, this is because 3D carries out 180 degree stripping tests, and the 3C sample carries out 90 degree stripping tests.
Once more the consumption of impact-resistant modified polystyrene (HIPS) being increased to 20 weight % (comparative sample 3A is to 3C) from 0 weight % causes stripping strength significantly to increase.Failure mode also is improved and becomes more bonding.The sample 3E that contains 30%HIPS shows the cohesive failure of high peel strength value (peeling off in the mode at 90 degree is 20.5kgf/25mm) and 100%.Should be noted that when using this about 132 ℃ " low lamination temperature " common employed product completely destroy in the commercial production.
Table 3: the tackiness agent of metallocene LLDPE base
Sequence number Component (a), weight % Component (b), weight % Component (c), weight % Component (d), weight % Component (e), weight % Stripping strength, kilogram force/25mm Failure mode
3A 59.9 20.0 20.0 0.0 0.10 N/A Bonding with aluminium
3B 49.9 20.0 20.0 10.0 0.10 26.9 Bonding with aluminium
3C 39.9 20.0 20.0 20.0 0.10 36.3 20% adhesion
3D 39.9 20.0 20.0 20.0 0.10 18.6 30% adhesion
3E 29.9 20.0 20.0 30.0 0.10 20.5 100% adhesion
Component (a)=density be 0.905 and MI be the metallocene ethylene-butene copolymer of 4.5dg/min
The high density polyethylene(HDPE) (HDPE) of component (b)=be 11dg/min with maleic anhydride graft and the MI of 1.0 weight %
Component (c)=Mooney (Moony) viscosity is ethylene/propene/norbornadiene multipolymer (EPDM) elastomerics of 20
Polystyrene (HIPS) elastomerics that component (d)=polyhutadiene is impact-resistant modified
Component (e)=hindered phenol antioxygen stablizer
Although show and described the present invention with embodiment preferred, but be understood that variation, change, increase and the deletion that to make other to those skilled in the art, and do not break away from the defined the spirit and scope of the invention of appended claim.

Claims (16)

1. one kind has bond properties and the resin combination of manufacturing by the parent material mixing that contains following component:
(a) 20-60 weight part linear low density of polyethylene;
(b) polyethylene of 10-30 weight part maleic anhydride graft;
(c) 10-35 weight part high-impact polystyrene;
(d) 0-30 weight part elastomerics is selected from ethylene-propylene diene elastomer, polyisobutene and polyisobutene styrene butadiene elastomerics; With
(e) Ren Xuan a small amount of additive is selected from primary and secondary oxidation inhibitor, stablizer, slip additive, antiblocking additive, dyestuff and pigment;
Wherein in the resin combination, component (a) and (b), (c), (d) and total amount (e) are 100 weight parts, and the adding of additive can influence the bond properties of resin combination sharply.
2. the resin combination of claim 1, wherein the polyethylene of maleic anhydride graft is selected from the high density polyethylene(HDPE) of maleic anhydride graft, the linear low density of polyethylene of maleic anhydride graft and the new LDPE (film grade) of maleic anhydride graft.
3. claim 1 or 2 resin combination, wherein elastomerics is the ethylene-propylene diene elastomer.
4. the resin combination of claim 3 is comprising 10-25 parts by weight of ethylene-propylene diene elastomerics.
5. one kind has bond properties and the resin combination of manufacturing by the parent material mixing that contains following component:
(a) 40-60 parts by weight of ethylene-vinyl acetate copolymer;
(b) new LDPE (film grade) of the linear low density of polyethylene of 10-30 weight part maleic anhydride graft or maleic anhydride graft;
(c) 10-35 weight part high-impact polystyrene;
(d) 0-30 weight part elastomerics is selected from ethylene-propylene diene elastomer, polyisobutene and polyisobutene styrene butadiene elastomerics; With
(e) Ren Xuan a small amount of additive is selected from primary and secondary oxidation inhibitor, stablizer, slip additive, antiblocking additive, dyestuff and pigment;
Wherein component (a) and (b), (c), (d) and total amount (e) are 100 weight parts in the resin combination, and the adding of additive can influence the bond properties of resin combination sharply.
6. the resin combination of claim 5, therein ethylene-vinyl acetate copolymer contains 3-40 weight % vinyl-acetic ester.
7. claim 5 or 6 resin combination, therein ethylene-vinyl acetate copolymer contains 5-30 weight % vinyl-acetic ester.
8. claim 5 or 6 resin combination, wherein elastomerics is the ethylene-propylene diene elastomer.
9. the resin combination of claim 8 wherein comprises the ethylene-propylene diene elastomer of 10-25 weight part.
10. one kind contains the binder composition that right requires each resin combination among the 1-4.
11. one kind contains the binder composition that right requires each resin combination among the 5-9.
12. the binder composition of claim 10 or 11, its melt flow rate (MFR) of measuring according to ASTM-1238E is between 0.1-100dg/min; According to the measured fusion peak value of DSC between 55 ℃-140 ℃.
13. the binder composition of claim 12, its melt flow rate (MFR) of measuring according to ASTM-1238E is between 0.5-50dg/min.
14. the binder composition of claim 13, its melt flow rate (MFR) of measuring according to ASTM-1238E is between 0.8-25dg/min.
15. a composite structure comprises
(a) metallic matrix;
(b) polymer layer; With
(c) adhesive composition layer of the claim 10 between metallic matrix and polymer layer.
16. a composite structure comprises
(a) metallic matrix;
(b) polymer layer; With
(c) adhesive composition layer of the claim 11 between metallic matrix and polymer layer.
CNB008141495A 1999-09-03 2000-09-01 Low activation temperature adhesive composition with high peel strength and cohesive failure Expired - Lifetime CN100354385C (en)

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