CN1188500A - Method of using acrylate-containing polymer blends - Google Patents
Method of using acrylate-containing polymer blends Download PDFInfo
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- CN1188500A CN1188500A CN96194938A CN96194938A CN1188500A CN 1188500 A CN1188500 A CN 1188500A CN 96194938 A CN96194938 A CN 96194938A CN 96194938 A CN96194938 A CN 96194938A CN 1188500 A CN1188500 A CN 1188500A
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Abstract
A method of priming a substrate comprising applying to the substrate a blend comprising (a) a modified block copolymer comprising (i) a polystyrene block and (ii) a polydiene block or a hydrogenated polydiene block, the polydiene block or hydrogenated polydiene block being modified to contain an average of one or more carboxyl groups; and (b) a polymer comprising a polymerization reaction product of two or more mono-ethylenically unsaturated monomers in which (i) at least one of the monomers is an acrylic or methacrylic acid ester of a non-tertiary alcohol having 1 to 14 carbon atoms, inclusive, and (ii) at least one of the monomers is a nitrogen-containing monomer; in particular, a method of enhancing adhesion between a substrate and an adhesive comprising the steps of priming the substrate by applying to the substrate the blend and applying the adhesive to the primed substrate.
Description
The background of invention
FIELD OF THE INVENTION
The present invention relates to blend polymer, they are as for example tackiness agent, priming paint, printing ink and coating.
The description of background technology
Low surface energy substrates, the critical surface tension when being moistening as polyethylene, polypropylene and other polyolefinic characteristics is about 35 dynes per centimeter or littler.These surfaces are because its relatively poor wetting capacity generally can not be accepted printing ink, coating and tackiness agent.Therefore, need to improve, make them with the same to the bounding force on high-energy surface to these surperficial bounding forces.
The general introduction of invention
The present invention relates to the method for primary coat ground, be included in and use blend on the ground, this blend comprises the segmented copolymer of (a) modification, this multipolymer comprises (i) polystyrene section and (ii) polydiene section or hydrogenant polydiene section, and described polydiene section or hydrogenant polydiene section are modified as and on average contain one or more carboxyls; (b) comprise the polymkeric substance of the polymeric reaction product of two or more monoene unsaturated monomers, wherein, (i) at least a monomer is acrylate or the methacrylic ester that contains the non-tertiary alcohol of 1 to 14 carbon atom, and (ii) at least a monomer is nitrogenous monomer.
Especially the invention still further relates to the method that strengthens the bounding force between ground and the tackiness agent, it may further comprise the steps: come the described ground of primary coat by use blend on described ground, described blend comprises the segmented copolymer of (a) modification, this multipolymer comprises (i) polystyrene section and (ii) polydiene section or hydrogenant polydiene section, and described polydiene section or hydrogenant polydiene section are modified as and on average contain one or more carboxyls; (b) comprise the polymkeric substance of the polymeric reaction product of two or more monoene unsaturated monomers, wherein, (i) at least a monomer is acrylate or the methacrylic ester that contains the non-tertiary alcohol of 1 to 14 carbon atom, and (ii) at least a monomer is nitrogenous monomer; Tackiness agent is applied on the ground of primary coat.In following preferable embodiment, ground is low-yield ground." low-yield ground " used herein is meant that the critical surface tension when moistening is not more than the ground of about 35 dynes per centimeter.Example comprises polyolefin polymer, as polyethylene and polypropylene.
No matter blend polymer provided by the present invention is for low-yield surface (for example polyolefine, as polyethylene and polypropylene), has still all shown good bounding force for high-energy surface (being that surface energy is greater than 35 dynes per centimeter, as metal and glass).This blend can be used as priming paint (as being used for coating and paint), tackiness agent (as transition layer), pressure sensitive adhesive, printing ink and coating.
The detailed description of invention
Characteristics of the present invention are blends, and this blend comprises as the segmented copolymer (a) of the modification of listing in the overview section of inventing and contains acrylate or the polymkeric substance of methacrylic ester (b).
Segmented copolymer comprises one or more snippets polystyrene section.If have one section or two sections polystyrene sections, then segmented copolymer can be expressed as AB segmented copolymer (containing one section polystyrene section) and ABA segmented copolymer (containing two sections polystyrene sections), " A " represents polystyrene, " B " expression polydiene or hydrogenant polydiene.
The example of polydiene section or hydrogenant polydiene section for example comprises, polyhutadiene, polyisoprene, ethylene/butylene or ethylene/propene section.Term " polydiene " refers to the repeating unit of diene monomers.The residual degree of unsaturation of hydrogenant polydiene section should be less than 10%, better less than 5%, in the original vol of the alkene degree of unsaturation of polydiene section.Can comprise carboxylic acid and acid anhydrides (as toxilic acid and maleic anhydride) with the example that the reaction of polydiene section or hydrogenant polydiene section obtains the compound of substituting group carboxyl.
Good especially segmented copolymer is the styrene-ethylene/butylene-styrene block copolymer of maleation.Term " maleation " is meant polydiene or hydrogenant polydiene section, for example with toxilic acid or maleic anhydride modified, makes polydiene or hydrogenant polydiene section on average contain one or more carboxyls.The example of better polymerization thing is the styrene-ethylene/butylene-styrene triblock copolymer that contains 2% (weight) Succinic anhydried (carboxyl source), (this multipolymer is available from Shell Chemical Company, Houston, TX, commodity are called " Kraton FG-1901X ").The tensile strength of " Kraton FG-1901X " is about 5000 pounds/inch
2(psi), elongation is about 500, and Xiao A hardness is about 75, and the Brookfield viscosity when proportion is about 0.91,77 (25 ℃) is about 1250 centipoises (cps).
The weight ratio of the polystyrene section of segmented copolymer (a) and polydiene section or hydrogenant polydiene section is generally in 5: 95 to 95: 5 scope, better in 10: 90 to 50: 50 scope.
Polymkeric substance (b) is the polymeric reaction product of two or more monoene unsaturated monomers, and wherein, (i) at least a monomer is acrylate or the methacrylic ester that contains the non-tertiary alcohol of 1 to 14 carbon atom, and (ii) at least a monomer is nitrogenous monomer.
In addition, polymkeric substance (b) can also comprise component (iii), promptly contains the monomer of at least one carboxylic functionality, hydroxy functionality and epoxy functionalities, perhaps these monomeric mixtures.Monomer example (iii) comprises vinylformic acid, methacrylic acid, methylene-succinic acid, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate and glycidyl methacrylate.Be preferably vinylformic acid and methacrylic acid.When existing component (iii), its consumption is 1 to 10 weight part preferably, better is 1 to 5 weight part, in 100 parts by weight polymer (b).Under any circumstance, comprise component (i) and (ii), perhaps comprise component (i), (ii) and polymkeric substance (iii) (b) be not crosslinked.
Non-tertiary alcohol comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 1-methyl isophthalic acid-butanols, 1-methyl isophthalic acid amylalcohol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 2-ethyl-1-butanols, 3 preferably, 5,5-trimethylammonium-1-hexanol, 3-enanthol, sec-n-octyl alcohol, 1-decanol or 1-dodecanol.Good especially ester monomer is an Isooctyl acrylate monomer.
Nitrogenous monomer can comprise N-vinyl lactam (as N-vinyl pyrrolidone (N-vinylpyrolidone) or N-caprolactam), acrylamide, N-alkyl acrylamide (as N methacrylamide), N, N-dialkyl group acrylamide (as N,N-DMAA) or their mixture.Nitrogenous monomeric consumption depends on selected monomer.In general, nitrogenous monomeric consumption is at least 2 weight parts, is 5 to 40 weight parts preferably, in 100 parts by weight polymer (b).For example, when using N-vinyl lactam and N,N-DMAA respectively, nitrogenous monomeric better consumption is 5 to 30 weight parts.In addition, when independent use acrylamide, consumption generally is at least 5 weight parts; Yet when acrylamide used with the N-vinyl lactam, the consumption of acrylamide can be less than 5 weight parts, for example 1 to 4 weight part.When the nitrogenous monomer of the present invention is the N-vinyl lactam, it does not contain acrylate and methacrylate based group, but, when nitrogenous monomer is acrylamide, N-alkyl acrylamide or N, during N-dialkyl group acrylamide, it can contain acrylic or methacrylic acid or their derivative.
It is believed that nitrogenous monomer can strengthen the consistency of blend by the association with the carboxyl of the phenyl of vinylbenzene section and/or polydiene or hydrogenant polydiene section, thereby improve performance.
In embodiment preferably, the Tg of the homopolymer of acrylate or methacrylic ester is less than 20 ℃.Has Tg greater than 20 ℃, weight-average molecular weight is 2, more than 000, and can carry out polymerization with the acrylate or the methacrylic acid ester moiety of polymkeric substance with one or more snippets associating polymeric part (polymeric moiety) of segmented copolymer, described polymeric part for example, the polystyrene part that in the U.S. Patent No. that is entitled as " Pressure-Sensitive AdhesiveComposition " (contact adhesive composition) 5,143,972 of Groves, discloses.In this case, think and between the phenyl of described polymeric part and vinylbenzene section, also can associate.
Polymkeric substance (b) is preferably by using conventional polymerization technique that starting monomer is carried out photopolymerization that free radical causes or the incompatible preparation of hot polymerization.Then, the polymkeric substance of gained and the segmented copolymer of modification (a) are carried out physical blending.
The consumption of segmented copolymer (a) is enough to make itself and ground to associate, especially when ground is low-yield ground.The consumption of polymkeric substance (b) is enough to make itself and segmented copolymer (a) to associate.Used hereinly relate to interactional term " association " between ground and the segmented copolymer (a) or " association " and be meant the bonding (bonding) between ground and the segmented copolymer (a) or contact that this bonding or contact make that ground (especially low-yield ground) is easier to accept as this material of printing ink, coating and tackiness agent.That is to say, segmented copolymer (a), polymkeric substance (b) is at ground with desire to be bonded between the higher-energy material (as tackiness agent and/or coating) on the ground and produced energy gradient at last.Relate to the term " association " of polymkeric substance (b) and segmented copolymer (a) or " association " herein and be meant bonding or contact between polymkeric substance (b) and the segmented copolymer (a), this bonding or contact interact their.The weight ratio of segmented copolymer (a) and polymkeric substance (b) is preferably in 95: 5 to 5: 95 scope, better in 75: 25 to 25: 75 scope.
The example of better polymerization thing blend comprises: the blend of styrene-ethylene/butylene-styrene block copolymer of (1) maleation and Isooctyl acrylate monomer/N-caprolactam/acrylate copolymer; (2) blend of the styrene-ethylene/butylene-styrene block copolymer of maleation and Isooctyl acrylate monomer/N-caprolactam polymkeric substance; (3) blend of the styrene-ethylene/butylene-styrene block copolymer of maleation and Isooctyl acrylate monomer/N-caprolactam/acrylic acid/polystyrene macromolecular monomer-polymer; And the styrene-ethylene/butylene-styrene block copolymer of (4) maleation and the blend of Isooctyl acrylate monomer/acrylamide polymer.Can obtain the blend of priming paint and/or coating, printing ink or tackiness agent (as pressure sensitive adhesive) form by using additive (for example, as described below).
As priming paint, blend polymer especially can be used for low-yield ground." low-yield ground " used herein is meant that critical surface tension when moistening is no more than the ground of about 35 dynes per centimeter.The example of this ground comprises polyolefin polymer, as polyethylene and polypropylene.
Blend can come tackify by sneaking into tackifier, perhaps comes tackify by the polymer architecture that contains acrylate or methacrylic ester is carried out modification, and perhaps both combine.The tackifier that are applicable to the tackify blend comprise low-molecular-weight hydrocarbon resin and α-and beta-pinene base resin.Many tackifier can be buied, and the those of ordinary skill in an adhesive formulations field just can make one's options to best tackifier.The exemplary that is applicable to the tackifier of buying of blend comprises that commodity are called the resin of " Regalrez 1018 ", " Regalrez 1078 " and " REZ-D 2084 " (all available from Hercules Inc.Wilmington, DE); The resin of commodity " Escorez-143H " and " Escorez 5380 " by name (all available from Exxon Corp., Houston, TX); And the resin of commodity " Wingtack Plus " by name (available from Goodyear Tire and Rubber Company, Akron, OH).The consumption of tackifier contains in per 100 parts of blends in 20 to 250 parts the scope preferably in the blend.In general, when blend was the priming paint form, the content of tackifier was lower; When blend was the pressure sensitive adhesive form, the content of tackifier was higher.
Can comprise oxidation inhibitor in the blend, with oxidation that prevents tackifier and the viscosity loss that wears out and cause with blend.Suitable oxidation inhibitor is based on the organic metal salt of (1) hindered phenol or (2) sulfur-bearing.The example of hindered phenol comprises, ortho position replacement or 2, and the dibasic phenols of 5-, wherein, one or more substituting groups are the branched hydrocarbyl groups with 2 to 30 carbon atoms, as the tertiary butyl or tert-pentyl.Other can be used for hindered phenol of the present invention and comprises, the phenols of para-orientation, and substituting group is OR
1, and R
1It is propionic ester of methyl, ethyl, 3 replacements etc.The example of the hindered phenol that can buy comprises, available from Ciba-Geigy Corp., Hawthorne, the hindered phenol of the commodity of NY " Irganox 1076 " by name, and available from American Cyanamid Company, Wayne, the hindered phenol of the commodity of NewJersey " Cyanox LTDP " by name.The organic metal salt of suitable sulfur-bearing is the nickel derivative of dithiocarbamic acid dibutylester.
Blend can also comprise mineral filler, as lime carbonate, clay, talcum, silicon-dioxide, and limited amount carbon black, can also comprise organic filler, as wood powder and starch.The most frequently used is lime carbonate, clay and talcum.Blend can also come painted by sneaking into dry colour or colour batch (color concentrates) (normally polystyrene-based); When blend is filler or ink form, usually need painted.General pigment comprises titanium dioxide and carbon black.Can also comprise stablizer in the blend, as sterilant and mould inhibitor.
Other additive that can also comprise in the blend is silicane, titanate (titanic acid ester) and chlorinatedpolyolefins (" CPOs ").Other resin, as Resins, epoxy also can with segmented copolymer and acrylic ester polymer blend.
Can strengthen the ability of the UV degradation of blend by in blend, sneaking into ultraviolet inhibitor.In general, the ultraviolet inhibitor of the commodity of per 100 parts 1 part (phr) loading level " Cyasorb IV 531 " by name is (available from American Cyanamid Company, Wayne, NJ), perhaps the commodity of equal portions " Tinuvin 328 " by name are (available from Ciba-Geigy Corp, Hawthorne, NY) ultraviolet inhibitor and commodity " Uvinal 400 " by name are (available from GAF Corp., New York, the mixture of ultraviolet inhibitor NY) are enough to strengthen the UV degradation ability of blend.A kind of nickel chelate in a kind of and following trade(brand)name in above-mentioned three kinds of ultraviolet inhibitors of 0.5phr is mixed, the effect of the UV degradation that can be enhanced, these commodity " Cyasorb UV 1084 " by name are (0.5phr) (available from American Cyanamid Company, Wayne, NJ) or " NBC " (0.1phr) (available from E.I.du Pont de Nemours and Company, Wilmington, DE).Phr used herein unless otherwise noted, all is in the weight of the segmented copolymer in the blend.
Above-mentioned blend is particularly useful as the priming paint of tackiness agent (as pressure sensitive adhesive, thermosetting adhesive, thermoplastic binder and mixed adhesive).Term used herein " mixed adhesive " is meant that two or more different types of tackiness agents and two or more are applicable to the mixture of polymers that forms tackiness agent.
Thermosetting adhesive generally forms by polyaddition reaction.The example of thermosetting adhesive comprises polysulphide, polysiloxane, polyester, urethane, epoxide, anaerobic and aerobic acrylic acid or the like, the polymkeric substance and the vulcanized rubber of radiation-hardenable.Thermosetting adhesive is generally by heat, catalyzer or photoactivation or humidity activated curing.After the curing, thermosetting adhesive generally is insoluble, and promptly tackiness agent can not be dissolved in organic solvent or water, and thermosetting adhesive is infusible, and tackiness agent can not flow when promptly heating.
In general, pressure sensitive adhesive is after making, and its viscosity can not rise gradually, and on the contrary, they can forever keep viscous state.The example of pressure sensitive adhesive comprises segmented copolymer and the natural or elastomeric pressure sensitive adhesive from polyacrylic ester, this paper definition.Pressure sensitive adhesive generally all has visco-elasticity, therefore can show the characteristic of viscous liquid and Hookean body.
Thermoplastic binder are solvable and the fusile material.The example of thermoplastic binder comprises ethenyl adhesive, as polyvinyl chloride, polyvinyl butyral acetal, polyvinyl alkyl ester or ether, and vinyl-acetic ester-ethylene copolymer tackiness agent; Acrylic adhesives; Hotmelt; Cellulose binder; Bituminous cement.The form of thermoplastic binder can be emulsion, solution or solid.
Priming paint of the present invention can use various technology coatings, comprises that dip-coating, spraying, brushing, wheel change gravure coating (rotogravure), the Meier rod is coated with and scraper applies.A useful especially technology is that priming paint of the present invention is coated on the ground, then abrasion.Present technique plays the effect of inducing chemical reaction by mechanical effect as abrasion, and promptly machinery causes chemical reaction.Suitable abrasion product comprises no velveteen fabric, cloth or sand paper.When using sand paper, sand paper preferably wetting or exsiccant, and 50% abrasive sand granularity is preferably in 100 to 2 microns the scope.When to be bonded on the ground be pressure sensitive adhesive the time, the abrasive sand granularity is preferably in 8 to 2 microns scope, better in 5.5 to 2 microns scope.When to be bonded on the ground be construction adhesive (being epoxide and urethane) time, the abrasive sand granularity is preferably in 100 to 50 microns the scope.
Further specify the present invention by the following examples, and unrestricted the present invention.All percentage ratio unless otherwise noted, is weight percentage.
Embodiment
Testing method
A. priming paint
The FPL method of etch aluminum
The aluminium sample is generally 152.4mm * 50.8mm * 1.6mm, available from Vincent Metals, and Minneapolis, MN, commodity are called " 2024-T3 Alclad ".Forest ProductsLaboratory (timber laboratory) according to H.W.Eichner; Report number on April 1st, 1842,1954, Madison, WI, the etching method described in the USA is handled the aluminium sample.Particularly, the following processing of sample: the rinsing in acetone of each sample, dry air then.Then, degreasing was carried out in immersion in 10 minutes among the Oakite 164 (alkalis) of each sample 75 grams in every liter of distilled water.Then, with the rinsing 2 minutes in tap water of each sample, then in 71 ℃ of dippings 10 minutes in etch is bathed, etch is bathed by 1161 gram H
2SO
4, 156.8 the gram Na
2Cr
2O
72H
2O, the naked aluminum alloy sheet of 1.5 gram 202H-T3, and the distilled water of 3.5 liters of solution of formation of capacity is formed.In etch solution after the dipping, each sample was with tap water rinsing 2 minutes, 66 ℃ of dryings 10 minutes.
Static shear
According to following method measure with the pressure sensitive adhesive foaming adhesive tape of dual coating or pressure-sensitive transfering adhesive adherent through primary coat or without the shearing resistance of the ground of primary coat:
Preparation is through the aluminum strip of FPL etch (available from Vincent Metals, Minneapolis, MN, commodity are called " 2024-T3 Alclad "), and it is of a size of 50.8mm * 25.4mm * 1.6mm, and diameter is arranged is the hole of 7mm at the 10mm place on one side from aluminum strip in the central.Equally, prepare identically through primary coat with without the ground tape of primary coat, the thickness of every tape should make that this ground tape can not surrendered under test temperature and test load.
The pressure sensitive adhesive tape that has release liner that 12.7mm is wide is bonded on the solid-end (that promptly relative with hole one end is arranged end) of aluminum strip, and its length is trimmed to 25.4mm.Remove liner then, the solid-end of ground bar is bonded on the adhesive surface that exposes.The sample of gained is the level attitude placement, with the roller roll-in of 2.4kg, to guarantee the tight contact between the surface.After room temperature is keeping 24 hours, sample is placed on is preheated to 80 ℃ in the air circulation oven.After 15 minutes, the weight of 1kg is hung under the sample.With sample inclination to 2 ° of offset from perpendicular to eliminate peeling force.It is exactly " static shear value " that weight falls the required time (in second).If after 6,000 minutes, weight does not still fall, then termination test.
90 ° of peel adhesion-pressure sensitive adhesives
The pressure-sensitive foaming adhesive tape of measuring dual coating in order to following method for various through primary coat and (N/100mm) without the peel adhesion (peel adhesion) of the ground of primary coat:
Aluminium foil (1145-0-SB at 114mm * 15.9mm * 0.13mm, Lawrence FredrickCompany, Greenwood, matt one side IL) goes up to place and has the linerless one side that release liner is of a size of the foamed glue carry sample of 101.6mm * 12.5mm * 1.1mm.Then, the steel rider that coats vulcanite with 2.4kg roll-in three times back and forth on sample.
Then, shear the liner of about 50mm down from the one side that has liner of sample, then with sample near through primary coat or without an end of the 152.4mm * 50.8mm * 5.1mm plate of the ground of primary coat, aim at central authorities' placement.The steel rider that coats vulcanite with 2.4kg roll-in three times back and forth on the assembling sample again.Repeat this process then, at the other end of plate lamination second layer foaming adhesive tape-constructed of aluminium.
After at room temperature stopping to press the time of (dwell) length-specific, sample is placed on (PJ-90, Consultants INTL.Network in 90 ° the peel jig, Mentor OH), and is fixed on the Instron tensile testing machine (available from Instron Corp., Canton, MA) in.Move freely bringing in of aluminium foil-laminated foaming adhesive tape with the speed of 30.5 centimetres of per minutes and measure 90 ° of peel adhesion.The stripping strength of gained (in N/100mm) is three mean values of measuring.
90 ° of peel adhesion-thermosetting adhesives
Measure the peel adhesion (N/100mm) of polypropylene (PP) and new LDPE (film grade) (LDPE) and thermosetting adhesive adherent film by the following method:
The pressure-sensitive transfering adhesive of acrylic acid or the like that uses 0.25mm is (from Minnesota Mining andManufacturing Company, St.Paul, MN, commodity are called " F9473PC ") with membrane sample (175mm * 75mm * 0.25mm) be fixed on the planar surface.Make primer solution overflow on sample surfaces, with 80 microns abrasive grains of a slice is that the basic abrasive material of the back of the body is (from Minnesota Mining and ManufacturingCompany with the fabric, St.Paul, MN, commodity are called " 3M-ITE P220 ") evenly abrasion.After 1 minute, make primer solution overflow from the teeth outwards again, and the erosion 1 minute of regrinding.Membrane sample is respectively washed 3 times at room temperature dry 24 hours with dimethylbenzene and ethanol.With the bi-component epoxy tackiness agent (from Minnesota Mining andManufacturing Company, St.Paul, MN, commodity are called " Scotch-Weld 2216 B/A ") be coated on 152.4m * 101.6mm * 1.6mm on the 2024-T3 of FPL etch aluminium sheet, form the thick layer of 0.5mm.The roll-in pressure that use to coat the roller of TR thin rubber (light rubber) makes the one side and adhesives through primary coat of film.After 72 hours, film is cut into the test sample of three 12.5mm.With aluminium sheet be placed on 90 ° of peel jig (available from Consultant INTL Network, Mentor, OH) in, be fixed on the Instron tensile testing machine (available from Instron Corp., Canton, MA) on.Measure 90 ° of peel adhesion by freely bringing in of speed moving film bar with per minute 30.5cm.The preparation control sample that uses the same method, different is: without the primer solution overflow, but denude sample under the situation of no primer solution.The stripping strength of gained (N/100mm) is three mean values of measuring.
Cohesive strength
Measure the cohesive strength of the foaming adhesive tape that can buy on the market according to the method for 90 ° of peel adhesion tests, different is: adhesive tape is bonded in 152.4mm * 50.8mm * 1.6mm on the 2024-T3 of FPL etch gained aluminium sheet, make it stop pressing 2 hours, test then.The foaming adhesive tape is from Minnesota Miningand Manufacturing Company, St.Paul, the foaming adhesive tape and the model of the commodity of MN " Scotch " by name are " Y-4220 ", " VHB-4205 " and " VHB-4950 " (using the acrylic psa dual coating); " VHB-4952 " (with styrene butadiene rubbers (SBR) pressure sensitive adhesive dual coating); And the combination of " VHB-4910 " (acrylic acid or the like transfering belt that 1mm is thick).All foaming adhesive tapes are by in the cohesive failure of foamed core material and rupture.Result shown in the Table A is the mean value that each adhesive tape is measured for three times.These values are used as the benchmark value of following sxemiquantitative peel adhesion test.
Table A
| The adhesive tape kind | The tackiness agent kind | Cohesive failure (N/100mm) |
| ????“Y-4220” | Acrylic acid or the like | ????438 |
| ????“VHB-4205” | Acrylic acid or the like | ????1050 |
| ????“VHB-4952” | ????SBR | ????658 |
| ????“VHB-4910” | Acrylic acid or the like | ????702 |
| ????“VHB-4950” | Acrylic acid or the like | ????877 |
The sxemiquantitative peel adhesion
For can not quantitative assay through primary coat or without the adhesion levels (as ground is film and/or flexible film, or the rigid articles of predetermined size) of the ground and the pressure sensitive adhesive of primary coat, can carry out semiquantitative determination.Method according to 90 ° of peel adhesion tests prepares sample, and different is: use two or more foaming adhesive tapes, adhesive tape-aluminium foil laminate structure is fixed on the ground by the rubber-coated steel rider of hand pressure or 2.4kg.Stop pressing the specific time (after being generally 15 minutes), draw the free end of adhesive tape-aluminium foil laminate structure with hand from ground.If do not find the cohesive failure of foamed core material, the then bonding foaming adhesive tape (cohesive strength is by determining with reference to last Table A) that has near minimum cohesive strength is removed then.Repeat this process, the foaming adhesive tape is tested (Table A in the reference) one by one, until foamed core material generation cohesive failure.Then, reference table A determines through the ground of the primary coat sxemiquantitative level to the clinging power of the pressure sensitive adhesive of foaming adhesive tape.
Single lap shear (single overlap shear)
With two blocks of ground plates (every be of a size of 51mm * 25.4mm * 5mm) used saturated the soft fabric of heptane clean twice, use the ethanol rinsing then.After 15 minutes, use a cotton coating machine (cotton-tipped applicator) that primer solution is coated on the one side of every block of plate, make its dry 30 minutes.Then, two cyanacrylate tackiness agents (from Minnesota Mining and Manufacturing Company, St.Paul, MN, commodity are called " Pronto CA-40 ") are dripped on a surface of primary coat.Then, a remaining ground plate through primary coat is placed on the plate top of cyanoacrylate-containing, forms the overlap joint of 12.7mm.Kept the finger compaction pressure 0.5 minute in lap-joint.Measure three test assemblings of preparation sample for each, it was solidified 72 hours, test then.(from Instron Corp., Canton is MA) with the pinblock speed measurement bond strength of 1.47mm/min on the Instron tensile testing machine.
B. pressure sensitive adhesive
The test method that is used to evaluate the parameter of the flexible sheet that applies with contact adhesive composition of the present invention is the standard industry test method.Standard test is at American Society for testing and materials (ASTM), Philadelphia, and PA and Pressuresensitive Tape federation (PSTC), Glenview all has detailed description in the various publications of IL.Below describe standard test methods in detail, and provide the reference source of each standard test methods.
Shearing resistance
Reference: ASTM:D3654-78; PSTC-7
Shearing resistance is the cohesion of tackiness agent or measuring of internal intensity.It along the direction that is parallel to standard flat, is pulled away from strip of glue the size of required power based on certain pressure strip of glue being attached on the standard flat from standard flat.It is with under the stress of constant standard load, and the sheet material that applies through tackiness agent of standard area is pulled away from expression of required time of stainless steel test board (in branch).
To be attached to testing on the stainless steel plate on the bar that tackiness agent applies, the part of 12.5mm * 12.5mm of every closely contacts with plate, is freely but adhesive tape has an end.The plate that is stained with the bar through applying is hung on the rack, make plate be 178 ° of angles, then by on the free end of band, hanging the free end that weight applies 1 kilogram power stretch tape extension through applying.Be used for eliminating peeling force than 180 ° little 2 °, thus the just shearing force of guaranteeing to measure, the bonding hold facility of determination test adhesive tape more accurately thus.Record separates the used time (in branch) with each adhesive tape sample with test board, as shearing resistance.
180 ° of peel adhesion
Reference: ASTM:D3330-78; PSTC-1 (11/76)
Peel adhesion is with specific angle and removes speed measurement and will remove required power through the flexible sheet that applies from test board.In an embodiment, this power is with newton number (N/100mm) expression of the sheet material through applying of per 100 millimeters width.Measuring process is as follows:
(1) the sheet material through applying that 12.5mm is wide is attached on the horizontal surface of glass test board of cleaning, makes it at length direction 12.7 centimetres (12.7 linear cm) closely contact be arranged at least.Tape vulcanite roller roll-in.
The free end doubling of tape that (2) will be through applying is to almost making itself contact, and peel angle is 180 ° like this.Free end is bonded on the adhesion test scale.
(3) the glass test board is clamped in the anchor clamps of tensile testing machine, this trier can make plate leave moving of scale with the constant rate of speed of 2.3 meters of per minutes.
(4) record reading (in newton) on the scale when the tape stripping glass surface, the scope of the observed numerical value of record duration of test.
Logarithmic viscosity number
Measure logarithmic viscosity number with the method for routine: in being controlled at 25 ℃ water-bath, use the Cannon-Fenske#50 viscometer to measure the flowing time of the polymers soln (0.15g polymkeric substance/decilitre ethyl acetate) of 10ml.Embodiment tests under identical condition with the comparing embodiment that is used for comparison.
A. priming paint
Embodiment 1
Present embodiment has been described the of the present invention a kind of blend preferably as priming paint.
The preparation of block copolymer solution
The styrene-ethylene/butylene-styrene triblock copolymer that 25.0g is contained not free (bound) Succinic anhydried of 2% is (available from Shell Chemical Company, Houston, TX, commodity are called " Kraton FG-1901X ") and 0.25g oxidation inhibitor (available from Ciba-Geigy Corp., Hawthorne, NY, commodity are called " Irganox 1076 ") weight ratio that is dissolved in 75.0g is in 5.5: 3.5: 1.0 hexanaphthene, dimethylbenzene and the alcoholic acid solvent mixture, makes 25% solution of segmented copolymer.
The preparation of acrylic ester polymer
Be equipped with the terpolymer that weight ratio is Isooctyl acrylate monomer/N-caprolactam/vinylformic acid (IOA/NVC/AA) of 78: 20: 2 in order to the below legal system:
In the narrow-mouthed bottle of 237ml, add 39g IOA, 10g NVC, 1g AA, 0.1g Diisopropyl azodicarboxylate (available from E.I.du Pont de Nemours ﹠amp; Company, Wilmington, DE, commodity are called " VAZO-64 "), 52.5g ethyl acetate, 9.0g methyl isoamyl ketone and 13.5g dimethylbenzene.The solution of gained is used exsiccant argon purge 3 minutes, sealing.Then, the bottle with sealing rotated 24 hours in 55 ℃ rotary water bath.By the infrared spectrometer analysis, determine that transformation efficiency is 99.1%.Solution contains 40% solid, and viscosity is about 7500cps.The logarithmic viscosity number that records is about 0.72dl/g.
The preparation of blend
It is in 5.5: 3.5: 1.0 hexanaphthene, dimethylbenzene and the alcoholic acid solvent mixture that the acrylate polymer solution that block copolymer solution that 1.0g is as above prepared and 1.9g as above prepare is dissolved in the 30.4g weight ratio, making weight ratio is 1: 3 the segmented copolymer and the blend of acrylic ester polymer, and its solid total concn is 3.0%.
Embodiment 2-12
In a like fashion, the preparation weight ratio is 1: 3 the segmented copolymer of pressing embodiment 1 preparation and the blend of various acrylic ester polymers.The table 1 composed as follows of acrylic ester polymer is listed.
Table 1
| Embodiment | Polymkeric substance is formed |
| ????2 | ????IOA/NVC/AA(88/10/2) |
| ????3 | ????IOA/NVC/AA(83/15/2) |
| ????4 | ????IOA/NVC/AA(93/5/2) |
| ????5 | ????IOA/NVP/AA/ACM/PSM(71/20/1/1/7)1 |
| ????6 | ????IOA/ACM(95/5) |
| ????7 | ????IOA/NVC(95/5) |
| ????8 | ????IOA/NVC(90/10) |
| ????9 | ????IOA/NVC(85/15) |
| ????10 | ????IOA/NVC(80/20) |
| ????11 | ????IOA/DMACM/AA(78/20/2) 2 |
1ACM is an acrylamide.PSM be the polystyrene-based ethyl ester of methacrylic acid 2-(weight-average molecular weight is about 10,000g/mol, according to U.S. Patent No. 4,554,324 the preparation; Be 52% solid in the hexanaphthene).NVP is the N-vinyl pyrrolidone.
2DMACM is a N,N-DMAA.
With the blend of embodiment 1-11 preparation with brush be applied to new LDPE (film grade) (LDPE), (both are all available from Precision Punch and Plastics for polypropylene (PP), Minneapolis, MN) and TPO (TPO) (available from Himont USA, Inc., Lansing, MI, commodity are called " ETA 3163 ") 152mm * 51mm * 5mm plate on.After 10 minutes, by mode described in the test method of 90 ° of peel adhesion, aluminium foil-lamination foaming pressure sensitive adhesive tape sample is adhered on the zone of primary coat, wherein, the acrylic psa foamed glue that 1mm is thick brings the Company from Minnesota Mining and Manufacturing, St.Paul, MN, commodity are called " VHB-4205 ".After one hour, measure 90 ° of peel value; This value is listed in Table II, and it is three mean values of measuring.Also measure for contrast peel value, the results are shown in Table II without the plate of primary coat.
Table II
90 ° of peel value (N/100mm)
| Embodiment | ????LDPE | ????PP | ????TPO |
| Comparative examples | ????26.0 | ????26.0 | ????17.5 |
| ????1 | ????158.0 | ????281.0 | ????754.0 * |
| ????2 | ????158.0 | ????281.0 | ????667.0 |
| ????3 | ????158.0 | ????281.0 | ????719.0 * |
| ????4 | ????158.0 | ????263.0 | ????210.0 |
| ????5 | ????158.0 | ????491.0 | ????754.0 * |
| ????6 | ????175.0 | ????315.0 | ????631.0 |
| ????7 | ????175.0 | ????123.0 | ????88.0 |
| ????8 | ????175.0 | ????333.0 | ????421.0 |
| ????9 | ????175.0 | ????316.0 | ????561.0 |
| ????10 | ????175.0 | ????316.0 | ????719.0 * |
| ????11 | ????125.0 | ????614.0 | ????772.0 * |
*The foamed core material cohesive failure
The result of Table II shows: use blend of the present invention to come the low-yield surface of primary coat, can improve pressure sensitive adhesive and surperficial clinging power.
Embodiment 12
To be that 5.5: 3.5: 1.0 hexanaphthene, dimethylbenzene and alcoholic acid solvent mixture is diluted to 3% polymer solids content by the block copolymer solution of embodiment 1 preparation with by each personal weight ratios of acrylic ester polymer of embodiment 5 preparations, as mentioned above, they are coated on polypropylene (PP) and new LDPE (film grade) (LDPE) test board with brush.Measure peel value as stated above, with Table II listed according to the value of the segmented copolymer/acrylic ester polymer blend of embodiment 5 preparation relatively.The results are shown in Table III.
Table III
90 ° of peel value (N/100mm)
| ????LDPE | ????PP | |
| Segmented copolymer | ????88.0 | ????88.0 |
| Acrylic ester polymer | ????24.0 | ????70.0 |
| Embodiment 5 blends | ????158.0 | ????491.0 |
The result of Table III shows: blend component is used separately separately as priming paint, and performance is also bad, they is mixed can obtain higher peel adhesion.
Embodiment 13
The preparation weight ratio is the blend by the acrylic ester polymer of the segmented copolymer of embodiment 1 preparation and embodiment 5 of containing of 1: 3,1: 1 and 3: 1, be diluted to 3% polymer solids content, brush in a manner described on the test board of TPO (TPO).Use as embodiment 1 described adhesive tape " VHB-4205 " and measure peel value; The results are shown in Table IV.
Table IV
| Ratio of mixture | Peel off (N/100mm) for 90 ° |
| ????1∶3 | ????702 * |
| ????1∶1 | ????684 * |
| ????3∶1 | ????702 * |
*The foamed core material cohesive failure
The result of Table IV shows: the segmented copolymer/acrylic ester polymer of relative broad range is than the paint base composition that can effectively be used for low-yield surface.
Embodiment 14
Use blend coated that the fabric of no velveteen will prepare by embodiment 10 on polypropylene (PP) and new LDPE (film grade) (LDPE) test board.After 10 minutes, aluminium foil-laminated foaming adhesive tape is bonded on the ground of primary coat.Especially, used following adhesive tape: the acrylic psa foaming adhesive tape of dual coating (from Minnesota Mining and Manufacturing Company, St.Paul, MN, commodity are called " VHB-4205 "); The acrylic acid or the like transfer pressure sensitive adhesive tape that 1mm is thick (from Minnesota Mining andManufacturing Company, St.Paul, MN, commodity are called " VHB-4910 "); The styrene butadiene rubbers pressure sensitive adhesive foaming adhesive tape of dual coating (from Minnesota Mining and ManufacturingCompany, St.Paul, MN, commodity are called " VHB-4952 ").After 1 hour, measure 90 ° of peel value; Also measure value without the ground of primary coat.The results are shown in Table V.
Table V
90 ° of peel value (N/100mm)
| PP | LDPE | |
| Without primary coat | ||
| “VHB-4205” | 26.0 | 26.0 |
| “VHB-4910” | 52.0 | 26.0 |
| “VHB-4952” | 298.0 | 210.0 |
| Through primary coat | ||
| “VHB-4205” | 350.0 | 772.0 * |
| “VHB-4910” | 210.0 | 439.0 |
| “VHB-4952” | 421.0 | 702.0 * |
*The foamed core material cohesive failure
The result of Table V shows: use blend of the present invention as priming paint, can improve the peel adhesion between acrylic psa and styrene butadiene ribber (SBR) pressure sensitive adhesive and the low-yield surface.
Embodiment 15
In 3% the primer solution of pressing embodiment 1 preparation of about 109g, add 0.5g Resins, epoxy (available from Shell Chemical Company, Houston, TX, commodity are called " Epon 828 "), 3.0g Chlorinated Polypropylene III is (available from Eastman Chemical Company, Kingsport, TN, commodity are called " CP 343-3 "), the 0.5g silane coupling agent is (available from OSi Specialties, Danbury, CT, commodity are called " Silquest A 186 ") and 0.8g trolamine titanic acid ester (triethanolamine titanate) (available from E.I.du Pont de Nemours; Company, Wilmington, DE, commodity are called " Tyzor TE "), carry out modification.Is 5.5: 3.5: 1.0 hexanaphthene, dimethylbenzene and alcoholic acid solvent mixture with this solution of about 25g by the weight ratio that adds 109g, it is diluted to contain 1% solid.Primer solution is brushed on the test board of glass, aluminium (Al) and stainless steel (S.S.).After 10 minutes, aluminium foil-lamination adhesive tape (from Minnesota Mining and Manufacturing Company, ST.Paul, MN, commodity are called " VHB-4205 ", " VHB-4910 " and " VHB-4952 ") is bonded on the sample of primary coat.After 72 hours, measure 90 ° of peel value; Outcome record is in Table VI.
Comparing embodiment 15
Method by embodiment 15 is carried out, and different is: come primary coat glass, aluminium and stainless steel test board with the Chlorinated Polypropylene III priming paint buied (available from NortonPerformance Plastics, Granville, NY, commodity are called " Tite-R-Bond-2684 ").The results are shown in Table VI.
Table VI
90 ° of peel value (N/100mm)
| Primer solution | Glass | ????Al | ????S.S. |
| Without primary coat | |||
| ?????VHB-4205” | ????386 | ????684 * | ????315 |
| ????“VHB-4910” | ????263 | ????140 | ????210 |
| ????“VHB-4952” | ????386 | ????386 | ????351 |
| Embodiment 15 | |||
| ????“VHB-4205” | ????701 * | ????701 * | ????772 * |
| ????“VHB-4910” | ????649 | ????439 | ????368 |
| ????“VHB-4952” | ????614 | ????649 * | ????561 |
| Comparing embodiment 15 | |||
| ????“VHB-4205” | ????32 | ????351 | ????35 |
| ????“VHB-4910” | ????26 | ????351 | ????17 |
| ????“VHB-4952” | ????456 | ????491 | ????26 |
*The foamed core material cohesive failure
Table VI shows: primer solution of the present invention can improve ground (as glass, stainless steel and aluminium) the adherent clinging power of acrylic psa and styrene butadiene ribber (SBR) pressure sensitive adhesive and high surface energy.
Embodiment 16
To be coated on new LDPE (film grade) (LDPE) and polypropylene (PP) test board with the fabric of no velveteen (available from Kimberly-ClarkCorp., Roswell, GA, commodity are called " Kimwipe ") by 1% primer solution of embodiment 15 preparation.After 10 minutes, with aluminium foil-lamination adhesive tape (from Minnesota Mining andManufacturing Company, St.Paul, MN, commodity are called " VHB-4205 ", " VHB-4910 " and " VHB-4952 ") be bonded in as mentioned above on the sample of primary coat.After 1 hour, measure peel value, the results are shown in Table VII.
Comparing embodiment 16
Method by embodiment 16 is carried out, and different is: come primary coat LDPE and PP test board with the Chlorinated Polypropylene III priming paint buied (available from NortonPerformance Plastics, Granville, NY, commodity are called " Tite-R-Bond-2684 ").The results are shown in Table VII.
Table VII
90 ° of peel value (N/100mm)
| ????LDPE | ????PP | |
| Without primary coat | ||
| ????“VHB-4205” | ????26 | ????26 |
| ????“VHB-4910” | ????26 | ????52 |
| ????“VHB-4952” | ????210 | ????298 |
| Embodiment 16 | ||
| ????“VHB-4205” | ????789 + | ????824 * |
| ????“VHB-4910” | ????596 | ????421 |
| ????“VHB-4952” | ????702 * | ????526 |
| Comparing embodiment 16 | ||
| ????“VHB-4205” | ????298 | ????473 |
| ????“VHB-4910” | ????140 | ????351 |
| ????“VHB-4952” | ????351 | ????403 |
*The foamed core material cohesive failure
Table VII shows: the primer solution of embodiment 16 can improve the ground adherent clinging power of acrylic psa and styrene butadiene ribber (SBR) pressure sensitive adhesive and low surface energy.
Embodiment 17
(available from Consolidated-Thermoplastics Company, Schaumburg is on sample IL) will to brush LLDPE film (LLDPE) in 125mm * 75mm * 0.25mm by 1% primer solution of embodiment 15 preparation.After 15 minutes, aluminium foil-lamination foamed glue carry sample (from Minnesota, Mining and Manufacturing, St.Paul, Minnesota, commodity are called " VHB-4220 " and " VHB-4205 ") is bonded on the sample of primary coat.After 1 hour, remove adhesive tape by trying with hand and measure semiquantitative peel adhesion.Sample " VHB-4220 " can not be removed owing to the foamed core material cohesive failure.This shows that its peel adhesion is at least 425N/100mm.
Though, find that foaming adhesive tape " VHB-4205 " has good clinging power, it can be removed from the LLDPE through primary coat, and poly-foaming destroys in can not producing.After 12 hours, poly-foaming destroys in finding, this shows that its peel value is about 1000N/100mm.
Comparing embodiment 17
Process by embodiment 17 is carried out, and different is: the Chlorinated Polypropylene III priming paint buied (available from NortonPerformance Plastics, Granville, NY, commodity are called " Tite-R-Bond 2684 ") is brushed on the LLDPE sample.After 15 minutes, the adhesive tape that will foam (available from Minnesota, Mining and Manufacturing, St.Paul, Minnesota, commodity are called " VHB-4220 ") be bonded on the sample.After 1 and 12 hours, adhesive tape can easily be removed with hand at the interval.Estimate that peel value only is about 90N/100mm or littler.
Embodiment 18
To brush on the LLDPE of two 125mm * 75mm * 0.25mm membrane sample by 1% primer solution of embodiment 15 preparations by the method for embodiment 17.Then, will distinguish dry 15 minutes and 24 hours through the sample of primary coat.Then, with latex half light interior enamel (available from The Glidden Company, Cleveland, OH), interior usefulness/outward is that the high gloss enamel paint of base is (available from Carver Tripp in order to oil, Parks Corp.Somerset, MA) and the aerosol polyurethane paint (from Minnesota Mining and Manufacturing Company, St.Paul, MN, commodity are called PartNO-05904) apply sample through primary coat.LLDPE membrane sample without primary coat also applies in an identical manner.Drying is after 24 hours under envrionment conditions, with the filament tape sample of 125mm * 75mm * 0.25mm (from Minnesota Mining and Manufacturing Company, St.Paul, MN, commodity are called " Scotch Brand 898 ") with each surface (through primary coat or without primary coat) close adhesion through applying.After 15 minutes, adhesive tape is removed from each sample rapidly.Discovery is without all thoroughly delaminations of all coating on the LLDPE film of primary coat, and any one on the LLDPE surface of primary coat, all do not find the delamination of coating.
Comparing embodiment 18
Process by embodiment 18 is carried out, and different is: the Chlorinated Polypropylene III priming paint buied (available from NortonPerformance Plastics, Granville, NY, commodity are called " Tite-R-Bond 2684 ") is brushed on the LLDPE sample.As described in embodiment 18, apply and test sample through primary coat.Discovery is all thoroughly delaminations of all coating on the film of primary coat.
Embodiment 19
Adding 1g titanium dioxide dispersion in the primer solution of the 10g 3% that presses embodiment 15 preparations (available from HulsAmerica Inc., Piscataway, NJ, commodity are called " GPD 82-0082 ").Equally, and adding 1g carbon black dispersion in the identical primer solution of another 10g (available from Borden Chemical Company, Cincinnati, OH, commodity are called " Codispersion 31L62 ").After the mixing, two kinds of solution that add pigment are brushed on undressed LLDPE film, drying is 24 hours under envrionment conditions.Press embodiment 18 described modes with filament tape (from Minnesota Mining and Manufacturing Company, St.Paul, MN, commodity are called " Scotch Brand 898 ") close adhesion is on the surface through applying, and measurement adds the peel adhesion value of coating on the LLDPE film of pigment thus.When adhesive tape was removed rapidly, two kinds of coatings were not all found delamination.
Present embodiment shows: the present composition can be used to prepare coating, printing ink and paint, and fine bonding with low-energy polymer surfaces.
Embodiment 20
To brush TPO (TPO) in 50.8mm * 24.4mm * 5.1mm (available from Himont USA Inc. by 1% primer solution of embodiment 15 preparation, Lansing, MI, commodity are called " ETA 3163 ") test board on, use the foaming adhesive tape (from Minnesota Mining and Manufacturing Company, St.Paul, MN, commodity are called " VHB-4210 ") measuring it at the static shear on the 2024-T3 of FPL etch aluminium in 80 ℃ under the load of 1.0kg.Same test is without TPO (TPO) sample of primary coat.The results are shown in the Table VIII.
Table VIII
| Priming paint | The static shear value (minute) |
| Do not have | ????300 |
| Embodiment 15 | ????10,000+ |
The result of Table VIII shows: primer solution of the present invention has improved the high temperature adhesives hold facility of acrylic psa on the ground of low surface energy.
Embodiment 21
To brush on two sample panel by 3% primer solution of embodiment 15 preparation, one is that transparent soft PVC (PVC) membrane sample of 150mm * 150mm * 0.10mm is (available from Wiman Plastic Div., St.Cloud, Minnesota), another piece is that opaque TPO (TPO) membrane sample that does not add pigment of 150mm * 150mm * 0.35mm is (available from Himont USA Inc., Lansing, MI, commodity are called " HIFAX CA10A "), make its dry 30 minutes.0.25mm is had the pressure-sensitive transfering adhesive of acrylic acid or the like of release liner (from Minnesota Mining and Manufacturing Company, St.Paul, MN, commodity are called " F9473 PC ") use the vulcanite roll laminating of 2.4kg on the one side of every film.Similarly, be pressed on the aluminum foil strip of 130mm * 15.9mm * 0.13mm with the vulcanite roller of 2.4kg identical binder layer 126mm * 12.5mm.
Then, transfering adhesive is through the following measurement of the peel value on the adhesive tape backing of primary coat: with the rubber rollers of 2.4kg the sample layer of each transfering belt/backing structure of 150mm * 51mm is pressed in 152mm * 51mm * 1.6mm on the 2024-T3 of FPL etch aluminium sheet.Remove the liner of about 75mm from aluminium foil-laminated transfering adhesive sample, the adhesive tape sample on itself and the every block of aluminium sheet is bonding, to make two test samples of every kind of adhesive tape.The sample of gained has following structure: aluminium sheet/transfering adhesive/and through backing (two sides)/transfering adhesive/aluminium foil of primary coat.Prepare control sample in a similar fashion without primary coat.Peel value sees Table IX.
Table I X
| Peel value (N/100mm) | |
| Without primary coat | |
| ????PVC | ????175 |
| ????TPO | ????7 |
| Through primary coat | |
| ????PVC | ????702 * |
| ????TPO | ????702 * |
*Tackiness agent and film destroy
Present embodiment shows: bonding hold facility and the cohesive strength of tackiness agent of pressure sensitive adhesives adhesive tape on backing is suitable, and perhaps tensile strength or the yield strength with the backing that can make is suitable.
Embodiment 22
With the polypropylene (PP) of 51mm * 25.4mm * 5mm and high density polyethylene(HDPE) (HDPE) (available from Precision Punch ﹠amp; Plastics, Minneapolis, plate washed with heptane MN), and use the ethanol rinsing.After 15 minutes, will be coated on the one side of every block of plate by 1% primer solution of embodiment 15 preparations with a cotton coating machine.Then, will be glued together through the plate of primary coat, measure bond strength with the cyanacrylate tackiness agent.The results are shown in Table X.
Table X
| Ground | Bond strength (N/mm 2) |
| ????HDPE | ????2.5 |
| ????PP | ????4.6 |
Present embodiment shows: primer solution of the present invention has caused the polyreaction of cyanacrylate tackiness agent, makes can obtain very high bond strength between the ground of low surface energy.
Embodiment 23
Described in 90 ° of peel adhesion-thermosetting adhesive test methods, the structure of thermosetting adhesive is used in preparation.5% the solution that uses that Table X I lists.
Table X I
| Component | Consumption (g) |
| Weight ratio is 5.5: 3.5: 10 hexanaphthene, dimethylbenzene and an alcoholic acid solvent mixture | ????30 |
| Styrene block copolymer (available from Shell Chemical Company, Houston, TX, commodity are called " FG 1901X ") | ????0.23 |
| Chlorinated Polypropylene III (available from Eastman Chemical, Kingsport, TN, commodity are called " CP 343-3 ") | ????0.92 |
| Resins, epoxy (available from Shell Chemical Company, Houston, TX, commodity are called " Epon 828 ") | ????0.15 |
| The epoxy silane coupler (available from OSi Specialties Inc., Danbury, CT, commodity are called " Silquest A 186 ") | ????0.15 |
| Weight ratio is Isooctyl acrylate monomer/N-caprolactam/acrylate copolymer (40% solid) of 78: 21: 1 | ????1.8 |
| The trolamine titanic acid ester (available from E.I.du Pont de Nemours Company, Wilmington, DE, commodity are called " Tyzor TE ") | ????0.07 |
Originally, make the solution of the about 1.5ml of surperficial overflow of sample, by above-mentioned test method abrasion.Control sample is denuded under the situation of no primer solution.The results are shown in Table X II.
Table X II
| 90 ° of peel value | (N/100mm) | |
| Solution | ????LDPE | ????PP |
| Contrast | ????17.5 | ????14.0 |
| Embodiment 23 | ????163.0 | ????502 * |
*Film destroy has promptly surpassed film strength and has made film distortion.
Compare with ground, use solution of the present invention can improve 90 ° of peel value greatly without primary coat.
Embodiment 24
The TPO plate of 51mm * 25.4mm * 5mm (available from Himont USA, Inc., Lansing, MI, commodity are called " ETA 3163 ") is cleaned twice with ethanol, make its drying.To brush on the one side of every block of plate by 5% solution of embodiment 23 preparation, make its dry 24 hours.
Come bonding plate with bi-component epoxy tackiness agent (from Minnesota Mining and Manufacturing Company, St.Paul, MN, commodity are called " Scotch-Weld 2216 B/A "), form the overlap joint of 25.4mm * 12.7mm through primary coat.Sample was solidified 72 hours under the weight of 150g.Do not use any primer solution, the preparation control sample.The Instron tensile testing machine (available from Instron Corp., Canton, MA) in, with the pinblock speed measurement bond strength (N/mm of per minute 12.7mm
2).Among the Table X III, the value of embodiment 24 is three mean values of measuring, and the value of control sample is the value of one-shot measurement.
Table X III
| Bond strength (N/mm 2) | |
| Solution | ????TPO |
| Control sample | ????0.34 |
| Embodiment 24 | ????1.65 |
B. pressure sensitive adhesive
Embodiment 25
Present embodiment has been described the of the present invention a kind of preferable blend as pressure sensitive adhesive.
The component of consumption shown below added in 1 liter the container.
| Component | Consumption (g) |
| The styrene-ethylene/butylene-styrene elastomerics of maleation (available from Shell Chemical Company, Houston, TX, commodity are called " Kraton FG 1901 X ") | ????100 |
| Tackifier (available from Hercules Inc., Wilmington, DE, commodity are called " Regalrez 1018 ") | ????75 |
| Tackifier (available from Hercules Inc., Wilmington, DE, commodity are called " Rez-D 2084 ") | ????75 |
| Tackifier (available from Hercules Inc., Wilmington, DE, commodity are called " Regalrez 1078 ") | ????25 |
| Oxidation inhibitor (available from Ciba-Geigy Corp., Hawthorne, NY, commodity are called " Irganox 1076 ") | ????1 |
| Oxidation inhibitor (available from American Cyanamid Company, Wayne, NJ, commodity are called " Cyanox LTDP ") | ????1 |
| Ultraviolet inhibitor (available from Ciba-Geigy Corp., Hawthorne, NY, commodity are called " Tinuvin 328 ") | ????0.3 |
| Ultraviolet inhibitor (available from GAF Corp., New York, NY, commodity are called " Unvinal 400 ") | ????0.3 |
| Toluene | ????323 |
| Ethanol | ????16.5 |
This container that vibrates obtains solution until components dissolved, and the total solids that this solution contains is about 45%, and viscosity is about 1300cps (use the Brookfield viscometer, Model HAT, No. 4, measuring shaft, rotating speed is that 50rpm measures).This solution is called " segmented copolymer " herein.
The segmented copolymer of 43.3g Isooctyl acrylate monomer/acrylamide (IOA/ACM) multipolymer by embodiment 6 preparations with 26.2g is added in the container of 118ml, and the vigorous stirring blend mixes until it.Give the container cover upper cover, heated about 1 hour down at 65 ℃.Then, the vigorous stirring blend, and make its standing over night.Blend contains the IOA/ACM multipolymer of the segmented copolymer and 35% (weight) of 65% (weight).After appropriateness stirred, scraper gap was set to about 0.25mm, with the knife coater of laboratory 152mm blend was coated on the polyethylene terephthalate film of orientation that thickness is 0.025mm.Film that will be through applying was in 95 ℃ of dry airs 15 minutes, and the average coat weight that obtains is about 6.0mg/cm
2Prepare sample by above-mentioned test method, test its peel adhesion and shearing resistance glass, new LDPE (film grade) (LDPE), polypropylene (PP) and stainless steel (SS) surface.The results are shown in Table XIV.
Table X IV
| Tackiness agent | Peel value (N/100mm) | Shearing resistance (minute) | |||
| Glass | ??LDPE | ????PP | ????SS | ||
| Embodiment 23 | ????68 | ????29 | ????52.5 | ????61 | ????220 |
The result of Table X IV shows: can prepare useful pressure sensitive adhesive by blend of the present invention.
C. transition layer (tie layers)
Embodiment 26
Acrylic ester polymer described in block copolymer solution described in the 15g embodiment 1 and the 30g embodiment 1 is mixed, make blend.With this blend and 1g Resins, epoxy (available from Shell Chemical Company, Houston, TX, commodity are called " Epon 828 "), the 3.0g Chlorinated Polypropylene III is (available from Eastman ChemicalCompany, Kingsport, TN, commodity are called " CP 343-3 "), the 2.5g silane coupling agent is (available from OSiSpecialties, Danbury, CT, commodity are called " Silquest A 186 "), 4g trolamine titanic acid ester is (available from E.I.du Pont de Nemours; Company, Wilmington, DE, commodity are called " Tyzor TE ") and the 99g weight ratio be that 5.5: 3.5: 1.0 hexanaphthene, dimethylbenzene and alcoholic acid solvent mixture mixes, make to be about 18% solution.
(available from LawrenceFredrick Company, Greenwood is on lacklustre one side IL) at the aluminum strip of three 152.4mm * 24.5mm * 1.3mm with this solution-cast.Dry thickness is the solution coatings of 0.25mm, forms the adhesive coating that thickness is about 0.037mm on every.
To brush on TPO (TPO) plate at three 152.4mm * 24.5mm * 2.5mm (available from Himont USA, Inc., Lansing, MI, commodity are called " ETA 3095 ") as 3% primer solution of preparation among the embodiment 15, make its drying.Under low pressure in 200 ℃, the aluminum strip that will apply through tackiness agent is distinguished lamination 15,30 and 45 seconds with about 137mm's through the TPO of primary coat plate.The peel value that records is respectively 175.4N/100mm, 245.6N/100mm and 265N/100mm.
Present embodiment has illustrated the present composition as the tackiness agent transition layer that the differing materials lamination is got up.
Claims (4)
1. strengthen the method for the bounding force between ground and the tackiness agent, may further comprise the steps:
Come the described ground of primary coat by use blend on described ground, described blend comprises
(a) segmented copolymer of modification, this multipolymer comprises
(i) the polystyrene section and
(ii) polydiene section or hydrogenant polydiene section, described polydiene section or hydrogenant polydiene section are modified as and on average contain one or more carboxyls; With
(b) comprise the polymkeric substance of the polymeric reaction product of two or more monoene unsaturated monomers, wherein:
(i) at least a monomer be contain the acrylate of non-tertiary alcohol of 1 to 14 carbon atom or methacrylic ester and
(ii) at least a monomer is nitrogenous monomer; And
Tackiness agent is applied on the ground of primary coat.
2. the method for claim 1 is characterized in that described ground comprises low-yield ground.
3. the method for claim 1 is characterized in that described tackiness agent is selected from pressure sensitive adhesive, thermosetting adhesive, thermoplastic binder and mixed adhesive.
4. the method for primary coat ground is included in and is coated with blend on the ground, and this blend comprises
(a) segmented copolymer of modification, this multipolymer comprises
(i) the polystyrene section and
(ii) polydiene section or hydrogenant polydiene section, described polydiene section or hydrogenant polydiene section are modified as and on average contain one or more carboxyls; With
(b) comprise the polymkeric substance of the polymeric reaction product of two or more monoene unsaturated monomers, wherein,
(i) at least a monomer is acrylate or the methacrylic ester that contains the non-tertiary alcohol of 1 to 14 carbon atom, and
(ii) at least a monomer is nitrogenous monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194938A CN1188500A (en) | 1995-06-22 | 1996-05-08 | Method of using acrylate-containing polymer blends |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/493,570 | 1995-06-22 | ||
| CN96194938A CN1188500A (en) | 1995-06-22 | 1996-05-08 | Method of using acrylate-containing polymer blends |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1188500A true CN1188500A (en) | 1998-07-22 |
Family
ID=5128911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194938A Pending CN1188500A (en) | 1995-06-22 | 1996-05-08 | Method of using acrylate-containing polymer blends |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1188500A (en) |
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| US8703297B2 (en) | 2004-10-21 | 2014-04-22 | Nitto Denko Corporation | Charge-preventing optical film, charge-preventing adhesive optical film, manufacturing method thereof, and image display device |
| US8883251B2 (en) | 2003-04-21 | 2014-11-11 | Nitto Denko Corporation | Antistatic optical film, method for manufacturing the same and image viewing display |
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| CN105593275A (en) * | 2013-10-02 | 2016-05-18 | 3M创新有限公司 | Articles and methods comprising polyacrylate primer with nitrogen-containing polymer |
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| CN106661409A (en) * | 2014-08-29 | 2017-05-10 | 德莎欧洲公司 | Primer for adhesive tapes |
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-
1996
- 1996-05-08 CN CN96194938A patent/CN1188500A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8883251B2 (en) | 2003-04-21 | 2014-11-11 | Nitto Denko Corporation | Antistatic optical film, method for manufacturing the same and image viewing display |
| US8703297B2 (en) | 2004-10-21 | 2014-04-22 | Nitto Denko Corporation | Charge-preventing optical film, charge-preventing adhesive optical film, manufacturing method thereof, and image display device |
| TWI494222B (en) * | 2004-10-21 | 2015-08-01 | Nitto Denko Corp | Anti-charge adhesive optical film and image display device |
| CN105593275A (en) * | 2013-10-02 | 2016-05-18 | 3M创新有限公司 | Articles and methods comprising polyacrylate primer with nitrogen-containing polymer |
| CN105593323A (en) * | 2013-10-02 | 2016-05-18 | 3M创新有限公司 | Article comprising polyacrylate pressure sensitive primer and adhesive comprising polyacrylate component |
| TWI670350B (en) * | 2013-10-02 | 2019-09-01 | 美商3M新設資產公司 | Article comprising polyacrylate pressure sensitive primer and adhesive comprising polyacrylate component |
| CN105593275B (en) * | 2013-10-02 | 2020-10-30 | 3M创新有限公司 | Articles and methods including polyacrylate primers with nitrogen-containing polymers |
| CN106459714A (en) * | 2014-05-09 | 2017-02-22 | 德莎欧洲公司 | Primer for enhancing tape adhesion to hydrophilic surfaces |
| CN106459714B (en) * | 2014-05-09 | 2019-08-09 | 德莎欧洲股份公司 | For reinfored glue band to the priming paint of the adhesiveness of hydrophilic surface |
| CN106661409A (en) * | 2014-08-29 | 2017-05-10 | 德莎欧洲公司 | Primer for adhesive tapes |
| CN106661409B (en) * | 2014-08-29 | 2019-04-12 | 德莎欧洲股份公司 | Priming paint for adhesive tape |
| CN114085630A (en) * | 2021-11-24 | 2022-02-25 | 苏州德佑新材料科技股份有限公司 | Preparation method of coating adhesive |
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