CN1205733A - Blended pressure-sensitive adhesives - Google Patents

Abstract

A pressure-sensitive adhesive comprising a blend of at least two components, wherein the first component is at least one pressure-sensitive adhesive and the second component is at least one thermoplastic material, wherein the components form a blended composition having more than one domain and, wherein one domain is substantially continuous (generally, the pressure-sensitive adhesive) and the other domain is substantially fibrinous to schistose (generally, the thermoplastic material). The second component can be (a) at least one thermoplastic elastomer, (b) at least one elastomer with a tackifying resin or (c) at least one elastomer.

Description

The pressure sensitive adhesive of fusion

Technical field

The present invention relates to contact adhesive composition, it more specifically is the contact adhesive composition that forms by at least two kinds of polymer materialss, at least a in the polymer materials is pressure sensitive adhesive, the goods that also relate to the production method of blended pressure sensitive adhesive and be coated with this tackiness agent.

Background of the present invention

Continue to have the needs that improve pressure sensitive adhesive, to satisfy the requirement of new application.Generally in that additive is joined in the pressure sensitive adhesive must be very careful when changing their performance, to avoid losing peel adhesion and shearing resistance.This has hindered the widespread use of thermoplastic material as properties-correcting agent.

The pressure sensitive adhesive of main type comprises the natural rubber of tackify; Synthetic rubber is as isoprene-isobutylene rubber; And linear, the radiation shape of tackify, star and branching and taper styrene block copolymer, as styrene butadiene, styrene-ethylene/divinyl and styrene-isoprene; Urethane; Polyvinyl ether; Acrylic acid or the like especially has the acrylic acid or the like of chain alkyl; Poly-alpha-olefin and siloxanes.

When using additive to change the pressure sensitive adhesive performance, general additive need be miscible with pressure sensitive adhesive, or form uniform mixture at molecular level.The pressure sensitive adhesive of some type has been used thermoplastic elastomer, the thermoplastics and elastomer-modified of tackify.For example, thermoplastic material is added in the polymeric thermally melting acrylic pressure-sensitive adhesive, and this thermoplastics is a kind of wrapping material or callable tape backing.Under this class situation, control the type and the amount of thermoplastic material, make thermoplastic material can play wrapping material, avoid the deterioration of the bond properties of pressure sensitive adhesive simultaneously.

But, when the non-sticky thermoplastic additive is mixed with pressure sensitive adhesive, usually observe total bond properties decline (with only comparing) of this mixture for the performance of pressure sensitive adhesive.In the tackiness agent of styrene block copolymer, add thermoplastic polymer, the pressure sensitive adhesive viscosity in large-area screening glass is used that makes is descended.

No matter its whether modification, pressure sensitive adhesive applications is in existing over half a century of various uses.Generally use pressure sensitive adhesive in adhesive tape, this class adhesive tape comprises backing or base material and pressure sensitive adhesive.Typical pressure sensitive adhesive only need apply finger pressure just can be bonding, and be permanent adhesion.

In medical field, pressure sensitive adhesive tape can be applicable to the various different purposes of medical treatment and health field.During great majority were used, adhesive tape was applied directly to patient's skin.Therefore the very important point be pressure sensitive adhesive can with skin-compatible, skin irritation not, and can be adhered on the skin, can injured skin when taking off adhesive tape from skin or be coated with the goods of tackiness agent.Pressure sensitive adhesive tape and goods useful especially purposes in medical applications is through skin patch (transdermal patches).Such patch can or be used for the medicine transfer film is fixed on skin as the medicine transfer film.

Although pressure sensitive adhesive tape and goods are widely used in medical field, pressure sensitive adhesive tape and goods also have many other application.For example, transfering belt can be used for two surfaces are bonded together, and is adhered to the surface as the rim strip with wrapping material or fabric.But the transfering belt tackiness agent generally only has very little tensile strength, and the method for solution adds glass fibre exactly provides tensile strength.

Another application is the label field, because label has many kinds surface, so need various pressure sensitive adhesives.But pressure sensitive adhesive must be able to easily cut off, can wire drawing or slowly ooze out, enable to produce effectively.

Pressure sensitive adhesive requires that the comprehensive of good viscosity and elastic performance arranged, and promptly requires the comprehensive of sticking power, force of cohesion, stretching and elastic quadruple performance.Pressure sensitive adhesive generally comprises and is intrinsic tackiness or elastic elastomerics, or adds the thermoplastic elastomer of tackifying resin tackify.

The present invention's general introduction

On the one hand, the invention provides the pressure sensitive adhesive of the adulterant that comprises at least two kinds of components, wherein first component is a kind of pressure sensitive adhesive at least, second component is a kind of thermoplastic material at least, the blend composition that these components form has more than one zone, one of them zone is successive (generally being pressure sensitive adhesive) basically, and another zone is that fibril is to flaky (generally being thermoplastic material) basically.

Second component can also be (a) at least a thermoplastic elastomer, as by the proxy 1995,12,22 No.08/578 that propose, described in 010, (b) at least a using by the proxy 1995,12,22 No.08/577 that propose, the elastomerics of the tackifying resin tackify described in 603, or (c) at least a elastomerics.

The advantage of the pressure sensitive adhesive of fusion of the present invention has provided the tackiness agent with following one or more character.These improved properties the pressure sensitive adhesive before mixing with thermoplastic material.These character comprise:

(1) greater than the peel adhesion of only using pressure sensitive adhesive component, the shearing resistance similar to only using pressure sensitive adhesive component,

(2) greater than the shearing resistance of only using pressure sensitive adhesive component, the peel adhesion similar to only using pressure sensitive adhesive component,

(3) anisotropic peel adhesion,

(4) anisotropic shearing resistance and

(5) to any elongation up to extension at break, the tensile stress tensile stress at least big twice more horizontal on coiled strip is vertical than coiled strip.

But pressure sensitive adhesive component should be hot melt processing, and under use temperature, satisfy Handbook ofPressure-sensitive Adhesive Technology, Edited by D.Statas, p.172, the Dahlquist standard described in (1989).Typical pressure sensitive adhesive component is the 30-98% of composition weight, is 40-95% weight preferably, and 60-95% weight is better.And pressure sensitive adhesive component can be a kind of pressure sensitive adhesive, or the mixture of several pressure sensitive adhesives.

The thermoplastic material component is superpolymer normally, and this polymkeric substance is softening when heat treated, gets back to solid-state when being cooled to room temperature.Useful thermoplastic material is into fine thing, and is immiscible in pressure sensitive adhesive component basically under use temperature, although thermoplastics can be miscible in pressure sensitive adhesive under processing temperature.Usually, the thermoplastic material component is the 2-70% of composition weight, is 5-60% weight preferably, and 5-40% weight is better.And thermoplastic material component component can be a kind of thermoplastic material, or the mixture of several thermoplastic materials.

The scorification of the pressure sensitive adhesive that is used for fusion has also been described on the other hand.Two kinds of components melting mixing in a container forms the contact adhesive composition of fusion.Forming step can be (1) extrudes the fusion fusion under shear flow and/or extension stream condition a component, or the fusion adulterant is extruded and drawn in (2).The composition of cooling forming then.

The present invention also provides adhesive tape and the goods that have been coated with pressure sensitive adhesive.

The accompanying drawing summary

Fig. 1 is the curve of the pressure sensitive adhesive layer of embodiment 31 at base-material downward direction and stress-strain in a lateral direction.

Fig. 2 adopts laser light scattering test, the light scattering diagram of the pressure sensitive adhesive layer of embodiment 39.

Fig. 3 adopts scanning electronic microscope (SEM), at 4000X, and the cross-sectional view of the downward direction of the pressure sensitive adhesive layer of embodiment 44.

Fig. 4 adopts scanning electronic microscope (SEM), at 4000X, and the cross-sectional view of the horizontal direction of the pressure sensitive adhesive layer of embodiment 44.

Fig. 5 adopts laser light scattering test, the light scattering diagram of the pressure sensitive adhesive layer of embodiment 44.

Fig. 6 adopts SEM, at 4000X, and the cross-sectional view of the pressure sensitive adhesive layer downward direction of comparing embodiment C8.

Fig. 7 adopts laser light scattering test, the light scattering diagram of the pressure sensitive adhesive layer of comparing embodiment C9.

Fig. 8 adopts SEM, at 4000X, and the cross-sectional view of the pressure sensitive adhesive layer downward direction of embodiment 46.

Fig. 9 adopts SEM, at 4000X, and the cross-sectional view of the pressure sensitive adhesive layer horizontal direction of embodiment 46.

Figure 10 adopts laser light scattering test, the light scattering diagram of the pressure sensitive adhesive layer of embodiment 46.

Figure 11 is the cross-sectional view of transdermal matrix device of the present invention.

Figure 12 is the cross-sectional view that the transdermal drug in the tackiness agent of the present invention is stocked device.

Figure 13 is the cross-sectional view of the present invention through skin pastille adhesive device.

Figure 14 is the cross-sectional view through the skin multilayer stacking device of the present invention.

Figure 15 is the cross-sectional view of another kind of the present invention through the skin multilayer stacking device.

The description of embodiment preferably

The invention provides a kind of pressure sensitive adhesive, this pressure sensitive adhesive comprises the adulterant of at least two kinds of components, wherein first component is at least a pressure sensitive adhesive, and second kind of component is at least a thermoplastic material, and component forms the composition with zone more than of fusion.Second component can also be (a) at least a thermoplastic elastomer, as by the proxy 1995,12,22 No.08/578 that propose, described in 010, (b) at least a using by the proxy 1995,12,22 No.08/577 that propose, the elastomerics of the tackifying resin tackify described in 603, or (c) at least a elastomerics.

Pressure sensitive adhesive component can be to have Handbook of Pressure-sensitive Adhesive p.172, any material of the pressure sensitive adhesive character described in the paragraph 1 (1989).And but useful pressure sensitive adhesive is hot melt processing, and satisfies the Dahlquist standard under use temperature.Typical pressure sensitive adhesive component is the 30-98% of composition weight, is 40-95% weight preferably, and 60-95% weight is better.And pressure sensitive adhesive component can be a kind of pressure sensitive adhesive, or the mixture of several pressure sensitive adhesives.

The useful pressure sensitive adhesive of the present invention is comprised natural rubber, the synthetic rubber of tackify, styrene block copolymer, polyvinyl ether, acrylic acid or the like, poly-alpha-olefin and the siloxanes of tackify.

Useful natural rubber pressure sensitive adhesive generally contains the natural rubber of mastication, one or more tackifying resins of 25-300 part in per 100 parts of natural rubbers, usually and one or more oxidation inhibitor of 0.5-2.0 part.The natural rubber level range, comprises as CV-60 to dark ribbed smoked sheet from light grey wrinkle (rubber) glue, a kind of rubber rank of controlling viscosity, and SMR-5, a kind of rubber rank of ribbed smoked sheet.The tackifying resin that uses with natural rubber generally comprises but is not limited to the derivative of wood rosin and its hydrogenation; The terpine resin of various softening temperatures and petroleum base resin are as the ESCOREZ from the C5 aliphatic olefin deutero-resin of Exxon ^TM1300 series.Oxidation inhibitor is used to stop the attack of oxygenant to natural rubber, and the attack of oxygenant can cause losing the force of cohesion of caoutchouc adhesive.Useful oxidation inhibitor comprises but is not limited to amine, N for example, N '-two-betanaphthyl-1,4-phenyl diamines (can AgeRite D obtain); Phenols, as 2,5-two (tert-pentyl) quinhydrones (can be from Monsanto Chemical Co. with Santovar A ^TMObtain), methane (can be from Ciba-Geigy Corp. with IRGANOX for four [methylene radical 3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propianate] ^TM1010 obtain) and 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol) (can antioxidant 2246 obtain); And dithiocarbamate(s), as dithio dibutylamino zinc formate.To concrete purposes, can add other material in the caoutchouc adhesive, these additives comprise softening agent, pigment and are used for the solidifying agent of partially hardened pressure sensitive adhesive.

Another kind of useful pressure sensitive adhesive is to comprise elastomeric pressure sensitive adhesive.Such tackiness agent generally is elastomeric elastomerics, and they are autohensions or inviscid, need tackifier.

The synthetic rubber pressure sensitive adhesive of autohension comprises, for example isoprene-isobutylene rubber, iso-butylene and be less than multipolymer, polyisobutene, isoprene homopolymer, polyhutadiene or the styrene/butadiene rubbers of 3% isoprene.The pressure sensitive adhesive of isoprene-isobutylene rubber usually contains a kind of oxidation inhibitor, as zinc dibutyl dithiocarbamate.The polyisobutene pressure sensitive adhesive does not contain oxidation inhibitor usually.Need the synthetic rubber pressure sensitive adhesive of tackifier generally to be easy to melt-processed.These tackiness agents comprise polyhutadiene or styrene/butadiene rubbers, and the oxidation inhibitor that per 100 parts of rubber have 10-200 part tackifier and are generally 0.5-2.0 part is as IRGANOX ^TM1010.An elastomeric example is AMERIPOL ^TM1011A is a kind of styrene/butadiene rubbers that obtains from BF Goodrich.Spendable tackifier comprise rosiny derivative, for example FORAL ^TM85 (from Hercules, the stable rosin ester that Inc. obtains), SNOWTACK ^TMSeries (from the rosin series of Tenneco acquisition) and AQUATAC series (from the tallol rosin of Sylvachem); The synthetic hydrocarbon resin is as PICCOLYTE ^TMA series, from Hercules, the ESCOREZ of the polyterpene of Inc., C5 aliphatic olefin deutero-resin ^TMThe ESCOREZ of 1300 series and C9 aromatics/aliphatic olefin deutero-resin ^TM2000 series.Can add other material to specific purposes, the isoprene-isobutylene rubber, pigment, softening agent, fluid rubber that comprise hydrogenation are (as the VISTANEX that can obtain from Exxon ^TMLMMH polyisobutene fluid rubber) and be used for the solidifying agent of partially hardened tackiness agent.

The styrene block copolymer pressure sensitive adhesive generally comprises A-B or A-B-A type elastomerics and resin, and wherein A represents a kind of thermoplastic polystyrene block, and B represents the rubber-like block of polyisoprene, polyhutadiene or poly-(ethylene/butylene).The example of the useful various segmented copolymers of block copolymer pressure sensitive adhesives is comprised linear, radiation shape, star and the styrene-isoprene block copolymer that is tapered, as KRATON from Shell ChemicalCo. ^TMD1107P and from the EUROPRENE of EniChem Elastomers Americas Inc. ^TMSOL TE 9110; Line style vinylbenzene-(ethene-butylene) segmented copolymer is (as KRATON ^TMG 1657, can obtain from Shell Chemical Co.); Line style vinylbenzene-(ethylene-propylene) segmented copolymer is (as KRATON ^TMG 1750X can obtain from Shell Chemical Co.); And the styrene-butadiene block copolymer of linear, radiation shape, star, as KRATON from Shell Chemical Co. ^TMD 1118X and EniChem Elastomers Americas, the EUROPRENE of Inc. ^TMSOL TE 6205.Polystyrene block is tending towards forming the domain structure of spheroid, right cylinder or plate shape, and these shapes can make block copolymer pressure sensitive adhesives that two kinds of phase structures are arranged.The resin relevant with rubber phase be the general viscosity that forms in pressure sensitive adhesive.The example of the resin relevant with rubber phase comprises aliphatic olefin deutero-resin, as ESCOREZ ^TM1300 series and WINGTACK ^TMSeries (can obtain from Goodyear), rosin ester is as FORAL ^TMSeries and STAYBELITE ^TMEster 10 (two all can be from Hercules, and Inc. obtains); The hydrocarbon of hydrogenation is as ESCOREZ ^TM5000 series (can obtain) from Exxon; Polyterpene is as PICCOLYTE ^TMA series; From the terpene phenol resin in oil or terpene preface (terpentine) source, as PICCOFYN ^TMA 100 (can be from Hercules, Inc. obtains).The resin mutually relevant with thermoplastics can make the pressure sensitive adhesive sclerosis.The resin mutually relevant with thermoplastic comprises polyaromatic, as the PICCO of aromatic resins ^TM6000 series (can be from Hercules, Inc. obtains), coumarone-indene resin is as CUMAR ^TMSeries (can obtain) from Neville; And from the resin of the high solubility parameter of coal tar or oil, its softening temperature is approximately greater than 85 ℃, as the AMOCO of alpha-methyl styrene resin ^TM18 series (can obtain), PICCOVAR from Amoco ^TMThe PICCOTEX of 130 alkylaromatic hydrocarbon inden resin (can be from Hercules, Inc. obtains) and alpha-methyl styrene/vinyl toluene resin ^TMSeries (can obtain) from Hercules.Other material that can add specific purposes comprises rubber phase plastifying hydrocarbon ils, as TUEFLO ^TM6056 (can from Lydondell Petrochemical Co. obtain), from the polybutene-8 of Chevron, from the KAYDOL of Witco ^TMPolybutene and the SHELLFLEX that can obtain from Shell Chemical Co. ^TM371; Pigment; Oxidation inhibitor is as TRGANOX ^TM1010 and IRGANOX ^TM1076 (all can obtain), BUTAZATE from Ciba-Geigy Corp. ^TM(can obtain), CYANOX from Uniroyal Chemical Co. ^TMLDTP (can obtain) and BUTASAN from American Cyanamid ^TM(can obtain) from MonsantoCo.; Antiozonidate, as NBC, a kind of nickel dibutyl dithiocarbamate (can obtain) from Dupont; Fluid rubber is as VISTANEX ^TMThe LMHM polyisobutylene rubber; And ultraviolet inhibitors, as IRGANOX ^TM1010 and TINUVIN ^TMP (can obtain) from Ciba-Geigy Corp..

The character of the pressure sensitive adhesive that obtains to require, the polyvinyl ether pressure sensitive adhesive generally is the adulterant of the homopolymer of vinyl methyl ether, EVE or vinyl isobutyl ether, or the adulterant of Vinyl Ether homopolymer and Vinyl Ether and acrylate copolymer.According to the polymerization degree, homopolymer can be viscous oil, adhesive soften resin or rubber-like material are arranged.The polyvinyl ether that is used as raw material in the polyvinyl ether tackiness agent comprises the polymkeric substance based on following material: vinyl methyl ether, and as LUTANOL ^TMM 40 (can obtain), GANTREZ from BASF ^TMM 574 and GANTREZ ^TMM 555 (can be from ISP Technologies, Inc. obtains); EVE is as LUTANOL ^TMA25, LUTANOL ^TMA50, LUTANOL ^TM100; Vinyl isobutyl ether is as LUTANOL ^TMI 30, LUTANOL ^TMI 60, LUTANOL ^TMIC, LUTANOL ^TMI 60D and LUTANOL ^TMI 65D; Methacrylic ester/vinyl isobutyl ether/vinylformic acid is as ACRONAL ^TM550D (can obtain) from BASF.The oxidation inhibitor that is used for stablizing the polyvingl ether pressure sensitive adhesive comprises, for example IONOX ^TM30 (can obtain), IRGANOX from Shell ^TM1010 (can obtain) and the oxidation inhibitor ZKF that can obtain from Bayer Leverkusen from Ciba-Geigy.Other material that adds for specific purposes described in the BASF document comprises tackifier, softening agent and pigment.

The second-order transition temperature of acrylic pressure-sensitive adhesive generally is about-20 ℃ or lower, and it comprises the C of 100-80% weight ₃-C ₁₂The alkyl ester component, as Isooctyl acrylate monomer, vinylformic acid 2-ethyl-own ester and n-butyl acrylate, and the polar compound of 0-20% weight, as vinylformic acid, methacrylic acid, ethylene vinyl acetate, N-vinyl pyrrolidone and the big monomer of vinylbenzene.Acrylic pressure-sensitive adhesive comprises the vinylformic acid of 0-20% weight and the Isooctyl acrylate monomer of 100-80% weight preferably.Acrylic pressure-sensitive adhesive can be self-adhesion or by tackify.To the useful tackifier of acrylic acid or the like are rosin esters, as FORAL ^TM85 (can be from Hercules, Inc. obtains), aromatic resin are as PICCOTEX ^TMLC-55WK, aliphatic resin are as PICCOTAC ^TM95 (can be from Hercules, Inc. obtains) and terpine resins, as α-Pai Xi and beta-pinene, can PICCOLYTE ^TMA-115 and ZONAREZ ^TMB-100 obtains from Arizona Chemical Co..The solidifying agent that comprises isoprene-isobutylene rubber, pigment and the partially hardened tackiness agent of hydrogenation for other material of specific purposes adding.

The pressure sensitive adhesive of poly-alpha-olefin, also can be called poly-(1-alkene) pressure sensitive adhesive, but generally comprise a kind of uncrosslinked basically polymkeric substance or be grafted with the uncrosslinked polymkeric substance of the functional group of irradiation activation thereon, as United States Patent (USP) 5,209, described in 971 (people such as Babu), this patent is in this incorporated by reference.The poly-alpha-olefin polymkeric substance can be self-adhesion and/or comprise one or more tackify materials.If uncrosslinked, according to ASTM D 2857-93, " Standard Pratice for Dilute Solution Viscosity of Polymers " measures, and the logarithmic viscosity number of polymkeric substance is generally about 0.7-5.0 dL/g.In addition, polymkeric substance is general main is amorphous.Useful poly-alpha-olefin polymkeric substance comprises, for example C ₃-C ₁₈Poly-(1-alkene) polymkeric substance, be preferably C ₅-C ₁₂Alhpa olefin and they and C ₃Multipolymer, be C ₆-C ₈With them and C ₃Multipolymer better.The tackify material generally is can be miscible in the resin of poly-alpha-olefin polymkeric substance.The total amount of tackifying resin in the poly-alpha-olefin polymkeric substance is according to concrete purposes, in the scope of per 100 weight part poly-alpha-olefin polymkeric substance 0-150 weight part tackifying resins.Useful tackifying resin comprises by polymerization C ₅-C ₉The resin that obtains of unsaturated hydrocarbon monomer, polyterpene, synthetic polyterpene etc.These can buy based on C ₅The example of the resin of alkene fraction is WINGATCK ^TM95 and WINGATCK ^TM115 tackifying resins can obtain from Goodyear Tire and Rubber Co..Other hydrocarbon resin comprises the REGALREZ that can obtain from Hercules Chemical Inc. ^TM1078 and REGALREZ ^TM1126, and the ARKON that can obtain from Arakawa Chemical Co. ^TMP115.To concrete purposes, can add other material, comprise the linking agent of oxidation inhibitor, filler, pigment and irradiation activation.

Silicone pressure sensitive adhesive comprises two kinds of main ingredients, promptly a kind of polymkeric substance or natural gum and a kind of tackifying resin.This polymkeric substance generally is high-molecular weight polydimethylsiloxane or polydimethyl diphenyl siloxane, end at polymer chain has remaining silanol functional (SiOH), or comprises the segmented copolymer of poly-diorganosiloxane soft chain segment and terminal urea hard segment.Tackifying resin generally is three-dimensional silicate sturcture, and this structure is with trimethylsiloxy (OSiMe ₃) end-blocking, and also contain some remaining silanol functional.The example of tackifying resin comprises the Co. from General Electric, Silicone Resins Division, Waterford, the SR 545 of NY and from Shin-Etsu Silicones of America, Inc., Torrance, the MQD-32-2 of CA.At United States Patent (USP) 2,736, the production of typical silicone pressure sensitive adhesive has been described among 721 (Dexter).At United States Patent (USP) 5,214, the production of siloxane-urea block copolymer pressure sensitive adhesives has been described among 119 (people such as Leir).For specific purposes can add other material, comprise pigment, softening agent and filler.The general consumption of filler is per 100 parts of silicone pressure sensitive adhesive 0-10 part fillers.The example of operable filler comprises zinc oxide, silicon-dioxide, carbon black, pigment, metal-powder and lime carbonate.

Second component of contact adhesive composition of the present invention is that thermoplastic material maybe can be (a) thermoplastic elastomer (s), (b) the foregoing resilient material that tackifying resin is arranged, or (c) resilient material.The thermoplastic material component generally is a superpolymer, and polymkeric substance can soften during heating, recovers solid-state when being cooled to room temperature.Useful thermoplastic material is into fibre object, is immiscible in pressure sensitive adhesive component basically in use temperature, although thermoplastics can be miscible in pressure sensitive adhesive at melt processing temperature.Generally the thermoplastic material component is a 2-70% weight in contact adhesive composition, is 5-60% weight preferably, and 5-40% weight is better.And the thermoplastic material component can be a kind of thermoplastic material, or the mixture of several thermoplastic materials.

Can be used for thermoplastic material of the present invention comprises, polyolefine for example, as isotactic polyprophlene, low density or linear low density polyethylene, medium-density polyethylene, high density polyethylene(HDPE), polybutene, polyolefinic multipolymer or terpolymer, as ethylene/propene copolymer and their adulterant; Vinyl-vinyl acetate copolymer is (as the ELVAX that can obtain from Dupont Chemical Co. ^TM260), ethylene acrylic acid co polymer, ethylene methacrylic acid copolymer are (as the SURLYN that can obtain from Dupont Chemical Co. ^TM1702), polymethylmethacrylate, polystyrene, ethylene-vinyl alcohol, polyester, amorphous polyester, polymeric amide, fluorinated thermoplastic plastics, as poly(vinylidene fluoride), tetrafluoroethylene, ethylene fluoride/propylene copolymer and halogenated thermoplastics, as chlorinatedpolyethylene.Any single thermoplastics can with at least a pressure sensitive adhesive fusion.Also can use the adulterant of thermoplastic material, as long as the adulterant that makes when with at least a pressure sensitive adhesive melting mixing, produces at least two different zones in use temperature.

Thermoplastic elastomer (s) is generally at least two phases of 21 ℃ of formation, greater than 50 ℃ of temperature current downflow and show elastic performance.1995,12, further described useful thermoplastic elastomer (s) in 22 patent applications 08/578,010 that propose by the proxy.

Resilient material generally forms a phase at 21 ℃, and its second-order transition temperature is lower than 0 ℃, and shows elastic performance.The adding tackifying resin helps the fusion of pressure-sensitive component and resilient material component.1995,12, further described useful resilient material in 22 patent applications 08/577,603 that propose by the proxy.

It is better that every kind of component has similar melt viscosity.The ability that forms finely divided form is relevant with the ratio of the shear viscosity of each component under melt mix temperature.Adopt capillary rheometer near extruding the fusion condition, measure shear viscosity under the shear rate of promptly 100/ second and 175 ℃.When the component of viscosity higher existed as accessory constituent, the viscosity ratio of accessory constituent and main ingredient preferably should be less than about 20: 1, and was better less than about 10: 1.When more low viscous material existed as accessory constituent, the viscosity ratio of accessory constituent and main ingredient is preferably greater than about 1: 20, and was better greater than about 1: 10.By adding softening agent, tackifier or solvent, or, can change the melt viscosity of each component by changing mixing temperature.

The fusion fusion and coating operating period at least a component be easy to extend, form the finely divided form that fibril arrives the sheet zone that has, for example form sheet, band, fiber, spheroid etc.,, press base-material downward direction orientation in the continuous substantially of all the other polymer materialss or common successive zone.Preferably there is enough interface sticking power between pressure sensitive adhesive component and thermoplastic material component, can stands to form the shear and the tensile deformation that exist during the step, and promote to form continuous film.

If during the fusion fusion, there is not a kind of polymer materials fully to disperse, the coatings of pressure sensitive adhesive that makes is discontinuous generally, is granular texture.Suitable mixing condition, melt viscosity ratio and shear/stretching condition by adopt selecting during extruding make the thickness from fibril to the sheet zone thin as far as possible, can not take place from continuous or successive zone catastrophe leafing altogether basically.Fibril arrives the thickness in sheet zone preferably approximately less than 20 microns, and is better less than 10 microns approximately, preferably approximately less than 1 micron.

Among the present invention, adopt melt extrusion technology fusion and each component of coating.Can mix by making the equally distributed basically any method of each component.Use can provide dispersing and mixing, distribute mix or dispersing and mixing and distribution mixing bonded equipment, is in the component of fusion or soft state by melting mixing, prepares the adulterant of each component.Can adopt the method for intermittence and continuous fusion.The example of interrupter method comprises BRABENDER ^TMOr BANBURY ^TMThe interior mixing and the roller grinding.The example of continuous processing comprises that single screw rod is extruded, twin screw is extruded, disk is extruded, reciprocating type single screw rod is extruded and the single screw rod of bolt cartridge type is extruded.Continuous processing can comprise distribution member, bolt formula hybrid element and static mixing element and dispersive element, as Maddock hybrid element or Saxton hybrid element.

Behind the mixing step, remollescent or fused adulterant form the pressure sensitive adhesive coating of the fusion with different shape.Among the present invention, by relating to shear or tensile deformation or both methods, pressure sensitive adhesive component has formed successive zone basically, and the thermoplastic material component formed its character for from fibril to flaky discontinuous zone.

The method that forms comprises from film die head tractive contact adhesive composition continuously, contacts with the plastic matrix or other suitable substrates that move subsequently.Relevant continuous processing relates to the back lining materials of extruding contact adhesive composition and coextrusion from the film die head, forms the pressure sensitive adhesive band with postcooling.Other continuous forming method relates to makes the pressure sensitive adhesive adulterant directly contact with plastic matrix or other suitable substrates of rapid movement.In this method, can use the die head of the flexible die head shape of the mouth as one speaks such as reverse aperture coating mould, with use rotating rod other contact die head, the pressure sensitive adhesive adulterant is administered on the mobile base-material.After the formation, by adopting the quenching of direct method (as cooling roller or water-bath) and indirect method (as the collision of air or gas), cured pressure-sensitive adhesive agent coating.

Before or after pressure sensitive adhesive was coated on the backing, contact adhesive composition of the present invention can be crosslinked through radiation treatment.Suitable irradiation source comprises UV-light and electron beam.When adopting ultraviolet light irradiation, generally in the adhesive bleed compound, add light trigger.If exist, such light trigger is those light triggers that the technician in field of the present invention understands, can be perhaps useful to it mutually with concrete pressure sensitive adhesive.

One or more character below the advantage of the pressure sensitive adhesive of fusion of the present invention has provided.These improved properties with the thermoplastic material fusion before pressure sensitive adhesive.These character comprise:

(1) greater than the peel adhesion of only using pressure sensitive adhesive component and the shearing resistance similar to only using pressure sensitive adhesive component,

(2) greater than the shearing resistance of only using pressure sensitive adhesive component and the peel adhesion similar to only using pressure sensitive adhesive component,

(3) anisotropic peel adhesion,

(4) anisotropic shearing resistance and

(5) to any elongation up to extension at break, the tensile stress on coiled strip is vertical is than the big at least twice of coiled strip tensile stress transversely.

Observe and improved peel adhesion, than the big 20-200% of the value that pressure sensitive adhesive component is only arranged, shearing resistance does not significantly descend.This be since restricted interfacial layer from peeling off during the caused additional energy dissipation in interregional formation space.When being the thermoplastic material component, discontinuity zone observes this point.This also will depend on the type and the amount thereof of employed component.It is the 5-20% scope that the peel adhesion that improves generally occurs in thermoplastic component.For example, if use acrylic pressure-sensitive adhesive, can not show that the thermoplastic material component of the peel adhesion of raising comprises, as polystyrene, polymethylmethacrylate and amorphous polyester.Equally, show that the thermoplastic material of the peel adhesion that improves comprises, as linear low density polyethylene, new LDPE (film grade) and ethylene vinyl acetate.

Observing the shearing resistance ratio of being measured by the hold-time only has the big 25-200% of pressure sensitive adhesive component, and peel adhesion does not obviously descend.This is because thermoplastic material zone enhanced propertied, and can observe this point in the thermoplastic material scope of 5-25%.As if the type of thermoplastic material be not controlling factor.

The anisotropy peeling force is a uncommon character, promptly from PSA goods adherent surface it is peeled off required power, when along disalignment when measuring, it be worth difference.Promptly when from different directions with the PSA goods during from sur-face peeling, it shows different sticking power.When preparing pressure-sensitive adhesive article by extrusioning adhesive, elastomeric orientation preferably generally is " base-material downward direction " (or " DW "), promptly is parallel to extrusion coated direction.Generally be called " base-material horizontal direction " (or " CW ") perpendicular to extrusion coated direction.The peeling force of general parallel direction is less than 90% of higher peeling force (being the peeling force of vertical direction), preferably less than 50%, preferably less than 10%.This result is because the machine-direction oriented fibril of discontinuous phase arrives flaky form.When thermoplastic material had higher tensile strength, promptly polystyrene, polymethylmethacrylate, amorphous polyester and high density polyethylene(HDPE) when thermoplastic material is between 5-20%, were observed anisotropic peeling force.When thermoplastic material has low tensile strength, i.e. linear low density polyethylene, new LDPE (film grade) and ethylene vinyl acetate, it is in the scope of 20-40%.It is believed that the anisotropy peel adhesion is because the thermoplastic material of downward direction has been strengthened the PSA composition.

When pressure sensitive adhesive of the present invention shows the anisotropy peel adhesion, often observe anisotropic shearing resistance.In this case, the direction of higher shear intensity is generally corresponding to the direction of hanging down peel adhesion.But, do not occurring under the corresponding anisotropic peel adhesion anisotropic shearing resistance taking place.Relatively high shear strength is little by 80%, preferably little by 50%, preferably little by 10% in the shearing resistance of hanging down shear direction.

Observe can be up to the general extension of extension at break, the tensile stress on the base-material downward direction is than the big at least twice of base-material tensile stress in a lateral direction.The influence of the length-to-diameter ratio of the material type that tensile stress is selected, its concentration, discontinuity zone and the extension at break of thermoplastic material component.Observe structure of the present invention, tensile stress is in 0.69-20.7MPa (100 to 3000Psi) scope.By forming the fibrous flaky discontinuity zone that arrives on the spot, compare with the pressure-sensitive adhesive constructions of forming by the glass fibre that is placed in the pressure sensitive adhesive, can form thinner thermoplasticity fibril to sheet zone (less than 1 micron).Generally, use than the inflexible thermoplastic material and can obtain higher tensile stress, for example polystyrene, polymethylmethacrylate, amorphous polyester and high density polyethylene(HDPE).The tensile stress of high base-material downward direction and less extension at break also make contact adhesive composition of the present invention distribute performance preferably having as the transfering adhesive adhesive tape time.

Composition of the present invention, according to its concrete prescription, can utilize the anisotropic properties of some prescriptions, be used to produce various pressure-sensitive adhesive articles, pressure sensitive adhesive tape, pressure sensitive adhesive transfering belt, pressure sensitive adhesive medical adhesive tape (comprising) or directly be coated on pressure sensitive adhesive coating on the required goods such as the transdermal drug transfer device.Various pressure-sensitive adhesive articles can also utilize the contact adhesive composition that comprises at least a pressure sensitive adhesive component and at least a polymeric constituent, this polymeric constituent comprises it can being (a) a kind of thermoplastic elastomer (s), (b) a kind of foregoing resilient material that tackifying resin is arranged, or (c) a kind of resilient material that does not have tackifying resin.

Composition of the present invention also can be used for medical applications, comprises the transdermal drug transfer device.Such device relates generally in check sticking power to skin.Use for adhesion originally, this sticking power should be enough big, be not increased in time when removing can injured skin degree, or be reduced to the degree that this device can come off from skin surface in time.The transdermal drug transfer device of design can with the medicine of effective therapeutic dose by patient skin-communication or be delivered to patient's skin.The transdermal drug transfer device provides significant advantage; Different with injection, it is non-infringement; With oral different, it has been avoided at first by the metabolism of liver, and it reduces to gastrointestinal effect minimum, and stable blood levels is provided.

Various transdermal drug transfer devices are understood for people.Device known in the art comprises medicine is placed on matrix in the polymer materials of non-tackiness agent; Reservoir device, medicine are put in the liquid and by the speed control film and are delivered to skin; Medicine is placed in the medication device in tackiness agent in the binder polymer; The more complicated multi-layered devices that relates to which floor different layers, as contain medicine layer, contain vehicle layer, be used to control the layer of medicine and vehicle release rate and this device be fixed to layer on the skin.

All these devices combine tackiness agent, the peeling off wadding and protecting this device not make the backing of external contamination during use in protection this device (and removing) between the shelf lives that a kind of formula of medicine, a kind of maintenance contact with patient skin before this device is administered to skin.

Figure 11 shows that a kind of matrix means.Device 10 comprises a backing 12, contain matrix 14, the concentric binder layer 16 around matrix 14 of medicine and optional vehicle and peel off wadding 18.

Figure 12 shows that a kind of reservoir device.Device 20 comprises backing 22, contain medicine and optional vehicle liquid formulations 24, be used to control medicine and vehicle is delivered to film 25, the binder layer 26 of the speed of skin and peels off wadding 28.This binder layer also can be a concentric ring, and the concentric ring of painting with matrix means (Figure 11) is the same.

Figure 13 shows that and contain the medicine adhesive device.Device 30 comprises backing 32, contain the binder layer 37 of medicine and optional vehicle and peel off wadding 38.

Shown in Figure 14 is multi-layered devices.This device 40 comprises backing 42, contain medicine and optional vehicle binder layer 47, be used to control medicine and vehicle be delivered to skin speed second binder layer 43 and peel off wadding 48.

Figure 15 shows that second embodiment of multi-layered devices.This device 50 comprises backing 52, contain binder layer 57, film 55, second binder layer 56 of medicine and optional vehicle and peel off wadding 58.The film of selecting is used to control medicine and vehicle and is delivered to the speed of skin or provides physical stability for device.

Skin attachment power is a key request to any transdermal drug transfer device.Because useful for drug delivery is directly proportional with the contact area of skin, device must form and keep enough skin attachment power, is removed up to it.The tackiness agent that is used for skin contacting adhesive layer preferably has following character: good initial skin attachment power, i.e. viscosity; The sticking power of appropriateness during wearing; Can peel off neatly from skin; With with skin-compatible (do not stimulate and not sensitization).When tackiness agent is placed in the medicine that will use in setter and the vehicle, can keep these character extremely important.

In containing the layer of medicine and vehicle or the tackiness agent that uses in medicine and the vehicle layer that will pass through also must be compatible with medicine and vehicle.Preferably tackiness agent not can with medicine or vehicle generation chemical reaction.In many cases, medicine dissolution is in tackiness agent rather than to be dispersed in the tackiness agent also be preferably.Usually require or even be necessary for a kind of combine tackiness agent of special medicine/vehicle.

Make through the skin transfer device according to shape of products such as adhesive tape, patch, sheet, bandage or other shape well known by persons skilled in the art.General device is the patch shape that is suitable for transmitting predetermined amounts of pharmaceutical.Suitable peeling liner material package is drawn together relevant those of above-named and PSA band preparation.

Anisotropic sticking power character make pressure-sensitive adhesive article of the present invention (as adhesive tape or the sheet that has been coated with pressure sensitive adhesive) help to be used for graphic arts application (as cover band, pre-interval-zone, graphic arts film, die cutting product or the transfer literal of doing in advance, as by Satas, supra, the described graphic arts product of Chap.32).Anisotropy PSA goods of the present invention can also be used as decorating film or other structure that requires different peeling forces of diaper fixation adhesive tape, wall.

As described above, in the embodiment of pressure-sensitive adhesive article of the present invention, the type of pressure sensitive adhesive and thermoplastic material component and concentration are enough to make goods to have anisotropic peeling force.Goods with anisotropy peeling force can be used as graphic arts application of tape (comprise and cover band and pre-interval-zone in advance), and these are useful to the graphic arts works.For example, the figure of cross cutting is often taked the form of the used pattern of vinyl decal process (vinyl decal).Generally downcut the used pattern of formation decal process from being layered in the sheet of peeling off the vinyl film painted, coating adhesive on the wadding.Divest refuse or frippery, then figure is used the top layer that band application is used the used pattern of decal process of cross cutting, the used pattern of decal process is taken off and it is retained in the steady arm from peeling off wadding.Then with the used design transfer of this decal process on the target substrate that requires, and divest the graphical application band.Such figure is used band must enough chemical activities, to guarantee taking off all figure components (being the used pattern of decal process the present embodiment) from peeling off wadding, but after target substrate, still should be easy to take off in figure transfer, and should not drag down any figure from target.Reach so comprehensive usually be very difficult.Adopt pressure sensitive adhesive band of the present invention to use band, can draw,, it is administered on the target substrate, by drawing, remove figure and use band then in low sticking power direction to take off figure from wadding in the high adhesive force direction as figure.Other figure is used band and is not related to the cross cutting component, uses and has a direction that is very easy to take off but still an advantage that has is this figure, because figure can be very wide, is difficult to leave behind with common adhesive.When preparation has lowly when removing the common adhesive of power, weakened the ability that is fixed on the figure.Anisotropic pressure sensitive adhesive band of the present invention has high crystallized ability but still has the low power of removing.

The Another application of anisotropic pressure-sensitive adhesive article of the present invention is as large-area graphs or protective membrane, and this film can be adhered to the surface of using it by chemical activity, but can easily remove.Some purposes of this goods comprise the advertisement figure of truck one side, to the protective membrane of manufacturing, transportation, storage period motor vehicle lacquer painting, be used in the protective membrane of the little replicated surfaces in the graphic presentation on the optical screen.

The Another application of having utilized anisotropy stripping performance of the present invention is to produce the fixation adhesive tape of diaper.Such adhesive tape makes at low stripping force longitudinally and need not non-stick material once big volume raw material adhesive tape and can unclamp.Stock roll is being become in the process of each adhesive tape, can dicing tape, make horizontal (being the high adhesive force direction) of stock roll become the direction of delaminate on the diaper products of finishing.

It is the wall fitting film that pressure-sensitive adhesive article also has an application.Can make the wall fitting figure with anisotropic pressure-sensitive adhesive article, mode be the high adhesive force direction vertical or for the wall downward direction to prevent owing to breaking that gravity produces, special low sticking power direction is a level, and the direction of removing easily is provided, to avoid any damage to wall.

Another purposes of anisotropic pressure-sensitive adhesive article of the present invention is to cover application, in order to cover large-area base material, has used the screening agent sheet or the curtain that are adhesively fixed on base material.Screening agent sheet or curtain are used for automotive paints or polishing, and the wall of commercial and dwelling house paint, wherein paper or plastic film are bonded on body of a motor car or the wall with adhesive tape, to prevent the zone of coating splash to crested.If the screening agent sheet is quite long and heavy, can produce the constant peeling force in the direction of curtain, adhesive tape is broken away from from base material.Can prepare and have the tackiness agent that has more chemical activity, overcome the stress that the weight by curtain produces, but when paint operation is finished after, adhesive tape is very difficult be removed fully from base material.Anisotropic pressure sensitive adhesive tape of the present invention vertically has low peeling force, and high peeling force is laterally being arranged, and can be used for this application of covering.This adhesive tape can be made into laterally has high peel resistance or crystallized ability,, but low-down peeling force is only arranged or remove power at length direction because the peel stress that the weight of curtain produces to overcome, and can not damage base material when removing adhesive tape.

By well-known heat fusing coating process, use pressure sensitive adhesive and prepare pressure-sensitive adhesive article.Any suitable substrates be can use, paper and foam-back included but not limited to as fabric and glasscloth, metallized film and paper tinsel, polymeric film, nonwoven fabric, paper and coated polymeric.Polymeric film includes but not limited to polyolefine, as polypropylene, polyethylene, new LDPE (film grade), linear low density polyethylene and high density polyethylene(HDPE); Polyester is as polyethylene terephthalate; Polycarbonate; Rhodia; Polyimide is as KAPTON ^TMThe general nonwoven fabric of being made by the fiber of random orientation includes but not limited to nylon, polypropylene, vinyl-vinyl acetate copolymer, urethane, regenerated fiber etc.Foam-back includes but not limited to vinylformic acid, siloxanes, urethane, polyethylene, chloroprene rubber and polypropylene, and foam-back can be filled or not be filled.Lamellated backing also is suitable as polyethylene-aluminium film composition.

Under the Pressuresensitive Tape situation, generally use these materials by the preparation band structure, band structure comprises that one deck is coated on the pressure sensitive adhesive material on the backing.The surface applied that the PSA coating is exposed is to the surface that can break away from later on subsequently, or is applied directly on the base material of requirement.

Can prepare the transfering adhesive adhesive tape by coating composition between two waddings, this wadding all has been coated with release coating.Peel off wadding and often comprise the transparent polymer material that can see through UV-light, as polyolefine or polyester.To being used for pressure sensitive adhesive of the present invention, preferably each is peeled off wadding and at first is coated with a kind of non-stick material.

Further specify the present invention by the following examples, but these enforcement power are not construed as limiting to scope of the present invention.Test method below adopting is estimated the film surface of embodiment preparation below.

Embodiment

Further specify the present invention by the following examples, but these embodiment are not construed as limiting to scope of the present invention.Among the embodiment, unless point out, all parts, ratio and percentage ratio are weight part, weight ratio and weight percentage.Contact adhesive composition below test method below adopting characterizes among the embodiment.

Test method

Shear viscosity

Adopt high pressure capillary rheometer (RHEOGRAPH 2001, can obtain from Gotffert Co.), unless otherwise noted, measure shear viscosity at 175 ℃ with the capillary die of 1 millimeter of long 30 mm dia.With 100/ second shear velocity,, and be converted to true viscosity with the Weissenberg-Rabinovitch corrector by Poiseuille ' s Equation for Calculating apparent viscosity.

180 ° of peel adhesion tests

Wide 1.25 centimetres, long 15 centimetres pressure sensitive adhesive tape sample, test sample is to 180 ° of peel adhesion of the polypropylene screen of glass and/or slick curtain coating diaxial orientation.By roller roll-in adhesive tape with 2,1 kilograms (4.5 pounds), use four times, sample is bonded on the testing surface.Under controlled temperature and humidity condition (about 22 ℃, 40% relative humidity) aging after about 1 hour, (can be with 3M90 type slip/peeling tester from Instrumentors, Inc. obtain), unless otherwise noted, at 180 ° of peeling rates adhesive tape is tested by 30.5 cm per minute (12 inch per minute clock).

Shear strength test

(about 22 ℃, 40% relative humidity) test the shearing resistance by the set time decision on the pressure sensitive adhesive tape sample under the temperature and humidity condition of control.With the roller of 2.1 kilograms (4.5 pounds), use four 25.4 * 25.4 millimeters (1.0 * 1.0 inches) parts to be adhered on the stainless steel substrates with adhesive tape.On sample, hang 1000 grammes per square metre things.Write down this weight from the time that falls.This test stopped in the time of 10,000 minutes.

The laser light scattering test

The light scattering characteristic of test pressure sensitive adhesive tape sample.The He-Ne Lasers that to operate under 632nm wavelength and 3 millimeters big luminous points faces the plane of adhesive tape.The time of optical gate control bundle light beam exposure on sample, the scattering of light figure of generation is photographed on the Polaroid#55 film that is positioned at behind the adhesive tape sample 120 millimeters.The fibril of orientation causes scattered light intensity to become the unclear lines of thin or wide profile to the existence in sheet zone, lines and fiber or be arranged in 90 ° of orientations by the coiled strip longitudinal direction of membrane plane.There is not discrete areas or exists spherical discrete areas to produce spherical or isotropic scattering of light pattern.

Tension test

Tension test is used to obtain the stress-strain data of the pressure sensitive adhesive coating of various fusion.With being equipped with INSTRON ^TMThe INSTRON of series 9 software packages ^TMModel1122 is with the sample of pinblock speed trial wide 2.54 centimetres (1.0 inches) the thick 51-127 microns (2-5 Mill) of 102 cm per minute (40 inch per minute clock).Test sample on DW and CW direction.

The test of skin attachment power

The adhesive tape sample of 2.5 centimetres of wide 5 cm long is placed on by test people's back, carries out the test of skin attachment power.Once once oppositely depress each adhesive tape with 2 kilograms of rollers forward with the speed of about 30 cm per minute.The speed of removing according to 15 cm per minute is removed the sticking power of the required peeling force mensuration of adhesive tape to skin with 180 ° of angles.(T after initial application ₀) and use (T after 48 hours ₄₈) measure sticking power at once.Skin attachment power shows T preferably ₀Generally be about 50-100 gram (1.9-3.8N/dm), T ₄₈Be about 150-300 gram (5.8-11.5N/dm).The result of average 14 tests.

The adhering skin test that comes off

When finishing skin attachment power test in 48 hours, remove adhesive tape and check before, and press following scoring from the area in the zone of skin exfoliation (peeling off):

0: do not have macroscopic coming off

1: only come off at the edge of adhesive tape

2: have the 1-25% test area to come off

3: have the 25-50% test area to come off

4: have the 50-75% test area to come off

5: have the 75-100% test area to come off

Average 14 test-results.Surgical appliance adhesive generally has and is lower than 2.5 average score preferably.

The residual test of surgical appliance adhesive

When finishing skin attachment power test in 48 hours, visual control is positioned at the skin under the adhesive tape sample, the residual quantity of decision tackiness agent on skin surface, and it is as follows to mark:

0: do not have macroscopic residual

1: only residual at the edge of adhesive tape

2: residue covers the 1-25% test area

3: residue covers the 25-50% test area

4: residue covers the 50-75% test area

5: residue covers the 75-100% test area

Average 14 test-results.Surgical appliance adhesive generally has and is lower than 2.5 average score preferably.

Embodiment 1-17 and comparative example C1

Among the embodiment 1 and 2, at the twin screw extruder (LEISTRITZ of 34 millimeters synchronous rotations of meshing fully of diameter ^TMModel LSM34GL, can be from Leistriz, Inc. obtain) middle fusion fusion pressure sensitive adhesive of the present invention, acrylate component is (according to United States Patent (USP) RE24, the aqueous emulsion polymerization of the different monooctyl ester of 95% weight percent acrylic acid/5% weight percent acrylic acid of 906 (Ulrich) (in this incorporated by reference) preparation, shear viscosity is 150Pa-s, and dry) and thermoplastic material component ELVAX ^TM210, (vinyl-vinyl acetate copolymer, shear viscosity are 10Pa-s, can obtain from Dupont).Feed throat at forcing machine adds the thermoplastic material component, and 4 add pressure sensitive adhesive component in the district.Temperature 4 rises to 177 ℃ (100 °F-350 °F) from 38 ℃ from distinguishing 1 gradually to the district.The stacking area temperature remains on 177-191 ℃ (350 °F-375 °F).Among the embodiment 1 and 2, regulate input speed, provide pressure sensitive adhesive component and thermoplastic material component ratio to be respectively 95: 5 and 85: 15.

Under at least about 0.69MPa (100psi) pressure, twin screw extruder is discharged to 25.4 centimetres (10 inches) wide film die head (ULTRAFLEX continuously ^TM40 die heads, Model 89-12939 can be from Extrusion Dies, Inc. obtains).Die head temperature remains on 177-191 ℃ (350 °F-375 °F), and die gap is 0.5-0.8 millimeter (20-30 Mill).With the speed of 6.4 kilograms/hour (14 Pounds Per Hours), at 51 microns (2 Mill) thick biaxial orientation polyethylene glycol terephthalate's film be coated with the binder composition of input fusion between the paper substrate material of releasing agent.Remain on this film of input and base-material between the cold roller of 21 ℃ (70) with 13.7 meters/minute (45fpm) speed in temperature, form the pressure sensitive adhesive tape that the contact adhesive composition layer thickness is about 64 microns (2.5 Mills).The binder composition of some fusion can also be sent between two paper substrate material that have been coated with releasing agent, with further test adhesive layer or subsequently binder layer be transferred to different base materials.

Prepare embodiment 3,4 and 5 according to the mode identical with embodiment 1, difference is to add different thermoplastic material component ELVAX in pressure sensitive adhesive component ^TM240 (vinyl-vinyl acetate copolymer, shear viscosity are 210Pa-s), the ratio of pressure sensitive adhesive component and thermoplastic material component was respectively 95: 5,85: 15 and 70: 30.Prepare embodiment 6,7 and 8 according to the mode identical with embodiment 3,4 and 5 respectively, difference is to add different thermoplastic material component ELVAX in pressure sensitive adhesive component ^TM450 (vinyl-vinyl acetate copolymer, shear viscosity are 470Pa-s).Prepare embodiment 9,10,11 and 12 according to the mode identical with EXAMPLE l, difference is to add different thermoplastic material component ELVAX in pressure sensitive adhesive component ^TM240 (vinyl-vinyl acetate copolymer, shear viscosity are 600Pa-s), the ratio of pressure sensitive adhesive component and thermoplastic material component was respectively 95: 5,85: 15,70: 30 and 40: 60.Prepare embodiment 13,14 and 15 according to the mode identical with embodiment 3,4 and 5 respectively, difference is to add different thermoplastic material component ELVAX in pressure sensitive adhesive component ^TM660 (vinyl-vinyl acetate copolymer, shear viscosity are 730Pa-s).Prepare embodiment 16 and 17 according to the mode identical with embodiment 3 and 4 respectively, difference is to add different thermoplastic material component S URLYN in pressure sensitive adhesive component ^TM1702 (ethylene-methacrylic acid copolymer can obtain from Dupont).Prepare comparison power C1 according to the mode identical with embodiment 1, difference is only used pressure sensitive adhesive component, and does not have the thermoplastic material component to prepare pressure sensitive adhesive tape.

Measure each pressure sensitive adhesive tape sample discontinuous to basic successive component viscosity ratio and sample on the thickness of tackiness agent, and in vertical horizontal (CW) direction of (DW) and coiled strip of coiled strip, 180 ° of peel adhesion of carrying out on the polypropylene (BOPP) of 180 ° of peel adhesion test on glass, diaxial orientation are tested and shearing resistance.The results are shown in table 1.Table 1

Embodiment	Viscosity ratio	At DW/CW, to the peel adhesion (N/dm) of glass	At DW/CW, to the peel adhesion (N/dm) of BOPP	The shearing resistance of DW/CW (minute)
					?C1	????-	????39/48	????33/32	?230/190
?1	????1∶15	????43/42	????24/32	?210/230
					?2	????1∶15	????62/68	????27/30	?230/390
?3	????1.4∶1	????46/49	????27/28	?240/270
					?4	????1.4∶1	????70/65	????17/31	?370/420
?5	????1.4∶1	????70/61	????22/29	?170/650
					?6	????3.1∶1	????49/54	????29/33	?220/150
?7	????3.1∶1	????11/65	????28/40	?300/240
					?8	????3.1∶1	????1/40	????7/33	?190/130
?9	????4∶1	????47/50	????24/33	?210/290
					?10	????4∶1	????46/52	????25/36	?220/310
?11	????4∶1	????20/59	????20/23	?640/760
					?12	????4∶1	????5/11	????2/3	?120/40
?13	????4.9∶1	????39/49	????30/35	?270/200
					?14	????4.9∶1	????29/58	????25/30	?200/220
?15	????4.9∶1	????6/47	????10/21	?190/160
					?16	????-	????28/38	????27/15	?150/220
?17	????-	????56/44	????23/29	?430/340

Comparative example C1 has shown that to embodiment 17 fibril by the laser light scattering test determination is to flaky form.By the data in the table as can be known, in the acrylic pressure-sensitive adhesive component, add thermoplastic material component (ethylene vinyl acetate copolymer and ethylene methacrylic acid copolymer) and improved peel adhesion, the embodiment 1-4,8,9 of contrast tackiness agent (C1), 12 and 16 shearing resistance glass and/or Biaially oriented polypropylene.It is uncommon improving peel adhesion and shearing resistance simultaneously, because most of rubber/plastics pressure sensitive adhesive can only these two performances of compromise selection.Begin to occur the raising of these performances in about 5% thermoplastic material concentration.Raising to the embodiment peel adhesion that contains vinyl-vinyl acetate copolymer is the most obvious.The embodiment shearing resistance that contains ethylene methacrylic acid copolymer improves the most obvious.Embodiment 5-7,10-11 and 13-15 confirm to obtain the significant anisotropism peel adhesion, and promptly the horizontal peel adhesion of coiled strip is obviously greater than the peel adhesion of coiled strip longitudinal direction.

Embodiment 18-22

According to embodiment 3,4 and 5 preparation embodiment 18,19 and 20, difference is to add different thermoplastic material component TENIFE in pressure sensitive adhesive component respectively ^TM1550P (new LDPE (film grade), shear viscosity are 675Pa-s, can obtain from Eastman Kodak).According to embodiment 1 and 2 preparation embodiment 21 and 22, difference is to add different thermoplastic material component DOWLEX in pressure sensitive adhesive component respectively ^TM2517 (linear low density polyethylene, shear viscosity are 280Pa-s, can obtain from Dow Chemical).

Measure each pressure sensitive adhesive tape sample discontinuous to basic successive component viscosity ratio and sample on the thickness of tackiness agent, and in vertical horizontal (CW) direction of (DW) and coiled strip of coiled strip, 180 ° of peel adhesion of carrying out on the polypropylene (BOPP) of 180 ° of peel adhesion test on glass, diaxial orientation are tested and shearing resistance.The result lists in table 2 with the result of comparative example C1.

Table 2

Embodiment	Viscosity ratio	At DW/CW, to the peel adhesion (N/dm) of glass	At DW/CW, to the peel adhesion (N/dm) of BOPP	The shearing resistance of DW/CW (minute)
C1	-	36／43	30／29	230／190
18	4.5∶1	47／45	29／33	200／210
19	4.5∶1	37／59	24／38	180／80
20	4.5∶1	9／23	5／20	10／50
21	1.9∶1	24／49	31／38	270／350
22	1.9∶1	91／82	35／42	340／320

Embodiment 18-22 has shown the fibril form by the laser light scattering test determination.By the data in the table 2 as can be known, the thermoplastic material component of adding new LDPE (film grade) and linear low density polyethylene has improved the peel adhesion to glass and/or Biaially oriented polypropylene in the acrylic pressure-sensitive adhesive component, to embodiment 19,21 and 22, the shearing resistance of contrast tackiness agent (C1).It is anisotropy that embodiment 20-21 shows three kinds of performances.

Embodiment 23-29 and comparative example C2

According to embodiment 1 preparation embodiment 23-29, difference is, uses the pressure sensitive adhesive layer of different thickness, different thermoplastic material component, different pressure sensitive adhesive component and the ratio of thermoplastic material component.In embodiment 23-29 and comparative example C2, the pressure sensitive adhesive layer thickness is about 90 microns.Among the embodiment 23 and 24, the thermoplastic material component that adds in pressure sensitive adhesive component is FINA ^TMIts ratio of 3374X (polypropylene, shear viscosity are 700Pa-s, can obtain from Fina Oil and Chemical) is respectively 90: 10 and 85: 15.According to embodiment 23 and 24 preparation embodiment 25 and 26, difference is that the thermoplastic material component is ESCORENE respectively ^TM3860 (polypropylene can obtain from Exxon).Embodiment 27 uses DURAFLEX ^TM0200 (polybutene, shear viscosity are 682Pa-s, can obtain from Shell Chemical), ratio is 85: 15.Embodiment 28 and 29 uses PRIMACORE ^TM1430 (ethylene acrylate copolymer, shear viscosity are 630Pa-s, can obtain from Dow Chemical), its ratio was respectively 92: 18 and 87: 13.Comparative example C2 is for only there being pressure sensitive adhesive component in the contact adhesive composition layer.

Measure the discontinuous viscosity ratio of each pressure sensitive adhesive tape sample to basic successive component, and in vertical horizontal (CW) direction of (DW) and coiled strip of coiled strip, 180 ° of peel adhesion of carrying out on the polypropylene (BOPP) of 180 ° of peel adhesion test on glass, diaxial orientation are tested and shearing resistance.The result lists in table 3 with the result of comparative example C2.

Table 3

Embodiment	Viscosity ratio	At DW/CW, to the peel adhesion (N/dm) of glass	At DW/CW, to the peel adhesion (N/dm) of BOPP	The shearing resistance of DW/CW (minute)
					????C2	??????-	????52/50	????39/37	????100/130
????23	????4.7∶1	????64/59	????39/38	????110/180
					????24	????4.7∶1	????56/56	????30/34	????150/240
????25	??????-	????69/74	????50/40	????80/150
					????26	??????-	????62/58	????40/46	????250/280
????27	????4.5∶1	????68/66	????36/42	????130/180
					????28	????4.2∶1	????6868	????3432	????120150
????29	????4.2∶1	????62/55	????33/40	????110/150

Embodiment 23-29 has shown the fibril form by the laser light scattering test determination.By the data in the table 3 as can be known, in the acrylic pressure-sensitive adhesive component, add various polypropylene thermoplastic material components and improved to the polyacrylic peel adhesion of glass diaxial orientation and/or to embodiment 23-29 the shearing resistance of contrast tackiness agent (C2).Embodiment 23-27 shows that in three kinds of performances one or more be anisotropy.

Embodiment 30-33

According to embodiment 1 preparation embodiment 30-33, difference is, the temperature in district 4 is 204 ℃ (400 °F), and the ratio of using different thermoplastic material components, pressure sensitive adhesive component and thermoplastic material component is 85: 15.In embodiment 30 and 31, the thermoplastic material component is respectively Kodar ^TM6763 (amorphous polyester, shear viscosity are 3150Pa-s, can obtain from Eastman Chemical Products) and Styron ^TM615 (polystyrene, shear viscosity are 650Pa-s, can obtain from Dow Chemical).In embodiment 32 and 33, the thermoplastic material component is respectively Plexiglas ^TMVM100 (polymethylmethacrylate, shear viscosity are 1900Pa-s, can obtain from Ato Hass) and PETROTHENE ^TM3150B (high density polyethylene(HDPE), shear viscosity are 340Pa-s, can obtain from Quantum Chemical).The pressure sensitive adhesive layer thickness is 64 microns (2.5 Mills).

Measure discontinuous viscosity ratio to basic successive component, in vertical horizontal (CW) direction of (DW) and coiled strip of coiled strip, 180 ° of peel adhesion of carrying out on the polypropylene (BOPP) of 180 ° of peel adhesion test on glass, diaxial orientation are tested and shearing resistance.The result lists in table 4 with the result of comparative example C1.

Table 4

Embodiment	Viscosity ratio	At DW/CW, to the peel adhesion (N/dm) of glass	At DW/CW, to the peel adhesion (N/dm) of BOPP	The shearing resistance of DW/CW (minute)
C1	-	39／48	33／32	230／190
30	211	21／50	33／45	70／90
31	4.31	9／46	3／40	90／140
32	131	39／39	41／38	60／90
33	2.31	69／64	43／40	90／140

Embodiment 30-33 has shown the fibril form by the laser light scattering test determination.By the data in the table 4 as can be known, in the acrylic pressure-sensitive adhesive component, add various other thermoplastic material components and cause anisotropic peel adhesion and/or anisotropic shearing resistance glass and/or Biaially oriented polypropylene.

Adopt tension test and elongation test, also tested the tension force and the elongation performance of the pressure sensitive adhesive layer of embodiment 30-33 and comparative example C1.Fig. 1 draws the base-material downward direction (DW) of embodiment 31 and the stress-strain curve of base-material horizontal direction (CW).The corresponding yielding stress of embodiment 30-33 coiled strip longitudinal direction is respectively 3.5MPa (550 PSI), 20.7 MPa (3000 PSI), 2.2MPa (317 PSI) and 6.3 MPa (915 PSI).Embodiment 30-33 does not have yielding stress at the coiled strip horizontal direction, but is elasticity in nature.Comparative example C1 and embodiment 30-33 are respectively 1143%, 1125%, 650%, 962% and 911% at the extension at break of coiled strip longitudinal direction.Comparative example C1 and embodiment 30-33 are respectively 845%, 1638%, 1775%, 1970% and 1797% at the extension at break of coiled strip horizontal direction.

Owing to added in acrylic pressure-sensitive adhesive than the inflexible thermoplastic polymer, the stress of coiled strip longitudinal direction significantly improves, and extension at break reduces, and the extension at break of coiled strip horizontal direction increases.When only using pressure sensitive adhesive, will cause the fracture of cleaner pressure sensitive adhesive as the transfering adhesive adhesive tape.

Embodiment 34-35 and comparative example C3-C4

According to embodiment 33 preparation embodiment 34-35, difference is to use different pressure sensitive adhesive component and thermoplastic material component.Among the embodiment 34, pressure sensitive adhesive is similar to embodiment 33, and difference is that 0.3 part of acryloyl-oxy benzophenone is arranged, and thermoplastic material is ELVAX ^TM260.Among the embodiment 35, pressure sensitive adhesive is HRJ ^TM4326 (2-EHA, shear viscosity are 10Pa-s, can obtain from SchenectedyInternational), thermoplastic material is ELVAX ^TM240.According to the pressure sensitive adhesive tape of embodiment 34 and 35 preparation comparative example C3 and C4, difference is not have the thermoplastic material component.

Measure the discontinuous viscosity ratio of each pressure sensitive adhesive tape to basic successive component, and in vertical following horizontal (CW) direction of (DW) and coiled strip of coiled strip, 180 ° of peel adhesion of carrying out on the polypropylene (BOPP) of 180 ° of peel adhesion test on glass, diaxial orientation are tested and shearing resistance.The results are shown in table 5.

Table 5

Embodiment	Viscosity ratio	At DW/CW, to the peel adhesion (N/dm) of glass	At DW/CW, to the peel adhesion (N/dm) of BOPP	The shearing resistance of DW/CW (minute)
C3	-	51／50	44／43	80／90
34	41	64／73	45／41	100／150
C4	-	61／59	42／43	8580／6560
35	121	46／83	43／32	5640／5890

Embodiment 34-35 has shown the fibril form by the laser light scattering test determination.By the data in the table 5 as can be known, in different acrylic pressure-sensitive adhesives, add the anisotropic peel adhesion that the thermoplastic material component causes 35 pairs of glass of embodiment, embodiment 34 is caused improving peeling force to glass.

Embodiment 36-42 and comparative example C5-C6

According to embodiment 1 preparation embodiment 36-42, difference is by the different pressure sensitive adhesives and different thermoplastic material components of ratio use of different pressure sensitive adhesive component and thermoplastic material component, to change the thickness of contact adhesive composition.In addition, the pressure sensitive adhesive of some embodiment contains the tackify material.The pressure sensitive adhesive that uses among embodiment 36-42 and the comparative example C5-C6 is the acrylic pressure-sensitive adhesive of suspension polymerization, replaces the tackiness agent of the aqueous emulsion polymerization of use among the embodiment 1.According to United States Patent (USP) 4,833, following manner among 179 people such as () Young prepares the pressure sensitive adhesive of suspension polymerization: add 750 gram deionized waters in two liters of shuntings (split) reactor of the heating mantles that has been equipped with stainless steel agitator that condenser, thermowell, nitrogen inlet, motor drive and band temperature control, add 2.5 gram zinc oxide and 0.75 therein and restrain wetting ability silicon-dioxide (CAB-O-SIL ^TMEH-5 can obtain from Cabot Corp), and be heated to 55 ℃, feed nitrogen simultaneously and thoroughly disperse up to zinc oxide and silicon-dioxide.At this moment, with 480 gram Isooctyl acrylate monomers, 20 gram methacrylic acids, 2.5 gram initiator (VAZO ^TM64, can obtain from Dupont Co.) and 0.5 gram isooctyl mercaptoacetate chain-transfer agent mix.The solution that initiator and chain-transfer agent are arranged that makes is added in the initial water mixture, keeps vigorous stirring (700rpm) simultaneously, reach well suspended.Feed nitrogen and reacted at least 6 hours, monitoring reaction makes temperature of reaction keep below 70 ℃ during this period.The pressure sensitive adhesive that collection makes also is dried at least 90% weight solid.Among the embodiment 36-39, the thermoplastic material component is Styron ^TM615, the ratio of pressure sensitive adhesive and thermoplastic 6 materials is respectively 95: 5,90: 10 and 80: 20.Prepare the pressure sensitive adhesive tape of embodiment 40-42 respectively according to embodiment 36, difference is that pressure sensitive adhesive also contains aliphatic series/aromatics C9 tackify material ESCOREZ ^TM2393 (can obtain) from Exxon, the ratio of pressure sensitive adhesive and tackify material is respectively 76: 19,76: 19 and 64: 16, the thickness of contact adhesive composition is respectively about 46 microns, 30 microns and 33 microns.According to embodiment 36 preparation comparative example C5 and C6, difference is that pressure sensitive adhesive component is only arranged in contact adhesive composition.

Measure the thickness of tackiness agent on each pressure sensitive adhesive tape sample, and in vertical horizontal (CW) direction of (DW) and coiled strip of coiled strip, 180 ° of peel adhesion of carrying out on the polypropylene (BOPP) of 180 ° of peel adhesion test on glass, diaxial orientation are tested and shearing resistance.The results are shown in table 6.

Table 6

Embodiment	Thickness (micron)	At DW/CW, to the peel adhesion (N/dm) of glass	At DW/CW, to the peel adhesion (N/dm) of BOPP	The shearing resistance of DW/CW (minute)
					?C5	?46	????46/42	????24/26	?120/200
?C6	?33	????45/40	????23/23	?180/210
					?36	?46	????55/52	????6/24	?340/460
?37	?46	????22/56	????6/29	?290/390
					?38	?28	????21/54	????2/24	?240/390
?39	?46	????3/51	????2/19	?410/600
					?40	?46	????75/75	????11/17	?370/420
?41	?30	????58/71	????10/14	?440/700
					?42	?33	????44/63	????36/62	?360/430

Embodiment 36-42 has shown the fibril form by the laser light scattering test determination.By the data in the table 6 as can be known, in different acrylic pressure-sensitive adhesives, add the thermoplastic material component and cause anisotropic peel adhesion and anisotropic shearing resistance glass and/or Biaially oriented polypropylene.Shown in comparative example C5 and C6, in trial stretch, the performance of pressure sensitive adhesive is not obviously to depend on thickness.In pressure sensitive adhesive component, add the tackify material, make the higher and reduction anisotropic properties of peel adhesion value.

Embodiment 43-46 and comparative example C7-C9

At United States Patent (USP) 5,539, the mixing device of the synthetic and natural rubber pressure sensitive adhesive of the preparation of describing in 033 and apparatus for coating are in this incorporated by reference.Among the embodiment 43 and 44, fusion fusion synthetic rubber NATSYN in the twin screw extruder (Model ZSK 30 can obtain from Werner-Pfleiderer, and its length-to-diameter ratio is 47: 1) of synchronous rotation of the engagement fully of 30 millimeters of diameters ^TM2210 (synthetic polyisoprenes, shear viscosity are 1500Pa-s, can obtain from Goodyear), tackifier EXCOREZ ^TM1310LC and softening agent, mineral oil and thermoplastic material component S tyron ^TM615.Elastomerics and thermoplastic polymer are all sent into 1 district (barrel 1) of forcing machine.Tackifier are separately sent into 2 districts (barrel 6-10%) and 3 districts (barrel 8-90%).Softening agent is sent into barrel 10.Be increased to 204 ℃ from 1 district to 5 district temperature gradually from 60 ℃.The stacking area temperature remains on 170 ℃ (350 °F).Screw speed is 200 rev/mins.Regulate input speed, synthetic rubber and tackifier and softening agent ratio are 61: 32: 7 in the pressure sensitive adhesive component that provides, to embodiment 43 and 44, the ratio of pressure sensitive adhesive component and thermoplastic material component was respectively 90: 10 and 80: 20 in the contact adhesive composition that provides.

Contact die head with the band rotating rod is expressed into this adulterant on the polyethylene terephthalate film of 51 microns (2 Mill) thick diaxial orientation, is formed with the pressure sensitive adhesive tape of the pressure sensitive adhesive layer of 38 micron thickness.This film moves with 9 meters/minute (30fpm).Prepare embodiment 45-46 according to embodiment 43-44 respectively, difference uses natural rubber (CV-60) to replace synthetic rubber.According to embodiment 43 and 45 preparation comparative example C7-C9, difference is not add the thermoplastic material component respectively.Comparative example C8 is dissolved in embodiment 44 in the toluene, and is coated on the PET film of 51 microns (2 Mills).

Measure the thickness of tackiness agent on each pressure sensitive adhesive tape sample, and in vertical horizontal (CW) direction of (DW) and coiled strip of coiled strip, 180 ° of peel adhesion of carrying out on the polypropylene (BOPP) of 180 ° of peel adhesion test on glass, diaxial orientation are tested and shearing resistance.The results are shown in table 7.

Table 7

Embodiment	At DW/CW, to the peel adhesion (N/dm) of glass	At DW/CW, to the peel adhesion (N/dm) of BOPP	The shearing resistance of DW/CW (minute)
	C7	26／21	34／35	50／50
43	9／18	20／26	60／40
44	1／20	7／28	200／800
C9	7／4	13／14	4480／500
45	0／11	11／20	420／620
46	0／8	4／20	1300／1400
C8	18／20	-	60／70

Embodiment 43-46 has shown the fibril form by the laser light scattering test determination, and has drawn embodiment 44 and 46 in Fig. 5 and 10 respectively.Low temperature fracture (cryo-fracture) sem analysis by the painted sample of perosmic anhydride has also been determined this point, and embodiment 44 and 46 is plotted in respectively among Fig. 3-4 and Fig. 8-9.By the data in the table 7 as can be known, in natural or synthetic rubber, add the thermoplastic material component, cause anisotropic peel adhesion glass and/or Biaially oriented polypropylene.Also observe anisotropic shearing resistance in addition.Fig. 6 and 7 draws the globosity of comparative example C8.This globosity is compared with composition of the present invention, shows lower shearing resistance and isotropic peel adhesion.

Embodiment 47-50 and comparative example C10-C11

Prepare embodiment 47-50 and comparative example C10-C11 according to embodiment 43-46 and comparative example C7 and C9 respectively, difference be subsequently they through electron beam irradiation.Use ELECTROCURTAIN ^TMModel CB-175 (can be from Energy Sciences Incorporated, Wilmington, MA obtains) under the 125kV acceleration voltage, make each adhesive tape sample through electron beam irradiation.Carry out irradiation in inert atmosphere, the dosage of calculating is 4.0Mrads.

In vertical horizontal (CW) direction of (DW) and coiled strip of coiled strip, 180 ° of peel adhesion of carrying out on the polypropylene (BOPP) of 180 ° of peel adhesion test on glass, diaxial orientation are tested and shearing resistance.The results are shown in table 8.

Table 8

Embodiment	At DW/CW, to the peel adhesion (N/dm) of glass	At DW/CW, to the peel adhesion (N/dm) of BOPP	The shearing resistance of DW/CW (minute)
C10	21／20	23／26	6580／3870
47	12／21	16／28	2370／2860
48	2／16	5／23	2040／4470
C11	4／3	15／16	4060／4890
49	1／13	5／20	3390／4500
50	0／3	1／13	3170／31400

Embodiment 47-50 has also shown the fibril form by the laser light scattering test determination.Low temperature fracture sem analysis by the painted sample of perosmic anhydride has also been determined this point.By the data in the table 8 as can be known, the crosslinked general shearing resistance that improved subsequently reduces peel adhesion, but fails obviously to change anisotropic properties.

Embodiment 51 and comparative example C12

In embodiment 51 and comparative example C12, prepare pressure sensitive adhesive tape according to embodiment 37 and comparative example C5, difference is that the pressure sensitive adhesive layer thickness is 58 microns, and uses different base materials.This base material is a kind of not sorption, and promptly the braiding backing of ventilation property has 180 * 48 tabby acetic ester taffeta cloth on it, warp direction is 75 dawn fibers, is 150 dawn fibers at weft direction, can be from Milliken and Co., Spartanburg, GA obtains.

Using T ₀Back and use 48 hours T ₄₈After, test the skin attachment power of pressure sensitive adhesive tape at once, the coming off and 48 hours residual in skin adherence of 48 hours skin adherence of test in DW and CW direction.The results are shown in table 9.

Table 9

	Embodiment 51	Comparative example C12
T 0-DW(N／dm)	25	81
T 0-CW(N／dm)	43	74
T 48-DW(N／dm)	149	265
T 48-CW(N／dm)	199	264
T 48Come off-DW	0.1	0.1
T 48Come off-CW	0.1	0.4
T 48Residual-DW	0.6	1.1
T 48Residual-CW	0.6	1.1

By the data of table 9 as can be known, the pressure sensitive adhesive tape of embodiment 51 is to T ₀, T ₄₈Skin attachment power, have the anisotropy stripping performance, and be subjected to the control of the appropriate fusion of acryloid cement component and thermoplastic component.Therefore, when from a direction tractive, be easy to take off adhesive tape, but have good crystallized ability from skin.

Embodiment 52-57 and comparative example C13-C14

Tackiness agent of the present invention can be controlled the speed that discharges medicine by the program shown in the following demonstration from multilayer transdermal drug transfer device.According to embodiment 30,32,33,34,37 and 42 and the tackiness agent of the speed control used in the test patch of embodiment 52-57 and comparative example C13-C14 of comparative example C13-C14 preparation, difference is that every kind of tackiness agent is administered on the interleaving paper respectively.

Each the test patch form by 4 layers: backing, contain medicine first binder layer, second binder layer of speed control is provided and peels off wadding.Acrylic binder multipolymer (57.3/39/3.5 w/w/w Isooctyl acrylate monomer/vinylformic acid 2-hydroxy methacrylate/ELVACITE ^TMThe 50% solid polymethylmethacrylate big monomer of (ICI acrylic acid or the like) 1020 in ethyl acetate) and phenylethyl barbituric acid provide a uniform formulation for coating material in conjunction with mixing then.This prescription is coated on a backing (1109 SCOTCHPAK ^TMTan, the polyester film lamination can obtain from 3M company), then 43 ℃ of dryings 15 minutes.The coating that makes contains the phenylethyl barbituric acid of 5% weight, and thickness is 5 Mills (127 microns).The surface that to expose is added to and is stated from one and peels off on the binder layer of speed control of the present invention of wadding.Cross cutting test patch (circle, 5 centimetres from the lamination that makes ²).

For preventing that medicine from discharging at the patch edge, make each test patch tackiness agent veneer concentric arrangement.With tackiness agent veneer (circle, 25 centimetres ², at the thick polyisobutene layer in 1 Mill that is coated with on the backing (25 microns)) be laminated on the backing of test patch, make patch and veneer concentric arrangement.Take off and peel off wadding from the test patch.With (25 centimetres of circular veneers ², 22 millimeters of internal diameters, the thick polyisobutene layer in 1 Mill that on backing, is coated with (25 microns)) center facing to the test patch/veneer stacked, stacked together adhesive surface then, along the test patch around sealing the margin.To peel off wadding and put back on the test patch, then the whole assembly of cross cutting (circle, 12.5 centimetres ²), make the test patch concentric.Assembly is placed on heat seal in the paper tinsel bag, and makes its balance 8 days.

From bag, take out assembly then and be fixed in an end of sheet glass, the backing of assembly is directly contacted with double coated adhesive tape with double coated adhesive tape.Take off and peel off wadding from the test patch.This glass carrying tablet is suspended in the 120 milliliters high shape glass pots, and glass pot is equipped with magnetic stirring apparatus.With 6 liters of hplc grade waters; 2.2835 the gram sodium phosphate, a hydration monobasic salt; 9.7538 the gram sodium phosphate, seven hydration binary salts; Mix the preparation mold release solution with 46.4502 gram sodium-chlor.100 milliliters of parts of 32 ℃ of mold release solution are added in this jar.To test patch is immersed in this mold release solution fully.Add a cover on jar, place temperature to be controlled at 32 ℃ indoor then.Stir this mold release solution in the whole test.

In specific time point (1 hour, 6.5 hours, 24 hours, 72 hours, 168 hours and 336 hours), remove lower cover, take out 1.0 milliliters of demoulding solution examples, be placed in the HPLC sample hose.With RPLC (Waters LCl Module Plus; Post: the Supelcosil LC-ABZ of 4.6 millimeters internal diameters of 15 cm x, 5 micron granularities; Moving phase: 25mM potassiumphosphate monobasic salt buffer/25% acetonitrile v/v of 75%; Flow velocity: 2.0 ml/min; Detector: uv is at the 254nm of 0.005AUFS; Operating time: 10 minutes; Injection volume: phenylethyl barbituric acid content in the quantitative assay sample 20 microlitres).

The percentage ratio that equation can obtain to discharge below adopting: $R_i=\frac{[C_{i}x(100-(I-1))]+\underset{a=1}{\overset{i}{\mathrm{\Σ}}}{C}_{a-1}]}{(T.C.\mathrm{xS}.A.)}\×100$

Wherein:

R _iThe percentage ratio of=the phenylethyl barbituric acid that discharges in the time " i "

The ordinal number of i=time point (value: 1,2,3 ... n)

C _i=analyze at the HPLC of time point i sample concentration (mcg/ml)

C ₀=0

The theoretical content of T.C.=phenylethyl barbituric acid, microgram/centimetre ²

The surface-area of S.A.=test patch, centimetre ²

Following table has provided the thickness of tackiness agent of control speed and the accumulative total percentage ratio that discharges at each time point.Each value is the mean value of four different patch measured values.

Table 10

Phenylethyl barbituric acid release rate (percentage ratio)
								Embodiment	Thickness	1 hour	6.5 hour	24 hours	72 hours	168 hours	336 hours
????52	?63.5	????3	????13	????36	????77	????96	????100
								????53	?63.5	????4	????12	????36	????76	????95	????100
????54	?63.5	????3	????9	????29	????66	????91	????99
								????55	?127	????3	????9	????21	????51	????83	????97
????C13	?63.5	????4	????15	????41	????81	????97	????100
								????56	?45.7	????3	????9	????29	????63	????90	????99
????57	?45.7	????1	????5	????13	????33	????61	????84
								????C14	?45.7	????4	????11	????36	????73	????93	????100

The velocity of diffusion of medicine can change by adding the another kind of thermoplastic material component that is immiscible in pressure sensitive adhesive basically, and wherein accessory constituent forms and has the discontinuity zone of fibril to sheet structure.This has increased the difference absorption and the desorption of two polymer areas that have the zigzag path that causes during the binder layer that forms control speed.

Embodiment 58 and comparative example C15-C17

The tackiness agent that the present invention contains thermoplastic elastomer component can be controlled the speed that discharges medicine by the program shown in the following demonstration from multilayer transdermal drug transfer device.In embodiment 58, the acrylic pressure-sensitive adhesive component of embodiment 36 described aqueous suspension polymerizations and thermoplastic elastomer binder ingredients are (by the segmented copolymer KRATON of 50 parts of thermoplastic elastomers of fusion ^TMD1107P, 1 part of oxidation inhibitor IRGANOX ^TM1010 and 50 parts of tackifying resin ESCOREZ ^TM1310LC and prepare) fusion fusion in the twin screw extruder of rotation synchronously (ModelZSK30 has the barrel of 30 millimeters of diameters, and length-to-diameter ratio is 37: 1), acryloid cement and thermoplastic elastomer tackiness agent standard are 50: 50.Thermoplastic elastomeric block copolymers is sent into 1 district, and tackifying resin is in 2 districts, and acrylic pressure-sensitive adhesive is in 3 districts.Temperature remains between 249-165 ℃.The contact adhesive composition that makes is administered on the interleaving paper, and making binder layer thickness is 51 microns.

In comparative example C15, only the acryloid cement with embodiment 58 prepares pressure sensitive adhesive.Among the comparative example C16, by following preparation pressure sensitive adhesive.The acrylic binder of embodiment 36 is dissolved in 90/10 heptane/isopropanol mixture, and solid is 20%.With thermoplastic elastomer Kratorn ^TM1107 and tackifier ESCOREZ ^TM50/50 mixture of 1310LC is dissolved in toluene with 50% solid.

An amount of acrylic binder and kraton adhesive bleed compound are mixed the thermoplastic elastomer that preparation ratio is acrylate/tackify of 50/50.

Pressure sensitive composite in the blade coating solvent is also dry.Dried coat-thickness is 51 microns (2 Mills).Drying conditions is 43 ℃ (110) 5 minutes, 85 ℃ (185) 2 minutes, 107 ℃ (225) 2 minutes.

In comparative example C17, only the thermoplastic elastomer component with the tackify of embodiment 58 prepares pressure sensitive adhesive.

Each the test patch form by 4 layers: backing, contain medicine first binder layer, second binder layer of control speed is provided and peels off wadding.Acrylic binder multipolymer (59/39/2 w/w/w Isooctyl acrylate monomer/vinylformic acid 2-hydroxy methacrylate/ELVACITE ^TM(ICI acrylic acid or the like) 1020 be the big monomer of 51.9% solid polymethylmethacrylate in 95/5 ethyl acetate/Virahol) and phenylethyl barbituric acid provide a uniform formulation for coating material in conjunction with mixing then.This prescription is coated on a backing (1109 SCOTCHPAK ^TMTan, the polyester film lamination can obtain from 3M company) on, then 43 ℃ of dryings 15 minutes.The coating that makes contains the phenylethyl barbituric acid of 8% weight, and thickness is 15 Mills (328 microns).The upper layer that will expose is laminated to and is stated from one and peels off on the binder layer of the thick control speed in 2 Mills (51 microns) of wadding.Cross cutting test patch (circle, 5 centimetres from the sandwich that makes ²).

For preventing that medicine from discharging at the patch edge, make each test patch be equipped with a tackiness agent veneer.With tackiness agent veneer (circle, 25 centimetres ², be laminated to layer by layer at the thick polyisobutene in 1 Mill that is coated with on the backing (25 microns) on the backing of test patch, make patch and veneer concentric arrangement.Take off and peel off wadding from the test patch.With (25 centimetres of circular veneers ², 22 millimeters of internal diameters are at the thick polyisobutene layer in 1 Mill (25 microns) of backing coating) the center facing to stacked at test patch/veneer, adhesive surface is stacked together then, and the sealing of the surrounding edge of test patch is provided.To peel off wadding and put back to the test patch, then the whole assembly of cross cutting (circle, 12.5 centimetres ²), make the test patch placed in the middle.Assembly is placed on heat seal in the paper tinsel bag, and makes its balance 8 days.

From bag, take out assembly then and be fixed in an end of sheet glass, the backing of assembly is directly contacted with double coated adhesive tape with double coated adhesive tape.Take off and peel off wadding from the test patch.This glass carrying tablet is suspended in the 120 milliliters high shape glass pots, and glass pot is equipped with magnetic stirring apparatus.With 6 liters of hplc grade waters; 2.2835 the gram sodium phosphate, a hydration monobasic salt; 9.7538 the gram sodium phosphate, seven hydration binary salts; With the 46.4502 gram sodium-chlor preparation mold release solution that combine.100 milliliters of parts of 32 ℃ of mold release solution are added in this jar.To test that patch is intact to be immersed in this mold release solution fully.Add a cover on jar, place temperature to be controlled at 32 ℃ indoor then.Stir this mold release solution in the whole test.

In specific time point (1 hour, 4 hours, 8 hours, 24 hours, 97.5 hours, 168 hours, 264 hours and 336 hours), remove lower cover, take out 1.0 milliliters of demoulding solution examples, be placed in the HPLC sample hose.With RPLC (Waters LC1 Module Plus; Post: the Supelcosil LC-ABZ of 4.6 millimeters internal diameters of 15 cm x, 5 micron granularities; Moving phase: 25mM potassiumphosphate monobasic salt buffer/25% acetonitrile v/v of 75%; Flow velocity: 2.0 ml/min; Detector: uv is at the 254nm of 0.005AUFS; Operating time: 10 minutes; Injection volume: phenylethyl barbituric acid content in the quantitative assay sample 20 microlitres).

The percentage ratio that equation can obtain to discharge below adopting: $R_i=\frac{\left[C_{i}x(100-(I-1))\right]+\underset{a=1}{\overset{i}{\mathrm{\Σ}}}{C}_{a-1}]}{(T.C.\mathrm{xS}.A.)}\×100$

Wherein:

R _iThe percentage ratio of=the phenylethyl barbituric acid that discharges from sample in the time " i "

The ordinal number of i=time point (value: 1,2,3 ... n)

C _i=analyze at the HPLC of time point i sample concentration (mcg/ml)

C ₀=0

The theoretical content of T.C.=phenylethyl barbituric acid, microgram/centimetre ²

The surface-area of S.A.=test patch, centimetre ²

Following table has provided the tackiness agent of control speed and the percentage ratio of the accumulative total that discharges at each time point.Each value is the mean values of four tests of difference patch measured values.

Table 11

Benzene is than crust appropriate release rate (percentage ratio)
									Embodiment	1 hour	8 hours	24 hours	49 hours	97.5 hour	168 hours	264 hours	336 hours
?C15	?1	?3	?9	?16	?27	?41	?56	?64
									?58	?0	?0	?1	?1	?2	?4	?6	?7
?C16	?0	?1	?2	?3	?6	?11	?18	?22
									?C17	?0	?0	?0	?0	?1	?1	?2	?2

The velocity of diffusion of medicine can change by adding the another kind of thermoplastic material component that is immiscible in pressure sensitive adhesive basically, and wherein accessory constituent forms and has the discontinuity zone of fibril to sheet structure.By with embodiment 58 and comparative example C16 more as can be known, fibril adsorbs and desorption to sheet structure has increased by two polymer areas with the zigzag path that causes during the binder layer of formation control speed difference.

Embodiment 60

Among the embodiment 60, according to being similar to United States Patent (USP) 5,539, embodiment 19 described methods in 033, (Model ZSK-30 can be from Wemer ﹠amp at the twin screw extruder that meshes coaxial rotation fully of 30 millimeters of diameters; Pfleiderer Corp., Ramsey, NJ obtains, its length-to-diameter ratio is 36: 1) in fusion be blended in the pressure sensitive adhesive component described in the embodiment 36.Screw configuration that uses and United States Patent (USP) 5,539,033 shown in Figure 4 identical.Add elastomeric polymer NATSYN in 1 district ^TM2210.Add acrylic pressure-sensitive adhesive in 9 districts.The ratio of elastomerics and acrylic pressure-sensitive adhesive is 50: 50.Screw speed is 475rpm.Inject air in 3 districts and maintain the temperature at 133 ℃, to reduce elastomeric molecular weight so that its better heat fusing handle.Die head temperature is 154 ℃.Pressure sensitive adhesive is administered to on 9.1 meters/minute mobile thick 30 microns polyethylene terephthalate films with the layer of 42 micron thickness.This pressure sensitive adhesive layer is non-grain basically, and sense of touch is clamminess, and is measured by light scattering test and is shown as fibrillar structure.

Concerning the technician in field of the present invention, various modifications and changes clearly of the present invention do not exceed scope and spirit of the present invention, and the present invention is not subjected to the restriction of top described content, and foregoing only plays illustration.

Claims (25)

1. contact adhesive composition, it comprise at least a pressure sensitive adhesive component and at least a use temperature not with the adulterant of the miscible thermoplastic material component of pressure sensitive adhesive, the thermoplastic material component that said composition comprises the pressure sensitive adhesive component of (1) at least 40% weight and at least 5% weight and (2) comprise the form in different at least two zones, the first area for basically continuously second area be that fibril arrives sheet, and has at least a character of following pressure sensitive adhesive character, (a) greater than the peel adhesion of only using pressure sensitive adhesive component, the shearing resistance similar to only using pressure sensitive adhesive component, (2) greater than the shearing resistance of only using pressure sensitive adhesive component, the peel adhesion similar to only using pressure sensitive adhesive component, (3) anisotropic peel adhesion, (4) anisotropic shearing resistance, (5) to any elongation up to extension at break, the tensile stress on coiled strip is vertical is than the big at least twice of coiled strip tensile stress in a lateral direction.

2. contact adhesive composition as claimed in claim 1 is characterized in that this pressure sensitive adhesive component is from following material: vinylformic acid, styrene block copolymer, natural rubber, synthetic rubber, siloxane-urea polymkeric substance, urethane, polyvinyl methyl ether and their adulterant.

3. contact adhesive composition as claimed in claim 1 is characterized in that this thermoplastic material component is ethane-acetic acid ethyenyl ester, polyolefine, polystyrene, amorphous polyester, polymethylmethacrylate and nylon.

4. contact adhesive composition as claimed in claim 3, its feature are that also this thermoplastic material component is ethane-acetic acid ethyenyl ester, isotactic polypropylene, linear low density polyethylene, new LDPE (film grade), high density polyethylene(HDPE), polybutene or polystyrene.

5. contact adhesive composition as claimed in claim 1 is characterized in that it also further comprises a kind of tackifier.

6. contact adhesive composition, it comprise at least a pressure sensitive adhesive component and at least a use temperature not with the adulterant of the miscible thermoplastic material component of pressure sensitive adhesive, this thermoplastic material component is made up of polystyrene, amorphous polyester, polymethylmethacrylate or nylon, the thermoplastic material component that said composition comprises the pressure sensitive adhesive component of (1) at least 40% weight and at least 5% weight and (2) comprise the form in different at least two zones, the first area for basically continuously second area be that fibril arrives sheet.

7. contact adhesive composition as claimed in claim 6 is characterized in that this pressure sensitive adhesive component is from following material: vinylformic acid, styrene block copolymer, natural rubber, synthetic rubber, siloxane-urea polymkeric substance, urethane, polyvinyl methyl ether and their adulterant.

8. the method for preparing contact adhesive composition as claimed in claim 1, this method comprises the following steps:

(a) with in an at least a pressure sensitive adhesive component and at least a thermoplastic polymer components melting mixing to a container,

(b) is shearing or elongation is flowed (1), or extrude the component of described fusion fusion under both conditions of having concurrently, or

(2) extrude and the described fusion adulterant of tractive, form pressure sensitive adhesive component and

(c) make described composition cools.

9. method as claimed in claim 8 is characterized in that mixing under dispersion or the distributive condition or under their combination.

10. method as claimed in claim 8 is characterized in that adopting gap method or continuous processing to mix.

11. method as claimed in claim 10 is mixed in it is characterized in that adopting or roller grinds this gap method of carrying out.

12. method as claimed in claim 10 is characterized in that adopting single screw extrusion machine, twin screw extruder, disk forcing machine, reciprocating type single screw extrusion machine and bolt cartridge type single screw extrusion machine to carry out this continuous processing.

13. prepare the method for contact adhesive composition as claimed in claim 6, this method comprises the following steps:

(a) with in an at least a pressure sensitive adhesive component and at least a thermoplastic polymer components melting mixing to a container,

(b) is shearing or elongation is flowed (1), or extrude the component of described fusion fusion under both conditions of having concurrently, or

(2) extrude and the described fusion adulterant of tractive, form pressure sensitive adhesive component and

(c) make described composition cools.

14. method as claimed in claim 13 is characterized in that mixing under dispersion or the distributive condition or under their combination.

15. method as claimed in claim 13 is characterized in that adopting gap method or continuous processing to mix.

16. method as claimed in claim 15 is mixed in it is characterized in that adopting or roller grinds this gap method of carrying out.

17. method as claimed in claim 15 is characterized in that adopting single screw extrusion machine, twin screw extruder, disk forcing machine, reciprocating type single screw extrusion machine and bolt cartridge type single screw extrusion machine to carry out this continuous method.

18. a pressure sensitive adhesive tape, it comprises a kind of base material and the contact adhesive composition as claimed in claim 1 on this base material.

19. a pressure sensitive adhesive tape, it comprises a kind of base material and the contact adhesive composition as claimed in claim 1 on this base material.

20. preparation has the method for the pressure sensitive adhesive tape of contact adhesive composition as claimed in claim 1, this method comprises the following steps: that (a) is with in an at least a pressure sensitive adhesive component and at least a thermoplastic polymer components melting mixing to a container

(b) is shearing or elongation is flowed (1), or following component of described fusion fusion of condition that both have concurrently be expressed on a kind of base material, or

(2) described fusion adulterant is extruded and is pulled on a kind of base material, form the coating pressure sensitive adhesive structure and

(c) make described structure cooling.

21. preparation has the method for the pressure sensitive adhesive tape of contact adhesive composition as claimed in claim 1, this method comprises the following steps:

(a) with in an at least a pressure sensitive adhesive component and at least a thermoplastic polymer components melting mixing to a container,

(b) is shearing or elongation is flowed (1), or under both conditions of having concurrently the component of described fusion fusion is expressed on a kind of base material of coextrusion, or

(2) described fusion adulterant is extruded and is pulled on a kind of base material of coextrusion, form the structure be coated with pressure sensitive adhesive and

(c) make described structure cooling.

22. preparation has the method for the pressure sensitive adhesive tape of contact adhesive composition as claimed in claim 6, this method comprises the following steps:

(a) with in an at least a pressure sensitive adhesive component and at least a thermoplastic polymer components melting mixing to a container,

(b) is shearing or elongation is flowed (1), or under both conditions of having concurrently the component of described fusion fusion is expressed on a kind of base material, or

(2) described fusion adulterant is extruded and is pulled on a kind of base material, form the coating pressure sensitive adhesive structure and

(c) make described structure cooling.

23. preparation has the method for the pressure sensitive adhesive tape of contact adhesive composition as claimed in claim 6, this method comprises the following steps:

(a) with in an at least a pressure sensitive adhesive component and at least a thermoplastic polymer components melting mixing to a container,

(b) is shearing or elongation is flowed (1), or under both conditions of having concurrently the component of described fusion fusion is expressed on a kind of base material of coextrusion, or

(2) described fusion adulterant is extruded and is pulled on a kind of base material of coextrusion, form the structure be coated with pressure sensitive adhesive and

(c) make described structure cooling.

24. a pressure-sensitive adhesive article, it is included in the pressure sensitive adhesive as claimed in claim 1 in the device that a kind of transdermal drug transmits.

25. graphic arts film that comprises pressure sensitive adhesive as claimed in claim 1.

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