CN1219261A - Tamper indicating multilayer sheet - Google Patents
Tamper indicating multilayer sheet Download PDFInfo
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- CN1219261A CN1219261A CN97194712A CN97194712A CN1219261A CN 1219261 A CN1219261 A CN 1219261A CN 97194712 A CN97194712 A CN 97194712A CN 97194712 A CN97194712 A CN 97194712A CN 1219261 A CN1219261 A CN 1219261A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
- G09F3/0292—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time tamper indicating labels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2519/00—Labels, badges
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention refers to a multilayer sheet (1) comprising a flexible backing (2) and a pressure-sensitive adhesive layer (3) for attaching the multilayer sheet to a smooth and rigid surface (5), wherein the pressure-sensitive adhesive is completely removable from the surface (5) and is selected to exhibit for an adhesive layer with a thickness of 300 mu m a 90 DEG peel adhesion of between 20 and 85 N/inch from glass after a dwell time of 3 days at a temperature of 70 DEG C. The flexible backing (2) preferably comprises at least one damagable layer (4) and shows intralayer failure when peeling off the multilayer sheet (1) from the surface (5). The present invention furthermore refers to a pressure-sensitive adhesive which is obtainable by polymerizing a precursor comprising a) a monomer component which contains one or more alkyl acrylates, the alkyl groups of which have an average of 4-14 C atoms, and 2-8 phr of at least one copolymerizable monomer having a polar group, b) 5-15 phr of hydrophobic silica, c) one or more polymerization initiators, and d) one or more cross-linker compounds in a concentration resulting in a cross-link density obtainable by using hexanedioldiacrylate as a reference cross-linker compound in a concentration between 0.06 and 0.14 phr. The present invention furthermore refers to a pressure-sensitive adhesive which is obtainable by polymerizing a precursor comprising a) a monomer component which contains one or more alkyl acrylates, the alkyl groups of which have an average of 4-14 C atoms, and 8-20 phr of at least one copolymerizable monomer having a polar group, b) 5-15 phr of hydrophobic silica, c) one or more polymerization initiators, and d) one or more cross-linker compounds in a concentration resulting in a cross-link density obtainable by using hexanedioldiacrylate as a reference cross-linker compound in a concentration between 0.06 and 0.11 phr.
Description
FIELD OF THE INVENTION
The present invention relates to the multi-layer sheet that contact adhesive applies, this sheet material is used as movably paste, is used for smooth and hard surface, and as glass or japanning metal surface, paste takes this to show better anti-disturbance performance.The invention still further relates to the pressure sensitive adhesive material that is used for these multi-layer sheets.
The background of invention
Multi-layer sheet as anti-disturbance label and paste is known.For example, WO 95/29474 has described a kind of paste that is used to adhere to the vehicle window inboard.DE 4405946 has also described the anti-disturbance paste that is used for transparent surface such as windshield.DE 4314579 has described the anti-disturbance windshield that contains hologram.Knownly in the prior art will prevent that the disturbance paste is designed to smooth surface such as glass are had very high bounding force, can durable adhesion, only just can remove by means of solvent and/or machinery scraping.
In some cases, transparent polymer paper tinsel or sheet (as the polycarbamate paper tinsel) are laminated on the inside surface of windshield.For provisional paste, must use solvent and/or machine tool, this is inconvenient, and polymer sheet or paper tinsel can easily be damaged by solvent and scraping.Therefore, be necessary to provide the multi-layer sheet that for example is used as paste, it can easily remove from smooth and hard surface, also shows the interference guard dynamic characteristic better.
Be used to prepare that the paste with enough high adhesions makes its anti-disturbance and need not be unavailable in the prior art by solvent or the removable multi-layer sheet of machinery scraping.
Brief description of drawings
The present invention relates to multi-layer sheet (1), it comprises flexible liner (2) and is used for multi-layer sheet is bonded in the pressure-sensitive adhesive layer (3) of smooth and rigid surface (5), wherein contact adhesive can easily be removed and this contact adhesive is selected from surface (5), so that thickness is the bonding coat of 300 μ m, after 70 ℃ of temperature leave standstill 3 days when 90 ° of peel adhesion on glass are 20-85N/.In a preferred embodiment, flexible liner (2) comprises at least one deck can decrease layer (4), damages in display layer when multi-layer sheet (1) is peelled off on surface (5).
The invention still further relates to the contact adhesive that can obtain by the precursor polymeric that will comprise following material, these materials are:
A) a kind of monomer component, described monomer component comprises one or more alkyl acrylate, and its alkyl has an average 4-14 carbon atom, and comprises at least a copolymerisable monomer that polar group is arranged of 2-8phr,
B) 5-15phr hydrophobic silica,
C) one or more polymerization initiators and
D) it is that the hexanediyl ester of 0.06-0.14phr is made the available cross-linking density of reference crosslinker compound that one or more crosslinker compounds, its concentration can cause with concentration.
The invention still further relates to the contact adhesive that can obtain by the precursor polymeric that will comprise following material, these materials are:
A) a kind of monomer component, described monomer component comprises one or more alkyl acrylate, and its alkyl has an average 4-14 carbon atom, and comprises at least a copolymerisable monomer that polar group is arranged of 8-20phr,
B) 5-15phr hydrophobic silica,
C) one or more polymerization initiators and
D) it is that the hexanediyl ester of 0.06-0.10phr is made the available cross-linking density of reference crosslinker compound that one or more crosslinker compounds, its concentration can cause with concentration.
The detailed description of invention
Multi-layer sheet of the present invention (1) comprises flexible matrix (3) and is used for this film is bonded in pressure-sensitive adhesive layer (3) on the smooth and rigid surface (5) (as glass, metal or japanning metal surface).
When attempting to remove multi-layer sheet (1) from the surface, preferably damage in the display layer of flexible matrix (2), thus give multi-layer sheet (1) anti-disturbance feature.One deck or which floor flexible matrix (2) can comprise, preferably at least 2 layers.Flexible matrix (2) preferably comprises at least one deck can decrease layer (4), and this can decrease the thin spot that layer is designed to multi-layer sheet of the present invention (1), and therefore is predefined in the impaired loci when multi-layer sheet (1) is peeled off on surface (5).Can decrease the i.e. exposed surface not of internal layer that layer (4) is preferably multi-layer sheet (1), and have 2 adjoining courses of multi-layer sheet.Flexible matrix also can comprise for example overlayer (6) (not shown) or retroreflective layer (7).
Multi-layer sheet of the present invention (1) can be easily remove from surface (5) and not stay any residue.Term " can easily remove " and mean after the operating period available hand contact adhesive is removed from surface (5), and without chemicals such as organic solvent or machine tool such as pocket knife or scraper.
Because the unique combination of interference guard dynamic characteristic and the characteristic that (as glass or japanning metal) removes easily from the surface, comprise the multilayer film of the present invention that can decrease layer (4) and be particularly useful for making provisional label, as the anti-fake mark on paid labeling of the toll on the vehicle (toll vignettes) or the commodity.
The contact adhesive that selection is used for multi-layer sheet of the present invention (1) is to show the height bounding force to flexible matrix (2) the flexible matrix layer of pressure-sensitive adhesive layer (3) (promptly in abutting connection with).Can clearly peel off and not damage flexible matrix (2) from bonding coat for fear of flexible matrix, in comprising the multi-layer sheet of the present invention that can decrease layer (4), this bounding force must be higher than internal intensity or the cohesive strength that can decrease layer (4).With no damage from this sur-face peeling, contact adhesive and smooth and rigid surface (5) bonding also must be higher than the internal intensity that can decrease layer (4) for fear of multi-layer sheet (1).This bonding agent not only must at room temperature be not easy to peel off, but also must be bonding at elevated temperatures fine, and resist complete attempt of removing multi-layer sheet (1).On the other hand, the bounding force between pressure-sensitive adhesive layer and smooth, the hard surface must be not paramount to causing the durable adhesion of pressure-sensitive adhesive layer with surface (5).
We find, the contact adhesive (is the bonding coat of 300 μ m for thickness) that is used for multi-layer sheet of the present invention (1), after 70 ℃ of temperature leave standstill 3 days, record when 90 ° of peel adhesion on glass are 20-85N/ with following concrete test method, particularly during 30-75N/, more especially during 30-70N/.Pressure sensitive adhesive material with this test method evaluation is smooth for glass surface and other, (as metal or japanning metal surface is useful to rigid surface.This pressure sensitive adhesive material is particularly useful to glass surface.
Contact adhesive penetrability height of the present invention, the mark (4d) that consequently forms flexible matrix (a 2) part can be seen by bonding coat (3) as printed patterns.The visible light transmittance rate of contact adhesive is at least 80%, is preferably at least 90%.The contact adhesive that is used for multi-layer sheet of the present invention is more preferably on the optics clearly, and is promptly colourless.
We find that the concrete kind of contact adhesive that satisfies above-mentioned requirements can obtain by the precursor polymeric that will comprise following material, and these materials are:
A) a kind of monomer component, described monomer component comprises one or more alkyl acrylate, and its alkyl has an average 4-14 carbon atom, and comprises at least a copolymerisable monomer that polar group is arranged of 2-8phr,
B) 5-15phr hydrophobic silica,
C) one or more polymerization initiators and
D) it is that the hexanediyl ester of 0.06-0.14phr is made the available cross-linking density of reference crosslinker compound that one or more crosslinker compounds, its concentration can cause with concentration.
These contact adhesives are new materials, and they are theme materials of the present invention.The pressure-sensitive adhesive tape that contains hydrophobic silica is at US4, general description arranged in 749,5990.Originally these bands are displaceable allegedly, " but just can not move usually in several days " (49-50 is capable for US4, the 749,590, the 4th hurdle).US4,895,745 have described the black acrylic pressure-sensitive adhesive that contains hydrophobic silica and pigment such as carbon black pigment, the front type paste that needs the high-transmittance contact adhesive that such contact adhesive can not be used for for example below will describing.
Term " average 4-14 carbon atom " means the carbon atom average of the alkyl acrylate ester compounds that the quality weighting of alkyl acrylate ester compounds composition is obtained by percent by weight separately between 4-14, particularly between the 4-12.
Useful alkyl acrylate (being alkyl acrylate monomer) comprises the straight or branched list official acid esters unsaturated propylene of energy or the methacrylate of non-tert-alkyl alcochol, and its alkyl has 4-14 (particularly 4-12) carbon atom.The example that is used for these rudimentary alkyl acrylate of the present invention includes, but is not limited to n-butyl acrylate, isobutyl acrylate, Hexyl 2-propenoate, 2-EHA, Isooctyl acrylate monomer, the acrylic acid n-octyl, n octyl methacrylate, acrylic acid 2-methyl butyl ester, acrylic acid ester in the different ninth of the ten Heavenly Stems, acrylic acid ester in the positive ninth of the ten Heavenly Stems, the acrylic acid isopentyl ester, acrylic acid ester in the positive last of the ten Heavenly stems, isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, acrylic acid 4-methyl-2-pentyl ester and acrylic acid dodecane ester.Preferable rudimentary acrylate and methacrylate comprise Isooctyl acrylate monomer, n-butyl acrylate, 2-EHA, acrylic acid ester in the different ninth of the ten Heavenly Stems and acrylic acid dodecane ester.
Preferable precursor comprises and is no more than 5 kinds of (particularly 1-4 kind) alkyl acrylate.As mentioned above, the carbon atom average in the alkyl of alkyl acrylate is preferably 4-14, particularly 4-12, more especially 5-10.The concentration of alkyl acrylate composition is preferably at least 75 weight % with respect to the quality of pressure sensitive adhesive precursor, particularly at least 85 weight %.
Except alkyl acrylate, the precursor of described PSA can comprise unsaturated aliphatic carboxylic acid alkane ester for example maleic acid alkane ester and alkane fumarate ester (respectively based on maleic acid and fumaric acid).In this respect, preferable is dibutyl maleate, di-2-ethylhexyl maleate, dibutyl fumarate and dioctyl fumarate.The amount of unsaturated aliphatic carboxylic acid rather than acrylic acid ester compounds should not be too high, and particularly the quality with respect to the alkyl acrylate composition is no more than 25 weight %.
The term polar monomer comprises moderate polarity and strong polar monomer.Polarity (being the hydrogen bonding ability) is commonly used to be described such as " by force ", " moderate " and " weak ".The document of describing these and other solubleness term comprises " Solvents ", Paint Testing Manual, 3rd ed., G.G.Seward, Ed., American Societyfor Testing and Materials, Philadelphia, Pennsylvania and " A three-DimensionalApproach to Solubility ", Journal of Paint Technology, Vol.38, No.496, pp.269-280. the example of strong polar copolymerizable monomer is an acrylic acid, methacrylic acid and acrylamide, and the N-vinyl lactam is (as the N-vinyl pyrrolidone, the N-caprolactam, the amino propyl ester of vinyl cyanide and dimethylaminoethyl acrylate methyl base) be the exemplary of moderate polar monomer.
But described precursor comprises one or more copolymerization polar monomers of 2-8phr.If but the amount of copolymerization polar monomer surpasses 8phr, then too high from 90 ° of peel adhesion on glass, the contact adhesive durable adhesion that becomes.If but the amount of copolymerization polar monomer is lower than 2phr, then too low from 90 ° of peel adhesion on glass, can not guarantee that multi-layer sheet (1) can not intactly be removed from glass when applying such as high temperature.
But the amount of copolymerization polar monomer is good with 2-7phr, is special good with 3-6phr.
The contact adhesive that is used for multilayer film of the present invention also comprises the 5-15phr hydrophobic silica.In a good especially embodiment, the amount of hydrophobic silica is between 7.5-15phr, particularly between 10-15phr.
Hydrophobic silica has commercially available product, for example can derive from " Aerosil " R972, R974 and the R9976 of Degussa.According to the Degussa bulletin that was entitled as " product information " on June 4th, 1984, hydrophobic silica " Aerosil " R972, R974 and R976 are respectively 130,200 and 300m from the surface area that is called " Aerosil " 130,200 and 300 respectively
2The water wettability silicon dioxide of/g is made.Hydrophobic silica also can get Cabot Cab-O-sil Division freely, Tuscola, and Illinois, USA is called TS-720.Propose among the US2,859,198 (Sears et al.), the material (as silicon dioxide) that contains the inoganic solids silicon of segmentation can obtain hydrophobicity through the organosiloxane material processed.According to US4,136,081 (Schultz), silicon dioxide " available organosilicon material such as chlorosilane, silazane, alkoxy silane and cyclosiloxane is handled, and produces hydrophobic surface " (the 6th hurdle 47-52 is capable).
The detailed catalogue of the hydrophobic silica material that obtains above and some method for preparing hydrophobic material of selecting be interpreted as be illustrative rather than restrictive.The hydrophobic silica that is used to prepare PSA material of the present invention is at least 10m with surface area
2/ g is good, particularly 50m at least
2/ g.That the surface area of hydrophobic silica is good especially is 50-400m
2/ g (B.E.T. surface area).
In pressure sensitive adhesive precursor, add hydrophobic silica with concrete amount, give enough bounding forces of contact adhesive or interior intensity, make bonding agent have toughness and rubbery character.This can allow to accomplish to remove adhesive residue from for example glass surface, need only catch the edge of adhesive residue that it is pulled off on glass matrix fully.Thereby can remove the paste residue of whole adhesive residue or application of adhesive by hand.Be lower than 5phr if the concentration of hydrophobic silica is chosen as, find that contact adhesive splits when attempting to remove most of bonding agent, thereby must use machine tool and/or chemicals such as organic solvent.The concentration of hydrophobic silica is increased to more than the 15phr then to from 90 ° of release adhesive character on glass harmful effect being arranged.
Therefore, with suitable selected amount hydrophobic silica being added in the pressure sensitive adhesive precursor is that to set up needed contact adhesive (3) necessary from the removability of surface on (5).Other filler (as water wettability silicon dioxide or polysaccharide filler) is found has harmful effect to the optical property of contact adhesive such as transparency and/or engineering properties such as physical strength.
The pressure sensitive adhesive precursor that is used for multilayer film of the present invention also comprises bond strength and the tensile strength of one or more crosslinker compounds with the PSA material of increase gained.
Useful crosslinking chemical comprises benzaldehyde, acetaldehyde, anthraquinone, various benzophenone type and vinyl-halogenated methyl-s-triazine type compound, and as 2,4-two (trichloromethyl)-6-is to methoxyl-styrene-s-triazine.Preferable is many trifunctional acrylate monomers, as trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, 1,2-glycol diacrylate, tripropylene glycol and acrylate, 1,6 hexanediol diacrylate or 1,12-dodecanediol diacrylate.Above listed compound (can be substituted or unsubstituted) be illustrative rather than restrictive.
Being used for crosslinked composition of the present invention is good to contain 1-5 kind crosslinker compound, particularly 1-3 kind, more especially 1-2 kind.Good especially crosslinker compound is 1,6 hexanediol diacrylate and tripropylene glycol diacrylate.
Degree of crosslinking (crosslinked density) can be expressed as the number of crosslinks of every gram or per unit volume polymkeric substance, can estimate theoretically or measuring, for example, obtain (seeing Encyclopediaof Polymer Science and Engineering by swelling mensuration or through stress-strain diagram, 2nd ed., New Yorl 1988, col.4, p.355-357).Swelling is measured the detailed description of (preferably) and is seen P.J.Flory, Principles of Polymer Chemistry, CornellUniversity Press, Ithaca and London, 1952, pg.579.With crosslinking chemical composition difference and the identical two kinds of different precursors of others in same external reaction condition (as polymerizations such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerizations, temperature, pressure, irradiation in the ultraviolet polymerization reaction, or the like) under react, the cross-linking density of gained depends on the chemical nature of used crosslinking chemical, its functionality and concentration separately.In should using, the cross-linking density of being reported be hexanediyl ester (HDDA) with variable as reference crosslinking chemical composition in (the body photopolymerization of standard reaction condition, light trigger: Irgacure 651, Ciba Geigy supply, concentration is 0.24phr; The UV irradiation of uviol lamp is 900-1500mJ/cm
2, its emission 90% between 300-400nnm, emission maximum is at 351nm; Room temperature; Normal pressure; Starvation) available cross-linking density under.
The precursor that is used for multi-layer sheet of the present invention is preferably and comprises one or more crosslinker compounds, and its concentration is for obtaining the available cross-linking density with 0.06-0.14phr concentration HDDA.The concentration of HDDA is good with 0.08-0.14phr, and that good especially is 0.09-0.13phr.
If its concentration of crosslinker compound of using can reach the available cross-linking density of HDDA that is lower than 0.06phr with concentration, the bond strength of the contact adhesive of gained and tensile strength are too low like this.In this case, find that bonding coat can sever with for example razor, this removes and not impaired multilayer film from described surface, and multi-layer sheet can be adhered on other surface again.If its concentration of crosslinker compound of using can reach the available cross-linking density of HDDA that is higher than 0.14phr with concentration, too low from the 90 ° of peel adhesion in surface, can not guarantee when matrix is peelled off multilayer film, to contain the damage of the flexible liner (2) that can decrease layer (4).
Pressure sensitive adhesive material used in the multi-layer sheet of the present invention can obtain with common known polymerization (as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization).Because environment, for fear of with an organic solvent, bulk polymerization usually is desirable.
Polyreaction is advisable to start by polymerization initiator, is preferably through free radical polymerization mechanism and carries out.The example of useful polymerization initiator comprises that light can activate initiating agent, for example benzoin ethers is (as the benzoin ethers of benzoin methyl ether, benzoin isopropyl ether, replacement, as the anisoin methyl ether), the acetophenone class is (as 2,2-diethoxy acetophenone) or alpha-ketol (as 2-methyl-2-hydroxyl-Propiophenone) and/or the heat initiating agent that can activate, for example organic peroxide (as benzoyl peroxide and lauroyl peroxide) and 2,2 '-azo two (isobutyronotrile).The adding that photopolymerization and light can activate initiating agent is preferably.The initiating agent composition is preferably and comprises the 1-3 kind, particularly 1-2 kind initiator compounds; Good especially is the initiating agent composition that only comprises a kind of light trigger.The amount of initiating agent composition is advisable with 0.01-2.00phr, particularly 0.05-1.00phr, more especially 0.1-0.5phr.
In a preferable preparation method, part initiating agent composition is added in the alkyl acrylate composition, the latter is aggregated to the degree of typical 2-30% in common room temperature lower part, form a kind of apply viscosity (as 300-20, the 000cps) syrup of (Brookfield).The viscosity of syrup is preferably regulated by the amount of the hydrophobic silica that will add.In order to add a large amount of hydrophobic silicas, 12-15phr for example, the viscosity of syrup is to be no more than 1, and 000cps is advisable, particularly between 250-100cps.In order to add a small amount of hydrophobic silica, viscosity is to be not less than 1, and 500cps is advisable, and particularly 1,750cps or higher.The viscosity of precursor also can be regulated by adding a small amount of (typically be and be less than 5phr) polymeric additive (as the polyacrylate of WO 94/00,052 described photopolymerizable).Polyreaction is preferably carried out photopolymerization by US for example 4,182,752 is described.In a preferable embodiment, with UV black light (its emission spectrum (is preferably more than 75%) more than 60% between 280-400nm, intensity about 0.1 to about 25mW/cm
2) carry out polymerization.Exposure is typically at 900-1,500mJ/cm
2Between.Can stop polymerization by the oxygen of removing irradiation or thermal source and/or introduce as removing free radical.
The filler composition that then will mainly comprise hydrophobic silica is added in the syrup after the prepolymerization.When the amount of hydrophobic silica surpassed about 8phr, the discovery mixer that must use high shearing force was as paint mill, to obtain uniform dispersion liquid.Do like this, and by regulating the viscosity of prepolymerization syrup suitably, can obtain basically dispersion liquid uniformly, this dispersion liquid can be loaded up to 25phr.Used contact adhesive comprises the hydrophobic silica that is no more than 15phr in the multi-layer sheet of the present invention.
The dispersion liquid of gained is mixed with the remainder of initiating agent, and randomly with other adjuvant (for example chain-transferring agent, as EP0,349,216 or EP0,352,901 described polymeric additives, solvent, fire retardant, screening odorant agent and/or other adjuvant known in the art) mix.Pigment and colorant are good not to be incorporated as, because it is high and clear for good with penetrability to be used for the contact adhesive of multi-layer sheet of the present invention.If add pigment/colorant and/or paint, should select to make its color not have dysgenic to the transparency and the sharpness of gained PSA material.The example of suitable paint is to derive from SICPA Druckfarben, the Yellow PermalinkCTL-Druckfarbe of Backnang (printing paint).
In order to prepare the used PSA film of multi-layer sheet of the present invention, the as above dispersion liquid or the potpourri of gained are coated on liner, support fabric or the release liner, and are to carry out polymerization under the anaerobic atmosphere (as nitrogen atmosphere) in inertia.Above and term hereinafter " film " be used to describe the structure of a kind of its thickness much smaller than its length or width, it has two substantially parallel pros and cons.At this, this term comprises for example sheet material, ribbon, band and disk.
The decreased layer (4) that is used for anti-disturbance multi-layer sheet (1) of damage or irreversible transformation has description in the literature when throwing off multi-layer sheet (1).
One deck or which floor can decrease the layer (4) insert multi-layer sheet of the present invention (1) be choose wantonly but also be preferably.The present invention also comprises not containing and can decrease layer (4) and contain flexible liner (2) and make multi-layer sheet be attached to the multi-layer sheet of the pressure-sensitive adhesive layer (3) of smooth and rigid surface (5).
Can decrease the pattern (4a) of the adjusting bounding force material on the inside surface that layer (4) for example can comprise the pressure-sensitive adhesive layer that can discontinuous mode be applied to multi-layer sheet (1) and/or other layer.The material of this adjusting bounding force only covers an one deck or which floor a part in these layers, thereby produces the surface area that different bond propertiess are arranged.The material of regulating bounding force can be the material that reduces bounding force, as the agent that gets loose, and maybe can be to promote bonding material, as priming paint.
Reduce bounding force pattern (4a) and can be applied to for example inside surface of pressure-sensitive adhesive layer (3).In the zone that does not reduce the bounding force material, the bounding force height of pressure-sensitive adhesive layer (3) and flexible matrix adjoining course is having the zone that reduces the bounding force material, and pressure-sensitive adhesive layer (3) is very low with the bounding force of flexible matrix adjoining course.In having the zone that reduces the bounding force material, between the adjoining course of pressure-sensitive adhesive layer (3) and flexible matrix, in fact usually there is not bounding force.
In order to set up pattern (4a), available different materials is as reducing bounding force or anti-bonding material.These examples of material comprise carbamate, as deriving from Hoechst AG, the polyvinyl carbamic acid octadecane ester of Germany " Kalle releasecoat K " by name maybe can derive from Aderson Development Company, " the Escoat P20 " of USA.The suitable material that also has comprises the siloxane system, free radical siloxane acrylate mould wash, siloxane addition system, silicone condensation system and the cationic curing siloxane system curable as UV.
Siloxane and non-silicone base reduce the bounding force material and are found in for example US 561,535 in the more fully description of setting up the application on the pattern.
The material that is used for the adjusting bounding force of multi-layer sheet of the present invention (1) also can be the material that strengthens bounding force.Have the zone that strengthens the bounding force material, the bounding force of the layer on the two sides of enhancing bounding force material pattern all strengthens.Do not have the zone that strengthens the bounding force material, the interlayer adhesion of adjacency is limited or once in a while even do not have a bounding force.
There are a few class materials to can be used as the material that strengthens bounding force.They must customize especially in adjacent two-layer, and in this case, the material that strengthens bounding force must may all have good bounding force by adjacent two layers far from it to chemical property.Polyurethane-base priming paint and ethylene-acrylic acid base paint are found and are applicable to the present invention.
The types of patterns that is used to regulate the material of bounding force among the present invention is not crucial.
The pattern (4a) of regulating bounding force is preferably and strengthens the bounding force material and preferablely use with the notch board painting method.
The pattern (4a) of regulating bounding force provides the adjoining course of flexible matrix (2) has different fusible zones, causes adjoining course deformation and/or damage.On this meaning, the pattern (4a) of adjusting bounding force is called the decreased layer in the multi-layer sheet of the present invention.
Can decrease layer (4) and also can comprise crushability optical element or optical layers, as EP 0,253,089; EP 0,401, and 466 and US 5,066, the kinegram described in 041 (4b) or hologram (4b).When attempting disturbance, hologram can be broken.Kinegram can derive from Landis ﹠amp; Gyr, Zug, Switzerland and other company, hologram is very attractive from the viewpoint of aesthetics, they can be used for the photo that the user is specific or information is inserted in the film.Kinegram or hologram can only be used for the limited area of multilayer film, but also may use the holograph layer of the expansion in the reflection horizon that comprises structural sheet and choose wantonly.
This structural sheet can be formed with US 4,0856,857 described known methods more of the prior art.It can be made by the material such as polymethylmethacrylate, nitrocellulose and polystyrene.This structural sheet comprises the diffraction grating image of microstructure relief type holograph pattern or rational form or the pattern of reflection ray.In one embodiment, have the layer of the microstructure of embossed pattern to form like this: the material that will form this structural sheet has the plate of embossed pattern to contact heating and pressurizing with the non-deformable with microstructure embossed pattern.Perhaps, structural sheet can be prepared with any other suitable method, as hardening with radiation, and can be from making such as urethanes, epoxy compound, polyester and acrylate monomer and oligomer, these materials are prepared with light trigger, are cast on the non-deformation instrument with microstructure embossed pattern and hardening with radiation.
Reflection layer is being coated on the structural sheet of holograph layer (4b) before or after the embossing.The reflection horizon cans be compared to structural sheet most and has higher refractive index.In a preferable embodiment, the reflection horizon is transparent and colourless basically.The illustrative example of suitable reflector material includes, but is not limited to US 4,856, the bismuth trioxide described in 857, zinc sulphide, titania and zirconia.The material that transparency is lower also can use as the thin silver-colored or visual refractor of aluminium.Because the refractive index difference between structural sheet and the reflection horizon, reflection horizon increase the reflection of light by structural sheet.Therefore, in case the reflection horizon is coated on the structural sheet, the structural holographic photo-patterns is easier to be visually noticeable, and contact adhesive can directly be applied to structural sheet and not weaken the visibility of structure plan.
The transparent multilayer film of describing among the DE 4424148.8 comprises one deck can decrease layer or irreversible deformable layer (4c), and the latter comprises as hotmelt or contact adhesive, and they also can be used on the multi-layer sheet of the present invention (1).Can decrease the layer or irreversible decrease the layer (4c) also can comprise for example ply of paper, the internal intensity of ply of paper and thickness are chosen to make this ply of paper to become the predetermined disrupted beds of multi-layer sheet (1).
Can decrease layer and also can comprise mark (4d), its available any method (comprising transfer method or directly printing process) applies.With standard printing method (as screen printing) apply be labeled as good.The screen printing printing ink that is usually used in this purpose comprises 3M screen printing printing ink (800 series, 900 series), 45 ℃ of dryings 30 minutes (800 series) or 65 ℃ of dryings 45 seconds (900 series) in forced air oven.Printing ink should be selected can be in low relatively following short time of temperature dry and solidify, and helps making fast and the damage of the responsive to temperature layer that prevents to exist.Printed patterns and other mark have only when as multi-layer sheet have the internal layer of two-layer adjacent layer the time could play a part to decrease layer.For example, printed on top does not play to decrease layer usually.
Printed patterns is described in for example US 4,121,003 and US 4,184,701 as the situation that can decrease layer.
The above-mentioned specific embodiment that decreases layer is in order to set forth rather than limit the present invention.
Used term among the present invention " can decrease layer " but be meant that easy damage is rapid wear and/or non-resilient deformation layer, and they can be continuous or discontinuous.The internal intensity that can decrease layer is that bond strength is low, is removing or the predetermined break-up point of multi-layer sheet when attempting disturbance.But, should be noted that the mode of in fact seeing a lot of breaking-ups about multi-layer sheet of the present invention.The mode of damaging is quite complicated, be subjected to the influence of various parameters, as different layers elasticity or form separately, direction of delaminate and peel angle, peel strength and peeling rate of the tensile strength of fragility, material therefor and the bounding force between the adjacent layer, the thickness of different layers, discontinuous layer (if the words that have) separately and the temperature when peeling off.When one or more parameter changes, the mode of breaking-up can change.For example, when disturbance, because the result that can decrease macromolecular stretching in the layer and be orientated simultaneously, the internal intensity that type (4c) can be decreased layer can increase sometimes, thus one or several other zone of multi-layer sheet is had similarly in addition than can decrease layer littler internal intensity and/or and adjacent layer between bounding force.The non-one deck that decreases layer that this means multi-layer sheet in fact or which floor can be prior to decreasing layer and/or and can decreasing layer simultaneously and/or substitute and can decrease layer and deform and/or irreversible damage.No matter whether the mode mode of promptly no matter damaging of really damaging depends on and can decrease layer and/or other layer, and having the multi-layer sheet (1) that one deck or which floor can decrease layer (4) is theme of the present invention.
Multi-layer sheet (1) also can comprise overlayer (6) (not shown), and it forms the outlier with respect to bonding coat.
According to a kind of typically polymer film of overlayer (6) (not shown) of multi-layer sheet of the present invention, it is good with dimensionally stable, wear-resisting, anti-tear, anti-wear and/or anti-solvent.Overlayer can be made corona treatment, flame treatment, plasma treatment or use chemical prime treatment.
The surface-treated method is at for example G.Habenicht et al., Adhesion, and 1992 (5), pp.21-36 and K.W.Gerstenberg, Coationg, 1990, description is arranged among the pp.260-263.
Material is for example polyethylene terephthalate (PET) polymer film preferably for this purpose.The overlayer of dimensionally stable, wear-resisting, anti-tear, anti-wear and/or anti-solvent protects that each layer of the multi-layer sheet (1) below it is not frayed in the operating period, contamination, moisture and other harmful effect.
Overlayer is good with thickness 10-200 μ m, is more preferred from 10-150 μ m.Good especially is, and thickness is about 10 to about 75 μ m.In order to improve the bounding force with lower floor, this film is preferably with corona discharge or use chemical prime treatment.Priming paint can apply with the method for routine, and as being coated with paint stick, useful thickness is for being no more than 1 μ m.
Also can comprise reflection horizon (7) according to multi-layer sheet of the present invention (1), to increase its visibility.The insertion in reflection horizon (7) be choose wantonly but preferably.The reflection horizon can be a metal level, and the metal forming as thin maybe can comprise one or more reflecting materials, comprises microspheroidal reflecting material and cube--corner reflecting material.US 2,407, and the retroreflective layer of describing in 680 can comprise the glass microsphere individual layer of sealing, and it is spaced apart resin-coating, and the latter comprises for example polyvinyl butyral or polyester.Compartmentalized resin and microballoon match.The reflection horizon that is positioned under the Compartmentalized resin can comprise opaque material, as silver, aluminium, chromium, nickel or magnesium or highly transparent index reflecting material, as above-mentioned those materials (as zinc sulphide) or the reflection multilayer layer that is used for the holograph structural sheet, as US 3,700,305 is described.Therefore, the light that enters retroreflective layer is focused on by glass microsphere by Compartmentalized resin, the layer reflection of being reflected by Compartmentalized resin and glass microsphere to the observer.Other reflecting material that uses glass microsphere is at US 3,801, description arranged in 183.The microspheric reflecting material can derive from for example 3M, St.Paul, and USA is 3M
SCOTCHLITE HighIntensity Vehicle Markoing Sheeting Series No.790; 3M SCOTCHLITE
ValidationSecurity Sheeting Seeries No.5300,5350,5390,4250 and 4290; 3M
SCOTCHLITE
Label Sheeting Series No.5330; And 3M
SCHOTCHLITE
FaceAdhesive Verification Sheeting Series No.2500.
Retroreflective layer (7) also can comprise multiple cube corner retroreflective elements, replace glass microsphere and resin, for the cube corner retroreflective elements that protrudes, they can be by making such as vinyl, polycarbonate or acrylate copolymer, for the cube corner retroreflective elements of hardening with radiation, can make by urethanes, epoxy compound, polyester and acrylate oligomer and monomer.Cube corner element typically has surface area and is about 1.9 * 10
-3Mm
2To 0.1mm
2Three orthogonal.The cube corner retroreflective elements can be embossed into sheet material by pattern master under suitable temperature and pressure.This element also can be built like this: the radiation-hardenable resin-coating to master mold, at enough pressure laminated upper layer films, and is solidified this resin with irradiation method.
The thickness that forms each layer of flexible matrix (2) is good in the 10-1000 mu m range to be chosen in, and is more preferred from 15-500 μ m, and the best is 20-200 μ m.
The material that forms each layer of multi-layer sheet of the present invention (1) can stack and interosculates with various known coating and laminating method.Typically, with only adopting the transfer method of pressurization that pressure-sensitive adhesive layer (3) is laminated on the flexible matrix (2).Each layer of flexible matrix (2) combines under the temperature of room temperature or rising with laminating apparatus usually.
Under the situation of the discontinuous layer such as the pattern of regulating the bounding force material forms mark or pattern cambium layer, can apply these patterns by standard printing technology such as photogravure or screen printing.Discontinuous layer also can for example form on interim matrix such as release liner respectively, and by lamination transfer to other layer of multilayer film.Fig. 1 represents multi-layer sheet of the present invention (1), comprises pressure-sensitive adhesive layer (3), and this pressure-sensitive adhesive layer is bonded in and can decreases on layer or the irreversible deformable layer (4c), can decrease underlined layer (4d) on layer inside surface.Can decrease layer or irreversible deformable layer (4c) can be ply of paper for example.Attempting when matrix removes this multilayer film, mark layer (4d) fragmentation, then or be accompanied by the irreversible transformation and/or the damage of layer (4c) and/or bonding coat (3).
When using ply of paper to do to decrease layer or irreversible deformable layer (4c), the type of paper and the thickness of paper should be selected, and ply of paper are split and irreversibly damage when disturbance is arranged.
If can decrease layer or irreversible deformable layer when being opaque layer (as ply of paper), the multi-layer sheet of Fig. 1 a can be applied to as on glass surface or another kind of transparent, the smooth and hard material (as the polymethylmethacrylate sheet material), and observe from the another side of transparent material by clear binder.This structure (above and hereinafter being called preceding surface structure) can be used for for example windshield paste, and it is applied on the windshield from vehicle interior, can see from the outside.
Fig. 1 b shows the multilayer film that is similar to Fig. 1 a, and the order of its middle level (4c) and mark layer (4d) is anti-comes.This structure (above and hereinafter being called back side type structure) can be used for for example anti-disturbance and removable label or paste, and it is bonded in opaque surface through pressure-sensitive adhesive layer (3), on the japanning metal surface.In this case, the observer watches printed patterns or mark layer (4d).In this structure, printed patterns or mark layer (4d) do not form predetermined breakdown point, because this layer puts on the top of layer (4c), and do not form internal layer as shown in Figure 1a.
Another embodiment (not shown) of coming deriving from Fig. 1 a and 1b, can decrease layer or irreversible deformable layer (4c) to be replaced by retroreflective layer (7), anti-disturbance character is mainly based on mark layer (4d).
Fig. 2 a shows multi-layer sheet of the present invention (1), and it comprises the pressure-sensitive adhesive layer (3) of carrying symbols layer (4d).The holograph layer (4b) that bonding coat is bonding and transparent or semitransparent, bonding as microstructure holograph layer.The light that transparent holograph uses the patterned coatings of the enhancing bounding force material (4a) such as priming paint to be bonded in retroreflective layer (7) enters the surface.The patterned coatings of priming paint has strengthened the bounding force of thin, crisp holograph layer (4b) in the zone of its existence, thereby causes holograph layer (4b) and the irreversible damage of any mark (4d) that may be loaded with when attempting disturbance.
The embodiment of Fig. 2 a is preceding surface structure, and it is in sight by pressure-sensitive adhesive layer and the transparent material that adhered to thereof.
Fig. 2 b is the back side type structure corresponding to Fig. 2 a structure.In this structure, printed patterns or mark (4d) do not form predetermined break-up point, because this layer puts on the top of layer (4b), do not resemble yet and form internal layer the situation of Fig. 2 a.
About Fig. 1 and the described crumbling method of Fig. 2 embodiment is to illustrate and unrestricted, in fact observes other crumbling method, for example, and the crumbling method between described crumbling method.
The present inventor also finds, can obtain contact adhesive by the precursor polymeric that will comprise following material, and these materials are:
A) a kind of monomer component, described monomer component comprises one or more alkyl acrylate, and its alkyl has an average 4-14 carbon atom and comprises at least a copolymerisable monomer that polar group is arranged of 8-20phr,
B) 5-15phr hydrophobic silica,
C) one or more polymerization initiators and
D) it is that the hexanediyl ester (HDDA) of 0.06-0.11phr is made the available cross-linking density of reference crosslinker compound that one or more crosslinker compounds, its concentration can cause with concentration,
Described contact adhesive is presented at the 90 ° of favourable peel adhesion values on smooth and rigid surface such as glass or the japanning metal surface, and these pressure sensitive adhesive material are theme materials of the present invention.The concentration of reference crosslinking chemical HDDA is good with 0.06-0.10, is special good with 0.06-0.09.
Though being used to prepare the amount that the above-mentioned pressure sensitive adhesive material of the pressure-sensitive adhesive layer (3) of multi-layer sheet (1) comprises copolymerisable monomer is 2-8phr, but find to change the amount of copolymerisable monomer for being higher than 8-20phr with polar group, be preferably and be higher than 8-15phr, Te Jia can obtain from the high useful pressure sensitive adhesive material of 90 ° of peel adhesion values on glass when being higher than 8-10phr.This contact adhesive is new, is theme material of the present invention.As top described about the contact adhesive that is used for pressure-sensitive adhesive layer (3), in these pressure sensitive adhesive material, can select alkyl acrylate, have copolymerisable monomer, polymerization initiator and the crosslinking chemical potpourri of polar group, these materials can as noted abovely be prepared like that.
(as glass or painted metals) removes multi-layer sheet of the present invention (1) from hard surface easily, and they are for using temporary marker and the paste (as toll vignettes) that will throw off behind the certain hour particularly useful.In a preferable embodiment, multi-layer sheet (1) comprises one deck or which floor can decrease layer (4), and shows the unique combination of interference guard dynamic characteristic, and year throws off fully and easily.
The present invention is described further by the following examples, and these embodiment are illustrative and nonrestrictive.Following test method is used for characterizing material used among the embodiment.
Test method
From 90 ° of peel adhesion of glass
90 ° of peel adhesion tests are to derive from Pressure Sensitive Tape Council of Glenview, Illinois, the PSTC-3 revision of USA.In this test, flexible retroreflection sheet (3M
Scotchlite
4780, no EAA teleblem derives from 3M, and St.Paul USA) is substituted by the polymer film that is used as liner usually in this test.
Prepolymerization precursor between two-layer carries out photopolymerization and makes the bonding coat of testing with the biaxial orienting silication polyethylene terephthalate (PET) of thickness 50 μ m.The bar of the adhesive material between two polyester sheet is cut into wide 2.54cm, long 11cm, is used for this test.
Throw off one deck polyester sheet, the bonding agent surface layer that exposes is pressed onto on the reflex reflection face of commercially available retroreflection sheet (see above) with the rubber coated roller.But make roller pass through sample 5 times with the hand applied pressure.The bonding agent that to so make then/reflective sheet layer pressing plate stores 24 hours in 23 ℃.
Throw off second polyester sheet then, the bonding agent face that exposes is applied on the glass plate (not being exposed to the one side of metal bath in preparation process) of isopropyl alcohol cleaning.With the conventional mechanical laminator bonding agent/retroreflection sheet laminate is pressed onto on the glass surface.Rubber coated roller with heavy 6.8kg carries out lamination, and this roller passes through 4 times on sample with 300mm/ minute speed.
Then sample is stored under the various conditions, carries out peel adhesion again and measure.With tension tester with 300mm/ minute peeling rate, 23 ℃ of release adhesives tests of carrying out 90 ° of peel angle.
Each sample carries out 3 times and measures.With digital average, count N/in (N/2.54cm).
The removability test
Between two-layer transparent silication polyester sheet, carry out the photopolymerization of contact adhesive composition.Remove one deck polyester film from the adhesive phase of such formation, the adhesive surface that exposes is put on multi-layer gasket (2).With the rubber coated roller two kinds of material layers are forced together.With available hand applied pressure roller is passed through sample 5 times.Bonding agent/reflective sheet layer pressing plate of making is like this stored 24 hours in 23 ℃.
Remove the polyester sheet of remaining protection pressure sensitive adhesive layer then.Mechanical layer depressor with routine is bonded in final multilayer tablet (1) on the glass matrix.Rubber coated roller with heavy 6.8kg carries out lamination, and this roller passes through 4 times on sample with 300mm/ minute speed.
Attempting with hand from glass when peeling off multilayer tablet the character of qualitative evaluation multilayer tablet (1).
Embodiment 1-5 and comparative example 1-5
The potpourri of the Irgacure 651 (buying by Ciba-Geigy) of 0.04phr and the different monooctyl ester of 100 parts by weight of acrylic acid (IOA) is about 2 with the partially polymerized formation of ultraviolet light, and 000mPas can apply the syrup of viscosity.Then, as shown in table 1, in syrup, add various amounts hydrophobic silica,, hexanediol diacrylate (HDDA) and all add the Irgacure 651 (buying) of 0.2phr in all cases by Ciba-Geigy, then with laboratory stirrer mixing 90 minutes.Between two-layer transparent silication polyester film, carry out syrup coating and curing.The irradiation dose level is about 1,300mJ/cm
2By have 90% emission be between 300nm and 400nm, the peak lamp that is transmitted in 351nm carries out irradiation.The thickness of adhesive sample is chosen as 300 or 800 μ m.Used adhesive composition among table 1 embodiment
| Bonding agent | Isooctyl acrylate monomer | Acrylic acid | Hydrophobic silica (1) | ??HDDA(2) |
| ????A | ????96.5 | ????3.5 | ????15 | ????0.13 |
| ????B | ????95 | ????5 | ????10 | ????0.12 |
| ????C | ????96.5 | ????3.3 | ????10 | ????0.12 |
| ????D | ????98 | ????2 | ????10 | ????0.12 |
| ????E | ????92 | ????8 | ????10 | ????0.12 |
| ????cA | ????100 | ????0 | ????15 | ????0.3 |
| ????cB | ????90 | ????10 | ????15 | ????0.12 |
| ????cC | ????90 | ????10 | ????12.5 | ????0.12 |
| ????cD | ????90 | ????10 | ????10 | ????0.12 |
(1) hydrophobicity fumed available from Degussa, is called R-972
(2) HDDA=hexanediol diacrylate
Embodiment 1-5
As mentioned above, measure 90 ° of peel adhesion of the bonding agent of embodiment 1-5 and comparative example 1-5.Obviously, high under various conditions adhesion value begins just to be present in the bonding agent of embodiment 1-5, can keep bonding after wearing out.If apply enough power, bonding still can be separated, and bonding agent can remove fully.
In contrast, the contact adhesive composition of comparative example 1-5 is not that too high (C2-C5) is exactly too low (C1) to the bounding force of glass, the special purposes that can not be used to imagine.
The result of table 2 peel adhesion test
| Embodiment | Adhesive composition | Adhesive thickness (μ m) | Glass, 23 ℃ (N/in) peeled off in 23 ℃ in 20 minutes | Glass, 3 days, 23 ℃ (N/in) peeled off in 23 ℃ | Glass, 3 days, 70 ℃ (N/in) peeled off in 23 ℃ | Japanning metal 20 minutes ,-10 ℃ (N/in) peel off in-10 ℃ |
| ????1 | ????A | ?800 | ????76.0 | ????60.0 | ????74.9 | ?????- |
| ????2 | ????B | ?300 | ????73.2 | ????36.8 | ????52.8 | ?????- |
| ????3 | ????C | ?300 | ????32.8 | ????33.0 | ????41.5 | ????27.2 |
| ????4 | ????D | ?300 | ????29.2 | ????30.1 | ????33.4 | ????14.0 |
| ????5 | ????E | ?300 | ????38.9 | ????49.6 | ????80.9 | ??????- |
| ????C1 | ????cA | ?800 | ????10.6 | ????9.4 | ????9.4 | ??????- |
| ????C2 | ????cB | ?800 | ????28.6 | ????57.1 | ?????* | ??????- |
| ????C3 | ????cC | ?800 | ????47.1 | ????64.9 | ?????* | ??????- |
| ????C4 | ????cD | ?800 | ????62.9 | ????73.0 | ?????* | ??????- |
| ????C5 | ????cD | ?300 | ????57.9 | ????63.4 | ?????* | ??????- |
* structural failure, bounding force are too high, can not record, and can not remove bonding agent fully without solvent and/or machine tool.
Embodiment 6-8 and comparative example 6
Method with embodiment 1-5 obtains pressure sensitive adhesive material shown in the table 3.
Table 3
| Bonding agent | ????IOA | ????AA | Hydrophobic silica | ????HDDA |
| ????F | ????90 | ????10 | ????15 | ????0.06 |
| ????G | ????90 | ????10 | ????15 | ????0.08 |
| ????H | ????90 | ????10 | ????15 | ????0.10 |
| ????cE | ????90 | ????10 | ????15 | ????0.12 |
Use 90 ° of peel adhesion of the bonding agent that the mask body test method records embodiment 6-8 and comparative example 6.The results are summarized in table 4.
Table 4
| Embodiment | Adhesive composition | Adhesive thickness μ m | Glass, 3 days, 23 ℃, (N/1.27cm) |
| ????6 | ????F | ????800 | ????73.2 |
| ????7 | ????G | ????800 | ????77.9 |
| ????8 | ????H | ????800 | ????65.3 |
| ????c6 | ????cE | ????800 | ????47.1 |
Embodiment 9
Prepare multi-layer gasket (2) in the following method:
With polyester film (liner) heated lamination to aluminium side based on the retroreflection sheet of microballoon.Lamination liner/retroreflection sheet derives from 3M, St.Paul, USA, 3M by name
Scotchlite
FAVS sheet 2005E.
With simplify the hand-printing method with Neocryl A45 (available from Zenica, Netherlands) and Adcoate 50T4990 (available from Morton, USA) to put on the front side of top used retroreflection sheet be the face side to 70: 30 weight % potpourri ethylene, propylene acidic groups pattern of strengthening the priming paint of bounding force, forms the regularly arranged point of the about 3cm of diameter.The sheet of making like this is cut into the sample of about 6cm * 4cm.
3. will be loaded with the front surface of the transparent membrane heated lamination of hologram then to the reflector plate of the enhancing bounding force material that is loaded with patterning.Available from Crown roll Leaf, Inc.OfPeterson, the holograph film of New Jersey are transparent hologram divert films, and it is made up of polyester liner, polymethyl methacrylate base structural sheet, high index zinc sulphide reverberator and thin bonding agent.Under the condition of about 130 ℃, pressure 2 crust, speed 5cm/ minute, (Sallmetal, Raalte, The Netherlands) carries out lamination with commercially available thermosphere depressor.
4. use commercially available screen printing printing ink (3M screen printing printing ink 882 (redness)) to take a picture then and above the layer image is carried out screen printing at transparent holographic.Printing ink was in 45 ℃ of dryings 30 minutes.
Remove one deck protective lining earlier; apply the thick layer of 300 μ m of the contact adhesive of embodiment 2; cross sample 5 times can manual pressure to coat roll-in then, psa layer is pressed onto the surface of screen printing, prepare front type multi-layer sheet of the present invention (1) like this with rubber.
Estimate the usefulness of the multi-layer sheet structure of this bonding agent of finishing coating with the following method: remove second layer liner earlier, multi-layer sheet is adhered to the glass testing surface, described by top " test of removing property " method, assess removing property qualitatively.After removing multi-layer sheet, test the existence of several regional residues: 1) glass matrix; 2) once applied the zone of the retroreflective layer that strengthens the bounding force material; With 3) never apply the zone of the retroreflective layer that strengthens the bounding force material.The test of removing property the results are shown in Table 6 and 7.
Embodiment 10
Except the pressure-sensitive adhesive layer of embodiment 3 thickness with 300 μ m is applied to the surface of multi-layer sheet, use the method identical to prepare embodiment 10 with embodiment 9.The test of removing property the results are shown in Table 6 and 7.
Embodiment 11
Except 300 μ m psa layers with embodiment 4 are applied to the surface of multi-layer sheet, use the method identical to prepare embodiment 11 with embodiment 9.The test of removing property the results are shown in Table 6 and 7.
Embodiment 12
Except adopting different screen printing printing ink, use the method identical to prepare embodiment 12 with embodiment 9.The screen printing printing ink that puts on the priming paint patterned coatings on the retroreflective layer is 3M screen printing printing ink 910 (blueness), 65 ℃ of 45 seconds of drying.The test of removing property the results are shown in Table 6 and 7.
Embodiment 13
Except the polyester film of the aluminum coating side of omitting retroreflection sheet, embodiment 13 adopts as embodiment 12 described multi-layer sheets.As described in embodiment 12, the contact adhesive of one deck 300 μ m is arranged, be called B.This bonding coat is laminated to the aluminum coating side or the dorsal part of retroreflective layer, rather than the front, thereby the back side type multi-layer sheet that is applicable to japanning metal surface such as motorcycle body formed.
Embodiment 14-15
Except contact adhesive is C and D, adopts the 300 μ m thickness respectively, prepare embodiment 14 and 15 by embodiment 13 same methods.
The structure of table 5 embodiment 9-15 (structure of the order reflecting multilayer sheet material in the table)
| Embodiment | ???PSA,μm | Liner | Retroreflection sheet | Priming paint | Holograph | Printing | PSA,μm |
| ????9 | × | ????× | ????× | ????× | Printing ink 1 | ?B,300 | |
| ????10 | × | ????× | ????× | ????× | Printing ink 1 | ?C,300 | |
| ????11 | × | ????× | ????× | ????× | Printing ink 1 | ?D,300 | |
| ????12 | × | ????× | ????× | ????× | Printing ink 2 | ?B,300 | |
| ????13 | ????B,300 | ??????*) | ????× | ????× | ????× | Printing ink 2 | |
| ????14 | ????C,300 | ??????*) | ????× | ????× | ????× | Printing ink 2 | |
| ????15 | ????D,300 | ??????*) | ????× | ????× | ????× | Printing ink 2 |
*) 3M
Scotchlite
FAVS sheet material 2005E, no polyester liner
The result of removing property of table 6 test (1 hour, 23 ℃)
| Embodiment | Residue on glass | Prime residue on the zone | Do not prime residue on the zone |
| ????9 | Bonding agent, part hologram and printing ink | Hologram and printing ink | No residue |
| ????10 | Bonding agent, part hologram and printing ink | Hologram and printing ink | No residue |
| ????11 | Bonding agent, part hologram and printing ink | Hologram and printing ink | No residue |
| ????12 | Bonding agent, part hologram and printing ink | Hologram and printing ink | No residue |
Table 7
As pointed in the table, the bonding multi-layer sheet of embodiment 9-15 is stored under various conditions, remove from glass then.All broken situations show that the interference guard dynamic characteristic (opening as slabbing) of multi-layer sheet all is feasible.The complete available hand of adhesive residue on the glass matrix and/or liner residue removes.
| The paste temperature, ℃ | Glass temperature ℃ | Condition of storage time and temperature, ℃ | Remove about ℃ of condition temperature |
| ????23 | ?????23 | 1 hour, 23 ° | ?????23° |
| ????23 | ????-30 | 2 days ,-30 ° | ????-30° |
| ????23 | ????-30 | 2 days, 40 ° (90%r.h.) | ?????40° |
| ????23 | ????-30 | 1 week ,-30 ° | ????-30° |
| ????-6 | ????11 | 2 days, 23 ° | ?????23° |
| ????-6 | ????11 | 2 days ,-30 ° | ????-30° |
| ????-6 | ????11 | 1 week ,-30 ° | ????-30° |
| ????-6 | ????11 | 2 days, 40 ° (90%) | ????40° |
| ????-6 | ????11 | 1 week, 23 ° | ????23° |
Claims (9)
1. multi-layer sheet (1), comprise flexible liner (2) and be used for multi-layer sheet is bonded in the pressure sensitive adhesive layer (3) of smooth and rigid surface (5), wherein contact adhesive can easily remove and be selected from surface (5), so that thickness is the bonding coat of 300 μ m, after 70 ℃ of temperature leave standstill 3 days when 90 ° of peel adhesion on glass are 20-85N/.
2. multi-layer sheet as claimed in claim 1, wherein liner (2) comprises at least one deck and can decrease layer (4), when peeling off multilayer (1) from the surface, occurs in the layer broken.
3. multi-layer sheet as claimed in claim 1 or 2, wherein pressure sensitive adhesive layer (3) comprises contact adhesive, and described contact adhesive can obtain by the precursor polymeric that will comprise following material, and these materials are:
A) a kind of monomer component, described monomer component comprises one or more alkyl acrylate, and its alkyl has an average 4-14 carbon atom, and comprises at least a copolymerisable monomer with polar group of 2-8phr,
B) 5-15phr hydrophobic silica,
C) one or more polymerization initiators and
D) one or more crosslinker compounds, its concentration is that the hexanediyl ester of 0.06-0.14phr is made the available cross-linking density of reference crosslinker compound for causing with concentration.
4. as the described multi-layer sheet of one of claim 2-3, wherein can decrease layer (4) and comprise pattern (4a), kinegrams and/or the hologram (4b) of regulating the bounding force material, can decrease layer or irreversible deformable layer (4c) and/or printed patterns and/or mark (4d).
5. as the described multi-layer sheet of one of claim 2-4, wherein also comprise reflection horizon (7) and/or overlayer (6) (not shown).
6. as the described multi-layer sheet of one of claim 2-5, order with following each layer: (3)/(4d)/(4a)/(7), (3)/(7)/(4a)/(4d), (3)/(4d)/(4b)/(4a)/(7) or (6)/(4d)/(4b)/(4a)/(7)/(3).
7. the application of the described multi-layer sheet of one of claim 1-6 (1) on the provisional label of preparation or paste such as the paid labeling of toll.
8. the contact adhesive that can obtain by the precursor polymeric that will comprise following material, these materials are:
A) a kind of monomer component, described monomer component comprises one or more alkyl acrylate, and its alkyl has an average 4-14 carbon atom, and comprises at least a copolymerisable monomer with polar group of 2-8phr,
B) 5-15phr hydrophobic silica,
C) one or more polymerization initiators and
D) one or more crosslinker compounds, its concentration is that the hexanediyl ester of 0.06-0.14phr is made the available cross-linking density of reference crosslinker compound for causing with concentration.
9. the contact adhesive that can obtain by the precursor polymeric that will comprise following material, these materials are:
A) a kind of monomer component, described monomer component comprises one or more alkyl acrylate, and its alkyl has an average 4-14 carbon atom, and comprises the above at least a copolymerisable monomer with polar group of 8-20phr,
B) 5-15phr hydrophobic silica,
C) one or more polymerization initiators and
D) one or more crosslinker compounds, its concentration is that the hexanediyl ester of 0.06-0.11phr is made the available cross-linking density of reference crosslinker compound for causing with concentration.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96107988 | 1996-05-20 | ||
| EP96107988.6 | 1996-05-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1219261A true CN1219261A (en) | 1999-06-09 |
Family
ID=8222799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97194712A Pending CN1219261A (en) | 1996-05-20 | 1997-05-20 | Tamper indicating multilayer sheet |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0900433A1 (en) |
| JP (1) | JP2000511479A (en) |
| CN (1) | CN1219261A (en) |
| AU (1) | AU3072997A (en) |
| BR (1) | BR9709104A (en) |
| CA (1) | CA2252804A1 (en) |
| WO (1) | WO1997044769A1 (en) |
Cited By (3)
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|---|---|---|---|---|
| CN100469568C (en) * | 2003-03-04 | 2009-03-18 | 3M创新有限公司 | Method for bonding a fluoroelastomer layer to a silicone rubber layer, laminate for use in said method and article produced by said method |
| CN103945751A (en) * | 2011-11-11 | 2014-07-23 | 3M创新有限公司 | A cleaning surface with reactivatable adhesive |
| CN103971590A (en) * | 2013-02-01 | 2014-08-06 | 比亚迪股份有限公司 | Anti-counterfeiting trademark and manufacturing method thereof |
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| DE19808784A1 (en) * | 1998-03-03 | 1999-09-09 | Cit Alcatel | Electronic apparatus for attachment by suction to vehicle windscreen |
| US6372341B1 (en) * | 1998-04-27 | 2002-04-16 | 3M Innovative Properties Company | Tampa-indicating article for reusable substrates |
| US6537634B2 (en) * | 1999-12-29 | 2003-03-25 | Tesa Ag | Adhesive security tape for detecting unauthorized broaching of a package |
| DE19963709A1 (en) * | 1999-12-29 | 2002-12-05 | Tesa Ag | Security adhesive tape to prove unauthorized opening of a packaging |
| DE10030596A1 (en) * | 2000-06-21 | 2003-01-23 | Tesa Ag | Security adhesive tape to prove unauthorized opening of a packaging |
| US20040021312A1 (en) * | 2002-08-02 | 2004-02-05 | Dietz Timothy M. | Security label |
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| DE102007007413A1 (en) | 2007-02-12 | 2008-08-14 | Tesa Ag | security label |
| US20090061222A1 (en) * | 2007-08-31 | 2009-03-05 | Tesa Aktiengesellschaft | Multi-layer adhesive closure |
| DE102008013690A1 (en) | 2008-03-11 | 2009-09-17 | Tesa Se | security label |
| DE102008033323A1 (en) | 2008-07-16 | 2010-01-21 | Tesa Se | security label |
| DE102008057456A1 (en) | 2008-11-14 | 2010-05-20 | Tesa Se | Security tag for use as initial opening proof for e.g. container, has carrier with adhesive layer mark designed such that mark is not identified or complicatedly identified with non-stretched tag without using auxiliary aid |
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| DE102012019543A1 (en) * | 2012-08-27 | 2014-02-27 | Trautwein Gmbh & Co. | seal |
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| WO2016130822A1 (en) | 2015-02-11 | 2016-08-18 | Crane & Co., Inc. | Method for the surface application of a security device to a substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5202361A (en) * | 1991-12-23 | 1993-04-13 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive |
| GB9218216D0 (en) * | 1992-08-27 | 1992-10-14 | Payne P P Ltd | Improvements in or relating to tapes |
| CA2134521A1 (en) * | 1993-11-02 | 1995-05-03 | Raymond R. Gosselin | Tamper-indicating label |
-
1997
- 1997-05-20 CA CA002252804A patent/CA2252804A1/en not_active Abandoned
- 1997-05-20 WO PCT/US1997/008528 patent/WO1997044769A1/en not_active Ceased
- 1997-05-20 CN CN97194712A patent/CN1219261A/en active Pending
- 1997-05-20 JP JP09542650A patent/JP2000511479A/en active Pending
- 1997-05-20 AU AU30729/97A patent/AU3072997A/en not_active Abandoned
- 1997-05-20 EP EP97925654A patent/EP0900433A1/en not_active Ceased
- 1997-05-20 BR BR9709104A patent/BR9709104A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100469568C (en) * | 2003-03-04 | 2009-03-18 | 3M创新有限公司 | Method for bonding a fluoroelastomer layer to a silicone rubber layer, laminate for use in said method and article produced by said method |
| CN103945751A (en) * | 2011-11-11 | 2014-07-23 | 3M创新有限公司 | A cleaning surface with reactivatable adhesive |
| CN103971590A (en) * | 2013-02-01 | 2014-08-06 | 比亚迪股份有限公司 | Anti-counterfeiting trademark and manufacturing method thereof |
| CN103971590B (en) * | 2013-02-01 | 2017-02-22 | 比亚迪股份有限公司 | Anti-counterfeiting trademark and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9709104A (en) | 1999-08-03 |
| JP2000511479A (en) | 2000-09-05 |
| EP0900433A1 (en) | 1999-03-10 |
| CA2252804A1 (en) | 1997-11-27 |
| WO1997044769A1 (en) | 1997-11-27 |
| AU3072997A (en) | 1997-12-09 |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |