CN1956845A

CN1956845A - Microsphere containing electron beam cured pressure-sensitive adhesive tapes and methods of making and using same

Info

Publication number: CN1956845A
Application number: CNA200480043151XA
Authority: CN
Inventors: T·C·埃普尔; D·L·查普曼
Original assignee: Avery Dennison Corp
Current assignee: Avery Dennison Corp
Priority date: 2004-04-14
Filing date: 2004-04-14
Publication date: 2007-05-02
Also published as: EP1735147A4; BRPI0418750A; JP2007532751A; EP1735147A1; WO2005110737A1

Abstract

The present invention provides pressure sensitive adhesive tape including at least one electron beam cured (EB-cured), rubber-based pressure sensitive adhesive (PSA) core including microspheres. The core layer is coated on at least one side, and in one embodiment, on both sides, with a skin layer including an EB-cured rubber-based PSA that is substantially free of microspheres. The core layer may comprise a lamination seam, a second core layer or a non-woven support layer.

Description

The pressure-sensitive adhesive tape and production and preparation method thereof that comprises the electronic beam curing of microballoon

The invention technical field

[0001] the present invention relates to comprise the pressure-sensitive adhesive tape of microballoon, relate more specifically to comprise the rubber-based pressure-sensitive adhesive tape of the electronic beam curing of microballoon, and relate to the method for making and using described pressure-sensitive adhesive tape.

Background of invention

[0002] multiple double sided foam pressure-sensitive adhesion (PSA) band has been used to the structure bond in the various application, and it has replaced spot welding, tack weld (tack weld), rivet and other that object is installed in method on the substrate.These application comprise, for example, body side profiled member (body-side molding) is adhered on motor vehicle and other vehicles, the fiber glass body panel is adhered to caravan (motor home), the plexiglas observation window is adhered on the equipment box and similar application.The froth bed (foam layer) of these PSA bands has the polymer matrix based on polyethylene, polyurethane, polyvinyl chloride or polychlorobutadiene usually.Many difference property next to the shin that show on bent substrate in these bands, and/or for showing low viscosity such as painted surface or TPO (TPO) surface.In some cases, be necessary before placing object, to apply priming paint from the teeth outwards, to obtain enough viscosity.When using like this, it is separable that adhesive tape generally can not be tending towards.Yet special in the application such as motor vehicle or other outdoor application, adhesive tape may be exposed to sunlight, water, organic substance such as gasoline, and solvent is as being used for the alcohols of windshield cleaning fluid or anti-icing fluid.These factors will may cause being assemblied in substrate or lip-deep object undesirably and separate.

[0003] therefore, have the demand to foam PSA band, be used in these application, make object be connected to by force and enduringly and snugly on the substrate of expectation, this PSA band can be resisted and will expose wherein each kind of power and factor between its operating period.

Summary of the invention

[0004] the invention provides pressure-sensitive adhesive tape, it comprises at least one and comprises (EB-cured) microballoon, electronic beam curing rubber-based pressure-sensitive adhesive (PSA) nuclear.This core layer (corelayer) is at least simultaneously and be coated with top layer (skinlayer) in one embodiment on the two sides, and this top layer includes and do not contain rubber-based PSA microballoon, electronic beam curing substantially.Described core layer can comprise lamination seam (lamination seam), second core layer or nonwoven supporting layer (non-woven support layer).The invention still further relates to by using the PSA band, object is assembled to method on the substrate, this PSA band comprises at least one and comprises rubber-based PSA nuclear microballoon, electronic beam curing.Described core layer at least the one side and on the two sides, be coated with the top layer in one embodiment, this top layer includes and does not contain rubber-based PSA microballoon, electronic beam curing substantially.

[0005] described pressure-sensitive adhesive tape of the present invention presents high property next to the shin, and it derives from the low elasticity memory of described core layer.Described band also presents high inefficacy strain, high breakaway (cleavage peel) viscosity and tension viscosity and good anti-gasoline and psychometric performance.

[0006] in one embodiment, the present invention relates to pressure-sensitive adhesion (PSA) band, it comprises the rubber-based PSA top layer of electronic beam curing (EB-cured) rubber-based PSA nuclear and electronic beam curing, described PSA nuclear comprises non-rigid polymer microballoon, and has the first and second main faces (major face); Described PSA top layer is adhered to the described first main face, and the rubber-based PSA top layer of wherein said electronic beam curing does not contain microballoon substantially.In one embodiment, described band further comprises the rubber-based PSA top layer of second electronic beam curing, it has the first main face and the second main face, and wherein first of the rubber-based PSA top layer of the second electronic beam curing main face is adhered on the described second main face of rubber-based PSA nuclear of described electronic beam curing.In another embodiment, described band further comprises second and comprises rubber-based PSA nuclear non-rigid polymer microballoon, electronic beam curing, it is adhered to the second main face on the rubber-based PSA top layer of described second electronic beam curing, and even can further comprise the rubber-based PSA top layer that is adhered to the described second three electron-beam curing of examining.In another embodiment, the present invention relates to the PSA band, it further comprises the non-woven polymer supporting layer, and this layer is between the second main face of the rubber-based foam PSA of the first main face on the rubber-based PSA top layer of described second electronic beam curing and electronic beam curing nuclear.

[0007] in another embodiment, the invention further relates to the PSA band, it comprises the rubber-based PSA nuclear of electronic beam curing and the rubber-based PSA top layer of electronic beam curing, the rubber-based PSA nuclear of second electronic beam curing, the rubber-based PSA top layer of second electronic beam curing; The rubber-based PSA nuclear of described electronic beam curing comprises microballoon and has the first and second main faces; The rubber-based PSA top layer of described electronic beam curing is adhered to the described first main face, and microballoon is not contained on the rubber-based PSA top layer of wherein said electronic beam curing substantially; The rubber-based PSA nuclear of described second electronic beam curing comprises microballoon and has the first and second main faces; The rubber-based PSA top layer of described second electronic beam curing is adhered to the first main face of the rubber-based PSA nuclear of described second electronic beam curing, microballoon is not contained on the rubber-based PSA top layer of wherein said second electronic beam curing substantially, and the second main face of described first nuclear is adhered to the second main face of described second nuclear, formation lamination seam.

[0008] in another embodiment, the present invention relates to double-faced adhesive tape, but but but but it comprises the rubber-based PSA nuclear of first electronic beam curing, the rubber-based PSA top layer of first electronic beam curing, the rubber-based PSA nuclear of second electronic beam curing, the rubber-based PSA top layer of second electronic beam curing.But the rubber-based PSA of described first electronic beam curing nuclear comprises microballoon and has the first and second main faces; But the rubber-based PSA top layer of described first electronic beam curing is adhered to the first main face of the rubber-based PSA nuclear of described first electronic beam curing; But the rubber-based PSA of described second electronic beam curing nuclear comprises microballoon and has the first and second main faces, but but the first main face of the rubber-based PSA of wherein said second electronic beam curing nuclear is adhered to the second main face of the rubber-based PSA nuclear of described first electronic beam curing, but but wherein between the rubber-based PSA of the rubber-based PSA of described first electronic beam curing nuclear and described second electronic beam curing nuclear, form the lamination seam; But but the rubber-based PSA top layer of described second electronic beam curing is adhered to the first main face of the rubber-based PSA nuclear of described second electronic beam curing, but the rubber-based PSA top layer of wherein said first and second electronic beam curings does not all contain microballoon substantially.

[0009] in another embodiment, the present invention relates to double-faced adhesive tape, but but but it comprises the rubber-based PSA top layer of the rubber-based PSA nuclear electronic beam curing of first electronic beam curing, the rubber-based PSA nuclear and the lamination seam of second electronic beam curing; But the rubber-based PSA of described first electronic beam curing nuclear comprises microballoon and has the first and second main faces; But but the rubber-based PSA top layer of described electronic beam curing is adhered to the first main face of the rubber-based PSA nuclear of described first electronic beam curing, but wherein the rubber-based PSA top layer of electronic beam curing does not contain microballoon substantially; But the rubber-based PSA of described second electronic beam curing nuclear comprises microballoon and has the first and second main faces, wherein, but but the first main face of the rubber-based PSA of described second electronic beam curing nuclear is adhered to the second main face that the rubber-based PSA of described first electronic beam curing examines; But but described lamination seam is formed between the rubber-based PSA nuclear of the rubber-based PSA nuclear of described first electronic beam curing and described second electronic beam curing.

[0010] in another embodiment, the present invention relates to make and use the method for described adhesive tape.For example, in one embodiment, the present invention relates to object is assemblied in method on the substrate, it comprises provides object and object with the substrate that is bonded to; But provide the rubber-based PSA band of electronic beam curing; Object is adhered to the one side of described PSA band; And the another side that described PSA is with is adhered to described substrate.Required by various application, can described PSA with on core layer or top layer outside the plus.

The accompanying drawing summary

[0011] Fig. 1 is according to one embodiment of the present invention, has the schematic cross sectional view of the adhesive tape on a core layer and a top layer.

[0012] Fig. 2 is according to another embodiment of the invention, has the schematic cross sectional view of the adhesive tape on core layer and two top layers.

[0013] Fig. 3 is according to another embodiment of the present invention, schematic cross sectional view with adhesive tape of two core layers, top layer and non-woven polymer supporting layer, described top layer is positioned on one of core layer, and described non-woven polymer supporting layer is separated described core layer.

[0014] Fig. 4 is according to another embodiment of the present invention, schematic cross sectional view with adhesive tape of two core layers, top layer and separate layer (separator layer), described top layer is positioned on one of core layer, and described separate layer does not contain microballoon substantially.

[0015] Fig. 5 is according to another embodiment of the present invention, has two core layers, is positioned at the top layer on each core layer and do not contain the schematic cross sectional view of adhesive tape of the separate layer of microballoon substantially.

[0016] Fig. 6 is according to another embodiment of the present invention, has the schematic cross sectional view of the adhesive tape of two core layers, two top layers and the lamination seam between core layer.

[0017] Fig. 7 is according to another embodiment of the invention, has the schematic cross sectional view of the adhesive tape of two core layers, two top layers and the non-woven polymer supporting layer between core layer.

[0018] Fig. 8 is according to one embodiment of the present invention, has the schematic cross sectional view of the adhesive tape of two core layers, top layer and the lamination seam between core layer.

Will be appreciated that [0019] in order to simplify and clearly to illustrate, element shown in the drawings does not have necessity and proportionally draws.For example, for purpose clearly, some size of component is relative to each other amplified to some extent.In addition, in the place that sees fit, Reference numeral is repeated to use, to indicate corresponding element.

[0020] in addition, should recognize that hereinafter described processing step and structure are not formed for making the complete process flow of final PSA band.The present invention can put into practice in conjunction with being used in manufacturing of the prior art and operation technique at present, and has only comprised for understanding the common practice processing step that the present invention is necessity.

Describe in detail

[0021] as used in this specification and claims, term " lamination seam (1amination seam) " is defined as being stacked in the formed junction surface of a time-out when the contact adhesive of two curing.

[0022] as described above, the present invention relates to comprise rubber-based pressure-sensitive adhesive tape microballoon, electronic beam curing.This band comprises core layer and at least one top layer.Described band generally has about 5 thickness to about 100 mils, or has about 10 thickness to about 80 mils, or has about 15 thickness to about 70 mils.

Core layer

[0023] described core layer can be a single or multiple lift.This nuclear comprises the rubber-based pressure-sensitive adhesive and the microballoon of electronic beam curing.Described endorsing to comprise lamination seam, second core layer or nonwoven supporting layer.In one embodiment, the thickness range of nuclear from about 5 mils to about 100 mils, perhaps from about 10 mils to about 80 mils, or from about 15 mils to about 70 mils.

[0024] contact adhesive nuclear comprises the rubber-based adhesive of at least one electronic beam curing, and at least one microballoon.In one embodiment, the rubber-based pressure-sensitive adhesive that described EB solidifies on volume, account for described core layer about 35% to about 70%, or about 40% to about 65%, or about 50% to about 60%, the remaining filler by comprising microballoon is formed.Here and in whole specification and claims, the qualification of scope and ratio can be united use.Therefore, for example, in above open,, should expect that also this scope is within scope disclosed above though not have specifically to disclose from about 30% to about 60% scope.

[0025] useful in the present invention rubber-based PSA polymer matrix can be used as solvent-borne type, hot melt build or emulsion type adhesive and is prepared.In one embodiment, described adhesive is a hot melt, and is solvent-based adhesive in another embodiment.In one embodiment, the PSA parent that is adopted is based on diblock and triblock polymer and composition thereof.Can use other resin modified elastomer.In one embodiment, but the rubber-based core copolymer that EB solidifies have be lower than serviceability temperature about 15 ℃ to about 70 ℃ clean effectively glass transition temperatures (Tg).In another embodiment, the rubber-based core copolymer have be lower than serviceability temperature about 30 ℃ to about 60 ℃ clean effectively glass transition temperatures (Tg).The rubbery material that is suitable for use as the rubber-based PSA of electronic beam curing among the present invention is described in following document, for example, and the United States Patent (USP) the 3rd of Harlan, people's such as 239, No. 478, St.Clair United States Patent (USP) the 4th, 152, No. 231, No. the 3rd, 676,202, the United States Patent (USP) of Korpman, the United States Patent (USP) the 3rd of Korpman, 783, No. 072, the United States Patent (USP) the 3rd, 932 of Korpman, No. 328, and No. the 4th, 028,292, the United States Patent (USP) of Korpman; No. the 5th, 856,387, people's such as No. the 4th, 820,746, people's such as Rice United States Patent (USP) and Sasaki United States Patent (USP), the instruction that relates to rubber-based PSA material in all these patents is all incorporated this paper into way of reference.

[0026] in one embodiment, the rubber-based core copolymer that EB solidifies is a block copolymer, and it has or comprises four block structure A-B-A-D, three block structure A-B-A, and randomly as the diblock structure A-B of the less content of minor element.In these block structures, A representative is nonrubber shape or hyaloid during according to appointment-20 ℃ to about 50 ℃ scope or is the block of crystallization in operating temperature.B can be identical with D, and each is all represented and be rubber-like or flexible block under serviceability temperature.At elevated temperatures, described A, B and D block all are to flow fully, make that the rubber-based polymer that EB solidifies can be by co-extrusion modling.

[0027] in one embodiment, the rubber-based pressure-sensitive adhesive that EB used in this invention solidifies be in s-B-S, styrene-isoprene-phenylethene, styrene-butadiene and the styrene-isoprene block copolymer one or more, the KRATON that makes and sell by ShellChemical company for example ^Resin.

[0028] block copolymer that can be used comprises thermoplastic block copolymers, and it has linearity, radial or star-like configuration, and has A block and B block that formation generally is referred to as the ABA block copolymer.In one embodiment, the A block is mono alkenyl arene (monoalkenyl arene), mainly is polystyrene, and it has the molecular weight between about 4000 and about 50000, and in one embodiment, has the molecular weight between about 7000 and about 30000.Other proper A block can be formed by AMS, t-butyl styrene and other cycloalkylation styrene and their mixture.A block content is from about 10% to about 50%, in one embodiment, and between about 10% and about 30%.B is the elasticity conjugated diene, for example butadiene or isoprene, and it has from about 5000 to about 500000 mean molecule quantity, in one embodiment, has from about 50000 to about 200000 mean molecule quantity.In one embodiment, ABA three blocks and AB diblock copolymer constitute the major part of the elastomer block copolymer of adhesive, the percentage of diblock is the about below 95% of block copolymer, and is about in one embodiment below 85%, and about in one embodiment below 75%.Can use a spot of other conventional diene elastomer, but it is unlikely to the appreciable impact bond property.

[0029] in one embodiment, described nuclear is made up of selected thermoplastic elastomer (TPE).Interested herein thermoplastic elastomer (TPE) comprises any block copolymer that has or comprise three block structure A-B-A, wherein A representative be nonrubber shape or for glassy or be crystalline solid under serviceability temperature or room temperature, but be the block of fluid under higher temperature, and the B representative under operating temperature or room temperature rubber-like or flexible block.Except A-B-A three block structures, other possible structure comprises radial structure (A-B) _xA, wherein x is greater than 1; Diblock structure A-B; And the combination of these structures.Elastomer can comprise about 60 to 95% the rubber part of percentage by weight, and the nonrubber part of percentage by weight about 5 to about 40%.

[0030] in one embodiment, described nuclear comprises thermoplastic elastomer (TPE), and such as SBS, SIS, SI, S (IS) x and SEBS block copolymer and composition thereof, they are sold by Shell Chemical company, and name is called KRATON ^D1102, D1107, D1111, D1112, D1117, D1125 and D4141, and KRATON ^G1650.These elastomers have hardness, ShoreA value scope from 32 to 75, and styrene/rubber ratio from 14/86 to 29/71.

[0031] instantiation of ABA type styrene and isoprene copolymer is the KRATON of ShellChemical company ^1107 and KRATON ^1117.Can obtain ABA type SB from ShellChemical company, its name is called KRATON ^1101 and KRATON ^1102.Other commercial available copolymer adhesive comprises: can be from the ethene and the vinyl acetate random copolymer (ESCORENE of Exxon Chemical acquisition ^MOV-2514), it has that melt flow index is 2500, the vinyl acetate weight percent content is 14%; Can be from the styrene butadiene block synthetic rubber (FINAPRENE of Fina Chemical company acquisition ^411), its styrene weight percent content is 30%; Can be from the ethene and the vinyl acetate random copolymer (ELVAX of DuPont acquisition ^420), it has that melt flow index is 148, the vinyl acetate weight percent content is 18.5%; And ethene and vinyl acetate random copolymer ELVAX ^40W, it has, and melt flow index is 57, the vinyl acetate weight percent content is 40%.

[0032] tackifier additive used in this invention comprises rosin or rosin derivative, polyterpene, hydrocarbon resin and analog.The tackifier that useful commerce can get comprise rosin ester, terpene resin, described rosin ester for example can be from Hercules, Inc. the trade mark of Huo Deing is those of FORAL 85, described terpene resin for example can be from Hercules, and the trade mark that Inc. obtains is that those and the trade mark that can obtain from Arizona Chemical company of PICCOLYTE A-115 be those of ZONAREZ B-100.Other commercial tackifier that get comprise that REGALITER91, REGALITE R101, REGALITE RS100 and REGALITE RS260, REGALITE 1018, REGALITE 3102, REGALITE 6108 and REGALITE5095, ZONATAC LITE series are as ZONATAC 105Lite, ESCOREZ 5300 series, FORAL AX and FORAL 105 and Herculin D.

[0033] crosslinking agent can be added in the adhesive composition of the present invention.In one embodiment, crosslinking agent comprises polymercaptan.Useful polymercaptan comprise tetra hydrosulfuryl pentaerythritol tetraacetate (PETTG), dipentaerythritol four (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptopropionic acid ester) (PETMP), trimethylolethane trimethacrylate mercaptopropionic acid ester (TMETMP), trimethylolpropane tris mercaptoacetate (TMPTG), glycol dimercaptosuccinate; 2,2, dimercapto diethyl ether, polyethylene glycol dimercapto acetic acid esters, polyethylene glycol (3-mercaptopropionic acid ester), trihydroxy methyl (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester) are (TMPTMP) and analog.Trimethylolpropane tris (3-mercaptopropionic acid ester) is particularly useful.The concentration range of polymercaptan can reach the about 10% of most rubber weight, or based on the rubber gross weight about 0.3% to about 3%, or be weight percentage 0.5% to about 2%.

[0034] in one embodiment, coming as energy source in the situation of curing rubber base PSA with electron beam (EB), the energy level of EB can be from about 1 to about 100 kilograys (kGy), and in one embodiment, from about 10 to about 50kGy.Selectable energy sources such as ultra-violet radiation can be united use with the EB radiation.The UV irradiation may need to use light trigger.

[0035] as indicated above, core layer also can comprise at least one microballoon.In general, described microballoon can be solid, hollow or porous, and is rigidity or nonrigid.Microballoon can be made by any suitable material, comprises glass, pottery, polymer and material with carbon element.The size range of the microballoon of core layer is from about 10 microns to about 300 microns.In one embodiment, microballoon with the core layer volume about 30% to about 65%, or about 35% to about 60%, or the existence of about 40% to about 60% amount.

[0036] polymer microballoon can be made of any suitable polymers material.Can use the mixture of this low-density microballoon.Polymer microballoon can be viscosity or noncohesive.In one embodiment, can select the polymeric material of microballoon, with mutually crosslinked with the PSA polymer matrix at the EB setting up period.

[0037] polymer microballoon can be made of rigid material or elastomeric material.Suitable rigid polymer material comprises thermosetting polymer, and for example, phenol polymer or thermoplastic polymer are such as polyvinylidene chloride acrylonitrile copolymer (PVDC copolymer).In one embodiment, when using the EB radiation to come the cure polymer parent, thermoplastic polymer is micro-sphere crosslinked and be grafted on the polymer matrix.By crosslinked microsphere and be grafted to polymer matrix, can improve character such as tensile strength.

[0038] the elastomer microballoon is described in people's such as No. the 4495318th, the United States Patent (USP) of people's such as No. the 3691140th, United States Patent (USP), Baker No. the 3857731st, the United States Patent (USP) of Silver and No. 4166152, Howard and Mallya No. the 4810763rd, United States Patent (USP).The instruction that relates to polymer microballoon in these patents is all incorporated this paper into way of reference.Infusible low-density microballoon is disclosed in No. the 61258854th, No. the 4735837th, 4049483,4645783,4624893,4636432,4598112, United States Patent (USP) and the Japan Patent.The disclosure of microballoon is incorporated this paper at this into way of reference in these patents.Can improve the cryogenic property of foam band of the present invention in core layer in conjunction with the elastomer microballoon, particularly cold the hitting in the test (cold slam test) under the temperature of for example 20 ℃ and 30 ℃, for example General Motor Testing GM 9023P.

[0039] non-rigid polymer microballoon can be expandable microballoon, such as EXPANCEL ^Expended microsphere, its Casco Product of branch company by AKZO NOBEL produces, and can obtain from the Expancel Inc. of Georgia State, USA Duluth.EXPANCEL ^Microballoon is the pellet shapes plastic particle.Another example of the suitable and commercial expandable polymer microballoon that gets comprises can (Buffalo, N.Y) those of Huo Deing be called the product of " F30D ", " F80SD " and " F100D " from Pierce Stevens.This expended microsphere generally is made up of the gas or the vaporizable liquid of polymer shell encapsulation.Gas when in the enclosure is heated or liquid when evaporation, has increased pressure and the deliquescing of thermoplasticity shell, causes the rapid increase of microsphere volume.When complete expansion, the volume of microballoon may increase to more than 40 times of its initial volume.In other embodiments, other known non-rigid polymer microballoon can be used in the nuclear.For expandable microspheres, the density of these polymer microballoons can be from about 30 to about 70kg/m ³(about 0.03 to about 0.07g/cm ³).Before expanding, the density of these polymer microballoons can be from about 1000 to about 1300kg/m ³(about 1 to about 1.3g/cm ³).The expansion temperature of these polymer microballoons can be from about 60 ℃ to about 200 ℃, and in one embodiment, from about 80 ℃ to about 190 ℃.

[0040] in one embodiment, microballoon is a hollow.These microballoons generally can have wide density range and crushing strength.In some embodiments, ceramic hollow microsphere is useful, and this is because they show high crushing strength and often more cheap than glass, polymer or carbonaceous hollow microsphere.

[0041] can obtain brand name from the Eastech Chemical of philadelphia, pa is the hollow phenols microspheres product of the uncoated of PHENOSET.PHENOSET BJO-0840 microballoon is characterised in that 0.10-0.15 gram/cm ³Density and the grading curve with about 70 microns patterns.PHENOSET BJO-0930 microballoon is characterised in that 0.104 gram/cm ³Maximal density and the grading curve with about 90 microns patterns.

[0042] in one embodiment, microballoon complete expansion.In one embodiment, before extruding or apply the PSA band nuclear that wherein comprises microballoon, the microballoon complete expansion.In one embodiment, by heating steps microballoon is expanded, but the PSA component that EB solidifies in this heating steps is mixed.In one embodiment, microballoon is expanded, be dissolved in the solvent simultaneously but the PSA component that EB solidifies in this heating steps is mixed by heating steps.Will be described below useful solvent.In one embodiment, described solvent account for solution about 20% to about 90%, in solution, be dissolved with the PSA component.In another embodiment, solvent accounts for the about of solution and arrives about 80% more than 20%.

[0043] in one embodiment, microballoon is a rigidity, and can be made up of for example glass or phenols or styrene polymer.In these embodiments, microballoon expanded before it joins the rubber-based polymer composition that is used to examine.

[0044] in one embodiment, nuclear comprises rigid microspheres, and it is by for example having about 0.2 to about 1.0g/cm ³The glass or the pottery of density are made, and the useful load of microballoon is no more than approximately 45%, and this is because the core layer of higher useful load can be tending towards presenting the elongation performance of reduction.Using the about 0.2g/cm of density ³Following rigid polymer microballoon, for example in the embodiment of the phenols microballoon of hollow, useful load can reach about 60% of volume.If use non-rigid polymer microballoon, can use the useful load that accounts for volume about 60%.

[0045] in one embodiment, nuclear comprises the filler such as pyrolytic silicon dioxide.Filler such as pyrolytic silicon dioxide has reduced the elongation performance of nuclear and has increased the tensile strength of examining.Thus, select the amount of pyrolytic silicon dioxide, so that high elongation performance and high-tensile optimum balance to be provided.In one embodiment, filler exists with the amount of reaching of nuclear weight about 10%.In some embodiments, surpass about 10% useful load and may cause nuclear property deficiency too hard and next to the shin for some application.In one embodiment, the weight range of useful load is from about 3% to about 5%, and this scope has been given the good combination of tensile strength and elongation performance.

[0046] in some embodiments, can use optional filler, rigidity high density solid minimicrosphere for example, it has about 1g/cm ³Above density and about size or average diameter below 10 microns, and be about 0.1 micron to about 5 microns in one embodiment, as substitute such as the pyrolytic silicon dioxide filler, or be used in combination such as the pyrolytic silicon dioxide filler, with elongation performance that reduces core layer and the tensile strength that increases core layer.In one embodiment, this rigidity high density solid minimicrosphere can reach the amount existence of percentage by weight about 5%.In one embodiment, this rigidity high density solid minimicrosphere can reach the amount existence of percentage by weight about 1% to about 2%.

Will be understood that [0047] useful load of above-mentioned various fillers depends on the precise characteristics of requirement, and depend on the quantity of other filler that exists in the core layer.For example, in one embodiment,, then can use the solid packing of high relatively useful load, such as pyrolytic silicon dioxide or rigidity high density minimicrosphere if the useful load of low-density microballoon is low.Similarly, if the quantity height of microballoon then can use lower useful load.

[0048] in other embodiments, can in core layer, add many other fillers, for example calcium carbonate, potter's clay etc. on demand.

[0049] in one embodiment, core layer does not contain rigid microspheres.

The top layer

[0050] as indicated above, core layer has at least one top layer and is positioned on its surface.The top layer can be a single or multiple lift.Normally, the top layer is independent one deck.In one embodiment, the thickness range on top layer from about 10 to about 250 grams/square metre, it (supposes that PSA density is about 1g/cm corresponding to about 10 microns thickness to about 250 microns (0.25mm) ³).The top layer does not contain (for example by volume calculate, below 5%, or 1% is following) substantially or does not contain microballoon.In one embodiment, the top layer is unfilled EB curing rubber based polyalcohol layer.In one embodiment, the top layer can filler pigment.

[0051] rubber-based polymer of the electronic beam curing on top layer can be above disclosed any about examining.Selection is used for the concrete rubber-based polymer on top layer can be identical or different with the rubber-based polymer that is used to examine.

Band

[0052] PSA band of the present invention can pass through prepared by any suitable process.For example, in one embodiment, the mixture of rubber-based polymer parent, microballoon, any filler and solvent can be coated on the backing film (backing film) by required thickness.Before curing, remove solvent then by drying.The top layer can be applied on the dry core layer.On the contrary, the top layer can at first be coated on the backing film, then core layer is coated on the dried top layer.

[0053] in another embodiment, core layer and top layer can be extruded and be sheet or analogous shape, then this sheet are solidified.When the various embodiments of the band that will extrude are laminated together, also can use the calendering method.

[0054] in one embodiment, described nuclear comprises polymer matrix, is used for the solvent of polymer matrix and the adhesive composition of required filler is made by preparation at first.Composition is incorporated into extruder, and passes extruder by the rotary screw transmission.When in extruder, solvent is removed by vacuum evaporation in one or more removal of solvents unit.Then, the composition that is substantially free of solvent is extruded from extruder.As used herein, " do not contain solvent " and mean that the volume of the contained solvent of composition is about below 2%.

[0055] exemplary solvent comprises ethyl acetate, isopropyl alcohol, ethanol, hexane, heptane and toluene.The purpose of solvent is to reduce the viscosity of composition, makes composition be handled in a large number easily, for example, pours another container into from a container easily.In one embodiment, the amount of solvent is to be enough to viscosity is reduced to about 100 Pascal-seconds of following amount.For most compositions, it is enough for this purpose that about 40% quantity of solvent to about 80% solids content is provided.In one embodiment, the composition with about 80% above solid can have undesirable high viscosity.In another embodiment, the composition with about 40% following solid can comprise unnecessary solvent, that is, make viscosity be reduced to the solvent of easy usage level more than being enough to, and unnecessary solvent must be removed during the course.Required concrete viscosity depends on composition and is introduced in the method in the extruder and the type of employed removal of solvents system.Disclose a removal of solvents system in No. the 5100728th, United States Patent (USP), wherein relevant with removal of solvents instruction is incorporated this paper into way of reference.

[0056] in another embodiment, the adhesive composition on core layer and top layer does not need to add solvent and is manufactured.Core layer and top layer by coextrusion on carrier film (carrier film) or release liner (release liner).

[0057] comprise in the embodiment on two top layers at adhesive tape, the top layer need not have identical composition.It may be favourable using different adhesive compositions, and reason is not to be adhered on the analog material usually at the application mesexine that the present invention considers.Yet for the production purpose, using identical adhesive is easily often.The rubber-based pressure-sensitive adhesive that suitable EB solidifies as mentioned above.

[0058] in one embodiment, the PSA band that solidifies of EB substrate that will be adhered to or object or above-mentioned both comprise in thermoplastic, metal, glass, thermosetting resin or the paint one or more surface.In one embodiment, thermoplastic is TPO (TPO).In one embodiment, the surface is without priming.In one embodiment, TPO is without priming.In one embodiment, substrate is the vehicles.In one embodiment, the vehicles are motor vehicles.In one embodiment, described object is the body side profiled member of the vehicles.

[0059] it is particularly useful to the outer surface of substrate for bonding part that EB disclosed herein solidifies the PSA band, and these parts are body side profiled member, sign, pin stripe (pin-striping) and other object for example; Substrate is motor vehicle for example, motorcycle, bicycle, ship such as seagoing vessel, yacht, canoe and private ship, ROV and other type land, sea and day air transportation means.EB disclosed herein solidifies the factor that the special tolerance of PSA band runs into when using these substrates, comprise based on the material of oil such as gasoline, lubricating oil, material such as cleaning agent based on water, the windshield cleaning fluid, rainwater, the mixture (for example, " road dust and dirt (roadgrime) ") of salt solution and aforementioned item, it may be run into by motor vehicles when normal the use.In addition, EB disclosed herein solidifies the PSA band can resist physical force, has the peel strength of raising, and therefore avoids because physical force is bad as colliding, stabbing, deliberately destruction or other power are removed, and this physical force may can cause that also object removes from substrate.

[0060] Fig. 1 is the schematic cross sectional view according to the adhesive tape 10 of one embodiment of the present invention.Comprise the rubber-based PSA nuclear 12 of EB curing and the rubber-based PSA top layer 14 that EB solidifies with 10.According to the present invention, nuclear 12 comprises microballoon, and top layer 14 does not contain microballoon substantially.

[0061] Fig. 2 is the schematic cross sectional view according to the adhesive tape 20 of another embodiment of the invention.Comprise rubber-based PSA top layer 14a, the 14b that rubber-based PSA nuclear 12 that EB solidifies and a pair of EB solidify with 20, it is adhered on the first and second main faces of nuclear 12.According to the present invention, nuclear 12 comprises microballoon, and

top layer

14a and 14b do not contain microballoon substantially.

[0062] Fig. 3 is the schematic cross sectional view according to the adhesive tape 30 of another embodiment of the present invention.Comprise the rubber-based PSA top layer 14 of rubber-based PSA nuclear 12a, the EB curing that an EB solidifies, rubber-based PSA nuclear 12b and the supporting layer 16 between the first nuclear 12a and the second nuclear 12b that the 2nd EB solidifies with 30.According to the present invention, the first nuclear 12a and the second nuclear 12b comprise microballoon, and top layer 14 does not contain microballoon substantially.Supporting layer 16 can for example be woven or the polymer sheet of nonwoven.The thickness range that this supporting layer 16 can have is from about 25 microns to about 500 microns (about 1 mil is to about 20 mils), and in one embodiment, from about 50 microns to about 250 microns, about in another embodiment 60 microns to about 100 microns and in one embodiment thickness be about 75 microns (about 3 mils).The example of useful supporting layer is that the trade mark that commerce can get is the 0.3 mil non-woven material of Cerex.

[0063] Fig. 4 is the schematic cross sectional view according to the adhesive tape 40 of another embodiment of the present invention.Comprise that with 40 the rubber-based PSA that an EB solidifies examines 12a, be adhered to a pair of EB curing rubber base PSA top layer 14a, the 14b of the first and second main faces of the first nuclear 12a, and the rubber-based PSA nuclear 12b of the 2nd EB curing, it is adhered to the opposite face of top layer 14b.According to the present invention, the first nuclear 12a and the second nuclear 12b comprise microballoon, and the first top layer 14a and the second top layer 14b substantially do not contain microballoon.

[0064] Fig. 5 is the schematic cross sectional view according to the adhesive tape 50 of another embodiment of the present invention.Comprise the rubber-based PSA nuclear 12a that an EB solidifies with 50, be adhered to rubber-based

PSA top layer

14a, 14b that the first a pair of EB that examines the first and second main faces of 12a solidifies, be adhered to the 2nd EB curing rubber base PSA nuclear 12b of the opposite face of top layer 14b, and the 3rd top layer 14c that is adhered to the second main face of the second nuclear 12b.According to the present invention, the first nuclear 12a and the second nuclear 12b comprise microballoon, and each of the first top layer 14a, the second top layer 14b and the 3rd top layer 14c does not substantially contain microballoon.

[0065] Fig. 6 is the schematic cross sectional view according to the adhesive tape 60 of another embodiment of the present invention.Comprise the rubber-based PSA nuclear 12a that an EB solidifies and be adhered to an EB curing rubber base PSA top layer 14a of the first main face on the first nuclear 12a with 60, the rubber-based PSA that solidifies with the 2nd EB examines 12b, its first main face is adhered on the second main face of the first nuclear 12a, and be adhered to second examine 12b the second main face second through EB curing rubber base table layer 14b.Interface at the first nuclear 12a and the second nuclear 12b defines lamination seam 18.According to the present invention, the first nuclear 12a and the second nuclear 12b comprise microballoon, and the first top layer 14a and the second top layer 14b substantially do not contain microballoon.

[0066] Fig. 7 is the schematic cross sectional view according to the adhesive tape 70 of another embodiment of the present invention.Comprise the rubber-based PSA nuclear 12a that an EB solidifies and be adhered to the rubber-based PSA top layer 14a that first EB who examines the first main face on the 12a solidifies with 70, the rubber-based PSA that solidifies with the 2nd EB examines 12b, its first main face is adhered to the second main face of the first nuclear 12a, be adhered to the second nuclear 12b the second main face second examine the 12a and second supporting layer of examining between the 12b 16 through EB curing rubber base table layer 14b and first.Supporting layer 16 can be basic identical with the supporting layer 16 described in above-mentioned Fig. 3.According to the present invention, the first nuclear 12a and the second nuclear 12b comprise microballoon, and the first top layer 14a and the second top layer 14b substantially do not contain microballoon.

[0067] Fig. 8 is that it is similar to Fig. 1 according to the schematic cross sectional view of the adhesive tape 80 of another embodiment of the present invention, just comprises the lamination seam in the nuclear.Comprise the rubber-based PSA nuclear 12a that an EB solidifies and be adhered to the rubber-based PSA top layer 14 that first EB that examines the first main face on the 12a solidifies with 80, with the rubber-based PSA nuclear 12b that the 2nd EB solidifies, its first main face is adhered to the second main face of the first nuclear 12a.Lamination seam 18 is limited at the interface between the first nuclear 12a and the second nuclear 12b.According to the present invention, the first nuclear 12a and the second nuclear 12b comprise microballoon, and top layer 14 does not contain microballoon substantially.

[0068] the following examples relate to and are used to make the composition of electronic beam curing pressure-sensitive adhesive tape and the embodiment of process.

Embodiment 1

[0069] the rubber-based PSA nuclear that solidifies of EB is by being 50% solid by weight percentage in toluene, with solution form mixed weight (dry weight) percentage be 95.8% rubber-based adhesive solution, percentage by weight be 0.9% the trimethylolpropane tris as crosslinking agent (3-mercaptopropionic acid ester) (TMPTMP) and percentage by weight be that the mixture of the non-rigid polymer microballoon of hollow of 3.9% (percent by volume is 32%) prepares.This mixture is in stirring about one and a half hours in ∑ type paddle mixer (sigma bladder mixer) under 190 ℃.Binder solution comprises the s-B-S linear copolymer of percentage by weight about 19.3%, and it comprises the SB of about 31% styrene, percentage by weight about 16.1%; The α sobrerone tackifier of percentage by weight about 25.8%; The rosin ester tackifier of percentage by weight about 32.3%; And the compatible fragrancing liquid resin of percentage by weight about 6.4%.Solvent is removed by vacuum.

[0070] for the top layer, same EB curing rubber base PSA can prepare as core layer, just microballoon is not joined in the solution.Solvent is removed by vacuum.

[0071] adhesive tape is by top layer (the about 50g/m of coating weight with 50 microns ²) and the nuclear coextrusion of 0.8mm on release liner, prepare.Come out from extrusion device at adhesive tape, when forming structure shown in Figure 1, on its two sides, adhesive tape is carried out the electron beam irradiation of naked (open faced) with 275kv and 50kGR.Second release liner can be applied on the adhesive tape.(it should be noted that in actual use whether release liner applies at this moment and depend on adhesive tape and whether will be laminated on other band or other layer.)

Embodiment 2

[0072] but the rubber-based PSA composition that EB solidifies be prepared as embodiment 1 substantially, comprising that weight (dry weight) percentage is that 90.8% the adhesive, the percentage by weight that use are 3.8% the non-rigid polymer microballoon of hollow, the BJO0930 hollow phenols microballoon of percentage by weight 1.8% in embodiment 1---can obtain from the Eastech Chemical company of philadelphia, pa, and the Cab-O-Sil of percentage by weight 3.6% ^Pyrolytic silicon dioxide---from the Bostonian Cabot in Massachusetts company.Solvent is removed by vacuum.

[0073] for the top layer, but the rubber-based PSA that same EB solidifies can prepare as core layer, just microballoon is not joined in the solution.Solvent is removed by vacuum.

[0074] adhesive tape is by top layer (the about 50g/m of coating weight of 50 microns of coextrusion ²) and the nuclear of 0.8mm on release liner, prepare.When adhesive tape comes out, with 275Kv and 50kGR adhesive tape is carried out electron beam irradiation on the two sides of band from extrusion device.

[0075] will with one side be laminated to 0.127mm advanced in years draw polyester film (Mylar) to go up after, test its release adhesive (peel adhesion).Nuclear demonstrates the peel strength of 5300N/m certainly at the bottom of the stainless steel lining, and is 2960N/m on the TPO substrate.The top layer presents the peel strength of 9400N/m at the bottom of the stainless steel lining, and is 3130N/m on the TPO substrate.

Can expect that [0076] above-mentioned sample can be prepared the above-mentioned peel strength of not negative effect to improve high-temperature behavior with the TMPTMP that is used for electronic beam curing at least about 3%.

[0077] among the embodiment 1 and 2 prepared adhesive tape corresponding to the band that is shown among Fig. 1.The band that is shown among Fig. 1 does not show release liner (one or more).

Embodiment 3

[0078] be prepared as follows such as the double-faced adhesive tape that is shown in Fig. 2: coextrusion core layer and two top layers on the release liner, top layer are on each main face of this core layer, but its rubber-based PSA composition that uses EB prepared among the embodiment 2 to solidify.When described band comes out, on its two sides, can carry out electron beam irradiation with 275kv and 50kGR through the rubber-based PSA that EB solidifies to two-sided from extrusion device.Second release liner is applied to adhesive tape.The band that is shown in Fig. 2 does not show release liner.

Embodiment 4

[0079] is prepared as follows such as the laminate adhesive band that is shown in Fig. 3.But the preparation of the rubber-based PSA that EB solidifies band substantially as described in Example 1, comprises extruding with EB and solidify.The second main face of core layer is not covered.Second nuclear is prepared by preparing nuclear as described in Example 1, extrudes with EB to solidify this second nuclear.The second main face of second nuclear is not covered.Next, the nonwoven PET supporting layer of 3 mils is provided.The laminate adhesive band is prepared as follows: the second main face of unlapped first nuclear is applied on the one side of nonwoven PET supporting layer of described 3 mils, and the second main face of unlapped second nuclear is applied to the another side of this supporting layer, thereby forms laminate adhesive band shown in Figure 3.The band that is shown in Fig. 3 does not show release liner.

Embodiment 5

[0080] is prepared as follows such as the laminate adhesive band that is shown in Fig. 4.But the preparation of the rubber-based PSA that EB solidifies band as described in the embodiment 1, comprises extruding with EB and solidifies that the second main face of core layer is not covered substantially.But, comprise extruding and solidify that the top layer is not covered with EB as the rubber-based PSA band that preparation second EB as described in the embodiment 1 solidifies.Next, the unlapped top layer of described second band is in turn laminated on the not covering nuclear of first band, to form structure as shown in Figure 4.The band that is shown in Fig. 4 does not show release liner.

It should be noted that [0081] structure that is shown in Fig. 4 can prepare for all four layers by coextrusion.Yet, can expect and need solidify by more high-power EB, with the internal layer of this coextrusion thing of abundant curing.

Embodiment 6

[0082] be prepared as follows such as the two-sided laminate adhesive band that is shown in Fig. 5: coextrusion core layer and two top layers, top layer are on each main face of this core layer, but the rubber-based PSA composition that has used EB prepared among the embodiment 2 to solidify.When described band comes out from extrusion device, but the rubber-based PSA that on its two sides this two-sided EB is solidified carries out electron beam irradiation with 275kv and 50kGR.One of top layer is not covered.Substantially as preparation second adhesive tape as described in the embodiment 1, the face of its nuclear is not covered.Next, the top layer face that do not cover of first adhesive tape is in turn laminated to the face that does not cover nuclear of second adhesive tape, to form structure as shown in Figure 5.The band that is shown in Fig. 5 does not show release liner.

It should be noted that [0083] structure that is shown in Fig. 5 can prepare for all four layers by coextrusion.Yet, can expect and need solidify by more high-power EB, with the internal layer of this coextrusion thing of abundant curing.

Embodiment 7

[0084] is prepared as follows such as the two-sided laminate adhesive band that is shown in Fig. 6.Two adhesive tapes prepare as embodiment 1 substantially, the release liner of contiguous each band of its mesexine face, and the second main face of nuclear is not covered.Next, the not covering second main face of nuclear is laminated on together, to form structure as shown in Figure 6.The band that is shown in Fig. 6 does not show release liner.

It should be noted that [0085] structure that is shown in Fig. 6 can prepare for all four layers by coextrusion.Yet, can expect and need solidify by more high-power EB, with the internal layer of this coextrusion thing of abundant curing.

Embodiment 8

[0086] is prepared as follows such as the two-sided laminate adhesive band that is shown in Fig. 7.Two adhesive tapes prepare as embodiment 1 substantially, the release liner of contiguous two bands of its mesexine face, and the second main face of nuclear is not covered.Next, provide 3 mil nonwoven PET supporting layers.Two-sided laminate adhesive band is prepared as follows: the second main face that do not cover that applies nuclear is to each face of described 3 mil nonwoven PET supporting layers, thus formation laminate adhesive band as shown in Figure 7.The band that is shown in Fig. 7 does not show release liner.

Embodiment 9

[0087] the rubber-based PSA nuclear that solidifies of EB is by being 50% solid by weight percentage in toluene, with solution form mixed weight (dry weight) percentage be 95.8% rubber-based adhesive solution, percentage by weight be 0.9% the trimethylolpropane tris as crosslinking agent (3-mercaptopropionic acid ester) (TMPTMP) and percentage by weight be that the mixture of the non-rigid polymer microballoon of hollow of 3.9% (percent by volume is 32%) prepares.These compositions are in stirring one and a half hours in ∑ type paddle mixer under 190 ℃.Binder solution comprises the s-B-S linear copolymer of percentage by weight about 19.3%, and it comprises the SB of about 31% styrene, percentage by weight about 16.1%; The α sobrerone tackifier of percentage by weight about 25.8%; The rosin ester tackifier of percentage by weight about 32.3%; And the compatible fragrancing liquid resin of percentage by weight about 6.4%.Solvent is removed by vacuum.

[0088] for the top layer, same EB curing rubber base PSA can prepare as core layer, just microballoon is not joined in the solution.Solvent is removed by vacuum.

[0089] adhesive tape be by with the top layer with about 50g/m ²Coating weight be coated on the release liner and preparation.Nuclear is applied on the top layer with the thickness of about 0.8mm.Come out from extrusion device at adhesive tape, when forming structure shown in Figure 1, on its two sides, adhesive tape is carried out the electron beam irradiation of naked (open faced) with 275kv and 50kGR.One release liner is applied on the exposure of adhesive tape.(it should be noted that in actual use whether release liner applies at this moment and depend on adhesive tape and whether will be laminated on other band or other layer.)

Embodiment 10

[0090] but the rubber-based PSA composition that EB solidifies be prepared as embodiment 1 substantially, comprising that weight (dry weight) percentage is that 90.8% the adhesive, the percentage by weight that use are 3.8% the non-rigid polymer microballoon of hollow, the BJO0930 hollow phenols microballoon of percentage by weight 1.8% in embodiment 1---can obtain from the Eastech Chemical company of philadelphia, pa, and the Cab-O-Sil of percentage by weight 3.6% ^Pyrolytic silicon dioxide---from the Bostonian Cabot in Massachusetts company.Solvent is removed by vacuum.

[0091] for the top layer, but the rubber-based PSA that same EB solidifies can prepare as core layer, just microballoon is not joined in the solution.Solvent is removed by vacuum.

[0092] adhesive tape is by top layer (the about 50g/m of coating weight of 50 microns of coatings on release liner ²) prepare.Then, the nuclear of 0.8mm is applied on the top layer.Second top layer is applied on the core layer, and adhesive tape is carried out electron beam irradiation with 275kv and 50kGR.One release liner is applied on the exposure of adhesive tape.

Can expect that [0093] above-mentioned sample can be prepared the above-mentioned peel strength of not negative effect to improve high-temperature behavior with the TMPTMP that is used for electronic beam curing at least about 3%.

[0094] among the embodiment 1 and 2 prepared adhesive tape corresponding to the band that is shown among Fig. 1.The band that is shown among Fig. 1 does not show release liner (one or more).

Embodiment 11

[0095] is prepared as follows such as the laminate adhesive band that is shown in Fig. 3.But the preparation of the rubber-based PSA that EB solidifies band is substantially as described in the embodiment 9, and comprises that EB solidifies.Second nuclear prepares by it is coated on the release liner as described in embodiment 1.Next, provide 3 mil nonwoven PET supporting layers.The laminate adhesive band is prepared as follows: first of first band is examined the one side that is applied to described 3 mil nonwoven PET supporting layers, and second nuclear of second band is applied to the another side of supporting layer, thereby form laminate adhesive band shown in Figure 3.The band that is shown in Fig. 3 does not show release liner.

Embodiment 12

[0096] is prepared as follows such as the adhesive tape that is shown in Fig. 4.But the preparation of the rubber-based PSA that EB solidifies band as described in the embodiment 9, comprises that EB solidifies substantially.As described in embodiment 9, but the rubber-based PSA band that preparation second EB solidifies comprises that EB solidifies.Release liner removes from the top layer, and on the core layer with skin lamination to the first band that exposes.One release liner can be applied to the core layer of second band, with easier operation.The band that is shown in Fig. 4 does not show release liner.

Embodiment 13

[0097] is prepared as follows such as the two-sided laminate adhesive band that is shown in Fig. 6.Two adhesive tapes are substantially as embodiment 9 preparations, and the exposure core layer of two bands is laminated on together.The band that is shown in Fig. 6 does not show release liner.

Embodiment 14

[0098] laminate adhesive band as shown in Figure 8 is prepared as follows: will be substantially by the band of embodiment 9 described preparations with carry out lamination by core layer being coated in the band for preparing on the release liner.The exposure core layer of described band is laminated on together.

It should be noted that [0099] structure that is shown in Fig. 7 can prepare for all four layers by coextrusion.Yet expection needs more high-power EB to solidify, with the internal layer of this coextrusion thing of abundant curing.

Embodiment 15

[0100] but the rubber-based PSA that EB solidifies nuclear be prepared as follows: with the SBS block copolymer KRAYTON of percentage by weight 38.8% ^The SIS block copolymer KRAYTON of D1102, percentage by weight 9.7% ^The HERCULIN tackifier of the rosin ester resin FORAL 85 of D1107, percentage by weight 38.8%, the PICCOLYTE A-115 of percentage by weight 4.8%, percentage by weight 4.8%, the carbon black of percentage by weight 1% and the TMPTMP as crosslinking agent of percentage by weight 1.9% mix.In this rubber-based PSA, add the PHENOSET BJO-0840 microballoon of percentage by weight 18% (percent by volume 45%).For the top layer, but the rubber-based PSA that same EB solidifies can prepare as core layer, just microballoon is not joined in the composition.

[0101] adhesive tape is by being prepared 50 microns top layer and the core layer coextrusion of 0.8mm on release liner.Come out from extrusion device at adhesive tape, when forming structure shown in Figure 1, on the two sides of band, carry out naked electron beam irradiation with 275kv and 50kGR.Second release liner is applied on this adhesive tape.

[0102] embodiment 15 described core layers and top layer are used to make double-faced adhesive tape as shown in Figure 2.Similarly, the adhesive article of Fig. 3-8 can be made with embodiment 15 described core layers and skin combined thing.

Although the present invention is explained about its preferred implementation, should be appreciated that to those skilled in the art that [0103] after having read this specification, various changes will be conspicuous.Therefore, should be appreciated that invention disclosed herein is intended to cover these and changes, they all drop in the scope of appended claims.

Claims

1. pressure-sensitive adhesive tape, it comprises:

The rubber-based pressure-sensitive adhesive nuclear of electronic beam curing, it comprises non-rigid polymer microballoon, and has the first and second main faces; And

The rubber-based pressure-sensitive adhesive top layer of electronic beam curing, it is adhered on the described first main face,

The rubber-based pressure-sensitive adhesive top layer of wherein said electronic beam curing does not contain microballoon substantially.

2. adhesive tape according to claim 1, it further comprises the rubber-based pressure-sensitive adhesive top layer of second electronic beam curing, it has the first main face and the second main face, and the first main face on the rubber-based pressure-sensitive adhesive top layer of wherein said second electronic beam curing is adhered on the second main face of rubber-based pressure-sensitive adhesive nuclear of described electronic beam curing.

3. adhesive tape according to claim 1, wherein said microballoon is complete expansion.

4. adhesive tape according to claim 3, wherein said microballoon exists with about 30% to about 60% long-pending amount of described contact adhesive nucleome.

5. adhesive tape according to claim 1, the rubber-based pressure-sensitive adhesive of wherein said electronic beam curing has improved the cohesive to the TPO surface.

6. adhesive tape according to claim 5, wherein said TPO is without priming.

7. adhesive tape according to claim 2, it further comprises rubber-based pressure-sensitive adhesive nuclear of second electronic beam curing that comprises non-rigid polymer microballoon, and it is adhered on the second main face on rubber-based pressure-sensitive adhesive top layer of described second electronic beam curing.

8. adhesive tape according to claim 7, it further comprises the rubber-based pressure-sensitive adhesive top layer of the three electron-beam curing that is adhered to described second nuclear.

9. adhesive tape according to claim 2, it further comprises the non-woven polymer supporting layer, and it is between the second main face of the foam rubber based pressure-sensitive adhesive nuclear of the first main face on the rubber-based pressure-sensitive adhesive top layer of described second electronic beam curing and described electronic beam curing.

10. adhesive tape according to claim 1, it has first and second outer surfaces, further comprises the object of described first outer surface that is connected to described adhesive tape.

11. adhesive tape according to claim 10, described second outer surface of wherein said adhesive tape is adhered on the substrate.

12. adhesive tape according to claim 1, the rubber-based pressure-sensitive adhesive nuclear of wherein said electronic beam curing comprises the lamination seam.

13. pressure-sensitive adhesive tape according to claim 1, it further comprises:

The rubber-based pressure-sensitive adhesive nuclear of second electronic beam curing, it comprises non-rigid polymer microballoon, and has the first and second main faces;

The rubber-based pressure-sensitive adhesive top layer of second electronic beam curing, on the first main face that its rubber-based pressure-sensitive adhesive that is adhered to described second electronic beam curing is examined,

Wherein, the rubber-based pressure-sensitive adhesive top layer of described second electronic beam curing does not contain microballoon substantially, and the second main face of described first nuclear is adhered on the described second second main face of examining, and forms the lamination seam thus.

14. pressure-sensitive adhesive tape according to claim 13, one of rubber-based pressure-sensitive adhesive top layer of wherein said first and second electronic beam curings is adhered on the object.

15. pressure-sensitive adhesive tape according to claim 13, one of rubber-based pressure-sensitive adhesive top layer of wherein said first and second electronic beam curings is adhered on the substrate, and another of the rubber-based pressure-sensitive adhesive top layer of described first and second electronic beam curings is adhered on the object that is assemblied on the described substrate.

16. pressure-sensitive adhesive tape according to claim 15, the substrate that wherein said band is bonded to comprise in thermoplastic, metal, glass, thermosetting resin or the paint one or more surface.

17. pressure-sensitive adhesive tape according to claim 15, wherein said substrate is the vehicles.

18. pressure-sensitive adhesive tape according to claim 15, wherein said object are the body side profiled members of the vehicles.

19. pressure-sensitive adhesive tape according to claim 13, it further comprises the non-woven polymer supporting layer, and it is between the second main face of the foam rubber based pressure-sensitive adhesive nuclear of the second main face on the rubber-based pressure-sensitive adhesive top layer of described second electronic beam curing and described electronic beam curing.

20. a double-faced adhesive tape, it comprises:

But the rubber-based pressure-sensitive adhesive of first electronic beam curing nuclear, it comprises microballoon and has the first and second main faces;

But the rubber-based pressure-sensitive adhesive top layer of first electronic beam curing, but it is adhered to the first main face of the rubber-based pressure-sensitive adhesive nuclear of described first electronic beam curing;

But the rubber-based pressure-sensitive adhesive of second electronic beam curing nuclear, it comprises microballoon and has the first and second main faces, wherein, but but the first main face of the rubber-based pressure-sensitive adhesive of described second electronic beam curing nuclear is adhered to the second main face of the rubber-based pressure-sensitive adhesive nuclear of described first electronic beam curing

Wherein, but but between the rubber-based pressure-sensitive adhesive nuclear of the rubber-based pressure-sensitive adhesive of described first electronic beam curing nuclear and described second electronic beam curing, be formed with the lamination seam;

But the rubber-based pressure-sensitive adhesive top layer of second electronic beam curing, but it is adhered to the first main face of the rubber-based pressure-sensitive adhesive nuclear of described second electronic beam curing, wherein, but the rubber-based pressure-sensitive adhesive top layer of described first and second electronic beam curings does not all contain microballoon substantially.

21. a double-faced adhesive tape, it comprises:

But the rubber-based pressure-sensitive adhesive top layer of electronic beam curing, but it is adhered to the first main face of the rubber-based pressure-sensitive adhesive nuclear of described first electronic beam curing, and wherein, but the rubber-based pressure-sensitive adhesive top layer of described electronic beam curing does not contain microballoon substantially;

But but wherein between the rubber-based pressure-sensitive adhesive nuclear of the rubber-based pressure-sensitive adhesive of described first electronic beam curing nuclear and described second electronic beam curing, form the lamination seam.

22. a method of making pressure-sensitive adhesive tape, it comprises:

But the rubber-based pressure-sensitive adhesive nuclear of electronic beam curing is provided, and it comprises the polymer microballoon of expansion, and has the first and second main faces;

But the rubber-based pressure-sensitive adhesive top layer of electronic beam curing is applied on the described first main face;

By applying electron beam to described nuclear and described top layer, but but solidify the rubber-based pressure-sensitive adhesive nuclear of described electronic beam curing and the rubber-based pressure-sensitive adhesive top layer of described electronic beam curing, but the rubber-based pressure-sensitive adhesive top layer of wherein said electronic beam curing does not contain microballoon substantially.

23. method according to claim 22, it comprises that further but the rubber-based pressure-sensitive adhesive top layer that applies second electronic beam curing is to the described second main face, but and the rubber-based pressure-sensitive adhesive top layer of solidifying described second electronic beam curing, but the rubber-based pressure-sensitive adhesive top layer of wherein said second electronic beam curing does not contain microballoon substantially.

24. method according to claim 22, the polymer microballoon of wherein said expansion is non-rigid.

25. one kind is assemblied in method on the substrate with object, it comprises:

Provide object and described object with the substrate that is bonded to;

But the rubber-based pressure-sensitive adhesive nuclear of first electronic beam curing is provided, and it comprises the polymer microballoon of expansion and has the first and second main faces;

But the rubber-based pressure-sensitive adhesive top layer of first electronic beam curing is applied to the described first main face;

By electron beam being applied to described nuclear and described top layer, but but solidify the rubber-based pressure-sensitive adhesive nuclear of described first electronic beam curing and the rubber-based pressure-sensitive adhesive top layer of described first electronic beam curing, to form pressure-sensitive adhesive tape, wherein, but the rubber-based pressure-sensitive adhesive top layer of described first electronic beam curing does not contain microballoon substantially;

Described object is adhered on the one side of described pressure-sensitive adhesive tape; And

The another side of described pressure-sensitive adhesive tape is adhered on the described substrate.

26. method according to claim 25, it comprises that further but the rubber-based pressure-sensitive adhesive top layer that applies described second electronic beam curing is to the described second main face, but and the rubber-based pressure-sensitive adhesive top layer of solidifying described second electronic beam curing, wherein, but the rubber-based pressure-sensitive adhesive top layer of described second electronic beam curing does not contain microballoon substantially.

27. method according to claim 25, but it further comprises the rubber-based pressure-sensitive adhesive nuclear that second electronic beam curing is provided, and it comprises the polymer microballoon of expansion and has the first and second main faces;

But but the rubber-based pressure-sensitive adhesive top layer of second electronic beam curing is applied to the first main face of the rubber-based pressure-sensitive adhesive nuclear of described second electronic beam curing;

Examine and described second top layer by electron beam being applied to described second, but but the rubber-based pressure-sensitive adhesive nuclear of described second electronic beam curing and the rubber-based pressure-sensitive adhesive top layer of described second electronic beam curing solidified; And

But but the second main face that the rubber-based pressure-sensitive adhesive of described second electronic beam curing is examined is applied to the second main face of the rubber-based pressure-sensitive adhesive nuclear of described first electronic beam curing, thereby be formed on the compound pressure-sensitive adhesive tape that has the lamination seam between each described second main face.

28. method according to claim 25, the substrate that wherein said pressure-sensitive adhesive tape is bonded to comprise in thermoplastic, metal, glass, thermosetting resin or the paint one or more surface.

29. method according to claim 28, wherein said thermoplastic is a TPO.

30. method according to claim 28, wherein said substrate is without priming.

31. method according to claim 25, wherein said substrate is the vehicles.

32. method according to claim 25, wherein said object are the body side profiled members of the vehicles.

33. one kind is assemblied in method on the substrate with object, it comprises:

Object is provided;

Substrate is provided;

But the rubber-based pressure-sensitive adhesive nuclear of first electronic beam curing is provided, and it comprises microballoon and has the first and second main faces;

By electron beam being applied to described nuclear and described top layer, but but solidify the rubber-based pressure-sensitive adhesive nuclear of described first electronic beam curing and the rubber-based pressure-sensitive adhesive top layer of described first electronic beam curing, wherein, but the rubber-based pressure-sensitive adhesive top layer of described first electronic beam curing does not contain microballoon substantially;

But the rubber-based pressure-sensitive adhesive nuclear of second electronic beam curing is provided, and it comprises microballoon and has the first and second main faces;

But but the rubber-based pressure-sensitive adhesive top layer of second electronic beam curing is applied to the first main face of the rubber-based pressure-sensitive adhesive nuclear of described second electronic beam curing, wherein, but the rubber-based pressure-sensitive adhesive top layer of described second electronic beam curing does not contain microballoon substantially;

But but the second main face that the second main face that applies the rubber-based pressure-sensitive adhesive nuclear of described second electronic beam curing is examined to the rubber-based pressure-sensitive adhesive of described first electronic beam curing, described electron beam is formed on the pressure-sensitive adhesive tape that has the lamination seam between each described second main face;