CN1726137A - Marking film, receptor sheet and marking film for vehicles - Google Patents
Marking film, receptor sheet and marking film for vehicles Download PDFInfo
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- CN1726137A CN1726137A CN 200380106126 CN200380106126A CN1726137A CN 1726137 A CN1726137 A CN 1726137A CN 200380106126 CN200380106126 CN 200380106126 CN 200380106126 A CN200380106126 A CN 200380106126A CN 1726137 A CN1726137 A CN 1726137A
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- Prior art keywords
- film
- receptor
- marking
- adhesive phase
- adhesive
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/504—Backcoats
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B41M5/5281—Polyurethanes or polyureas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
- B44C1/105—Applying flat materials, e.g. leaflets, pieces of fabrics comprising an adhesive layer
Abstract
The present invention provides a marking film, which has good resistance to petroleum and moisture and is suitable as a marking film of a vehicle that moves using a petroleum fuel. A marking film comprising a receptor film having a front surface as a colorant-receptive surface, and a back surface, a colorant received on the front surface of the receptor film, and an adhesive layer provided on the back surface of the receptor film and comprising an adhesive which serves to adhere the receptor film to an adherent, wherein the adhesive layer has projections containing the adhesive, which are formed on an adhesion surface, and depressions surrounding the projections, and the depressions define conduits, which communicate with the atmosphere, between the surface of the adherent and the adhesion surface of the adhesive layer when the adhesive layer is being adhered to the adherent, characterized in that the receptor film comprises a receptor layer formed of a thermoplastic resin film having a surface which serves as the colorant-receptive surface, and the thermoplastic resin film comprises a resinous component containing at least one petroleum-resistant resin selected from the group consisting of polyurethane comprising polyol units derived from polycarbonate polyol, polyurethane comprising polyol units derived from polycaprolactone polyol and phenoxy resins, or the receptor film is a petroleum-resistant resin film containing a copolymer comprising a C<SUB>1</SUB>-C<SUB>8</SUB>-alkyl acrylate and methyl methacrylate.
Description
Invention field
The present invention relates to a kind of Marking film, it comprises and is used to accept receptor film (image display layer) or the dyed layer of colouring agent as the toner that forms image, and the adhesive phase with out-of-flatness adhesive surface.
Background of invention
Can use the acceptor sheet to make Marking film, the front surface of described acceptor sheet can form image (image display layer) or dyed layer by toner or the printing ink that applies as colouring agent.Described acceptor sheet has receptor film usually, and it comprises basic unit and receptive layers, and described receptive layers is included in the thermoplastic resin membrane who forms on the surface of base material.Usually, on the back of the body surface of receptor film, form adhesive phase, described acceptor sheet can be adhered on the adhesion.
Marking film can form image and waits and make by printing by static toner for example on the surface of acceptor sheet (being receptor film).In the time will protecting the surface (colouring agent of receptive layers is accepted the surface) of being printed, it can cover with protective film.Usually use the transparent protective film that can see toner (image etc.) through film, as the thin polymer film that forms by fluoropolymer polymer, acrylate copolymer, phthalate polyester (for example, PET) etc.
The thermoplastic resin membrane of described receptive layers can be formed by various resin combinations.For example, JP-A-9-507309 discloses the application of flexible thermoplastic resin film as the receptive layers of receptor film, and described resin film comprises polyurethane-acrylate copolymer latices rubber, acrylic resin, vinyl chloride copolymer such as vinyl chloride vinyl acetate copolymer and plasticizer.JP-B-3080674 discloses the application as the resin material of receptive layers or basic unit such as acrylic resin, polyolefin, polyethylene acetal, polyvinyl chloride, polyurethane.But, and unexposed phenoxy resin is as the resin material of receptive layers or basic unit.
JP-A 2002-19303 discloses the window film that uses polymethyl methacrylate film, and it can heat shift.But the pliability of conventional polymethyl methacrylate film is low, and is therefore poor to the adaptability (followability) of curved surface.Therefore, this film is not enough to as the Marking film that adheres on curved surface such as the car body surface.
When described Marking film (or receptor film) adheres on (being applied to) adhesion, also knownly on the bonding surface of Marking film adhesive phase, form out-of-flatness, to prevent entrained air between adhesive phase and adhesion (that is, bubble can being overflowed).This adhesive phase has projection and the sunk part around described projection, and by described sunk part groove that form and that be communicated with atmosphere, the i.e. conduit that between the adhesive surface of adhesion surface and adhesive phase, forms.
By the irregular peeling paper of stripper surface (liner) is laminated to the out-of-flatness that forms on the adhesive phase on the adhesive surface.In WO00/6985, U.S. Patent No. 6,203,885, JP-A 2001-507732, JP-utility model-2,503,717, JP-utility model-2,687,198 grades disclose the Marking film that uses this out-of-flatness peeling paper.Also known formation comprises the projection of elastic microsphere body on adhesive surface by add the elastic microsphere body in adhesive phase, forms sunk part thus effectively around projection.The Marking film that uses this elastic microsphere body is disclosed in JP-A-8-113768.
Under the situation of Marking film with out-of-flatness adhesive surface, finish apply film after, between adhesion and adhesive phase, have above-mentioned conduit usually.Therefore, when the adhesion of this Marking film and when being used on the surface of car body (as bus or truck), the petroleum fuel that overflows around oil filler in refueling process can be filled described conduit because of capillarity, and diffusion in large tracts of land adhesive surface (or adhesion surface).Someone finds that the fuel that spreads by this way can see through the inside that adhesive phase infiltrates film, and with described films swell.Because of fuel, especially the swelling that causes of diesel oil is unfavorable to the outward appearance of Marking film, and this is that perhaps each of Marking film layer meeting peeled off because Marking film can be peeled off from adhesion.
Above neither one patent gazette has been mentioned any improvement of vehicle with Marking film, and described Marking film adheres on the surface of the car body that uses petroleum fuel such as diesel oil.That is, they do not disclose concrete resin choice and use, suppress the above-mentioned outward appearance infringement that swelling that Marking film causes because of petroleum fuel such as diesel oil occurs with effective raising.For example, when described receptor film comprised polyolefin, the outward appearance infringement that occurs because of swelling was clearly.The less swelling of receptive layers that comprises polyurethane, but the moisture-proof gas of polyurethane is low usually, therefore, when described Marking film is used for outdoorly (being exposed to the relative down time of growing of wind and weather conditions, for example 6 months) time, the edge of described Marking film tends to peel off from adhesion, and perk.
Summary of the invention
In order to address the above problem, the invention provides a kind of Marking film, described film comprises:
(a) have the receptor film that colouring agent is accepted front surface and the back of the body surface relative with described front surface,
(b) colouring agent of accepting on the front surface of described receptor film and
(c) be fixed on the described lip-deep adhesive phase of thin film back of accepting, it comprises the described film of accepting is adhered to adhesive on the adhesion,
Wherein, described adhesive phase has projection (being formed on the bonding surface that adheres on the described adhesion) and the sunk part around described projection that comprises described adhesive, when described adhesive phase adheres on the described adhesion, form conduit between the described bonding surface that is recessed in adhesion surface and adhesive phase, be used for being communicated with atmosphere.
And described receptor film comprises the receptive layers that is formed by ardent hope property resin film, has the surface of accepting the surface as colouring agent; Described thermoplastic resin membrane comprises the resinite component, it comprises the resin of at least a anti-oil, is selected from the polyurethane that comprises the polyol unit of being derived by polycarbonate polyol, the polyurethane that comprises the polyol unit of being derived by PCL polyalcohol and phenoxy resin; Perhaps described receptor film is the film of anti-Petropols that comprises copolymer, and described copolymer comprises at least a acrylic acid C1-C8 alkane ester and methyl methacrylate.
Brief Description Of Drawings
Fig. 1 is the sectional view of an embodiment of Marking film of the present invention.
The preferred embodiment for the present invention
In Marking film of the present invention, described receptive layers comprises the resin of at least a anti-oil, is selected from the polyurethane that comprises the polyol unit of being derived by polycarbonate polyol, the polyurethane that comprises the polyol unit of being derived by PCL polyalcohol and phenoxy resin; Perhaps described receptor film is the film of anti-Petropols that comprises copolymer, and described copolymer comprises at least a acrylic acid C1-C8 alkane ester and methyl methacrylate.Therefore, Marking film of the present invention can prevent to infiltrate the swelling that causes in the receptive layers because of petroleum fuel such as diesel oil or gasoline see through adhesive phase effectively.Therefore, when Marking film being adhered to and being used on the car body surface, can prevent from effectively to cause the Marking film cosmetic damage because of infiltrating fuel.In addition, the resin of described anti-oil has moisture-proof gas, and this is because described resin hydrolysis.Therefore, when being used in when being exposed to outdoor under rain and the weather conditions, Marking film of the present invention can suppress the edge curl of Marking film effectively.
If the surface of described receptor film may contact with diesel oil, the so more handy protective film that comprises fluororesin is protected the image formation surface (accepting the surface of colouring agent) of described receptor film.And the protective film that uses the resin combination of the resin comprise at least a anti-oil to make is that effectively the resin of described at least a anti-oil is selected from the above.
Described receptor film has basic unit between receptive layers and adhesive phase, though better only have receptive layers and adhesive phase.When the thickness of described Marking film reduced, the pliability of described Marking film integral body can improve, and can improve the adaptability of Marking film to adhesion with curved surface effectively.
When described receptor film comprises basic unit, described basic unit better comprises the resin of at least a anti-oil, it be selected from the polyol unit that polycarbonate polyol derives polyurethane, comprise the polyurethane of the polyol unit of deriving by PCL polyalcohol and phenoxy resin; Perhaps described receptor film is the film of anti-Petropols that comprises copolymer, and described copolymer comprises at least a acrylic acid C1-C8 alkane ester and methyl methacrylate.Therefore, the effect of barrier layer is played by described basic unit, can suppress more effectively fuel infiltrate as diesel oil as described in receptive layers.
In the present invention, film or the layer that comprises anti-Petropols can be designed to not comprise substantially polyvinyl chloride.Today, need to be substantially free of the Marking film of polyvinyl chloride, the Marking film of promptly so-called not vinyl-chloride-containing on the market.The present invention can provide a kind of Marking film that satisfies this requirement and have the not vinyl-chloride-containing of good resistance to petroleum.
Marking film
A preferred implementation of Marking film of the present invention illustrates by shown in Figure 1.
Fig. 1 schematically illustrates an embodiment of Marking film of the present invention.The receptor film (1) of described Marking film (100) is made up of the acceptor individual layer, and described individual layer is made by thermoplastic film.Described thermoplastic film comprises the resin of anti-oil, as mentioned above.Receptor film (1) has front surface (11) and rear surface (12), and front surface (11) is accepted colouring agent, i.e. toner (2).Toner (2) forms image, and described image sees through described protective film (3) as seen from outermost surface (31) one sides of protective film (3).
Described adhesive phase (4) can be fixed on the rear surface (12) of receptor film (1).Though do not show among Fig. 1, but the described projection that comprises the adhesive (not shown) and go up at the adhesive surface (41) of adhesive phase (4) around the depression (not shown) of projection forms, and when Marking film and adhesion bonding, between adhesive surface (41) and adhesion surface, form the conduit (not shown), it by be recessed to form and and atmosphere communicate.
The adhesive of adhesive phase (4) does not have any restriction, and contact adhesive normally, and it comprises from adhering polymer.As for pressure sensitive adhesive layer, better use for example comprises the individual layer pressure-sensitive adhesive film of polymer of adhering certainly, or comprises two coat binding sheets of two kinds of pressure sensitive adhesive layers.
In order protective film (3) to be adhered on the receptor film (1), can to use usually another adhesive phase (30) that is used for protective film.The adhesive that is used for the adhesive phase (30) of protective layer does not have any restriction; normally comprise contact adhesive from the polymer of adhering; this is to go up the uneven surface that toner (2) forms because this adhesive phase can be fitted by receptor film surface (11); protective film (3) and receptor film (1) can closely be adhered mutually, between them, can not form bubble simultaneously.Described bubble has reduced the observability of image, therefore preferably prevents to produce bubble.
The acceptor sheet
Acceptor sheet of the present invention is the receptor film with adhesive phase, has applied colouring agent such as toner on the described receptor film, and described adhesive phase is adhered to receptor film on the adhesion.
Usually, receptor film (i) is the monolayer thermoplastic resin film that comprises anti-Petropols, perhaps (ii) comprises the laminated film that has receptive layers and have basic unit between receptive layers and adhesive phase.Situation (ii) in, described basic unit better also is the resin film that comprises anti-Petropols.
The resistance to petroleum of the described resin film of evaluation as described below:
Resin film with concrete size sample is provided.On the surface of this sample, drip last one (about 0.01-0.02g) diesel oil, at room temperature static 10 minutes, the described sample of visual observations then.If do not form wrinkle, judge that described resin film has good resistance to petroleum.If described resin film then can prevent described swelling to other petroleum fuel such as gasoline effectively to the tolerance height (using the resistance to petroleum of diesel oil) of diesel oil.
The resistance to petroleum of evaluation acceptor sheet as described below (having adhesive phase):
The acceptor sheet sample that will have concrete size is adhered to the test adhesion, for example on the sheet of Hong Kao coating melamine.In this step, between the surface of adhesion and adhesive phase, form and conduit that atmosphere communicates.At room temperature will be adhered to sample on the adhesion and partly be impregnated in the diesel oil 8 hours, from diesel oil, take out then, and at room temperature dry in the shade (not having direct light) 16 hours.The described dry-eye disease of perusal.If do not form wrinkle, can not peel off for then described with adhesion, perhaps form layering (between receptor film and adhesive phase etc.), judge that described acceptor sheet has good resistance to petroleum.As mentioned above, the resistance to petroleum of evaluation mark film in an identical manner.
Usually, the moisture-proof gas of evaluating resin film as described below:
With adhesive resin film is adhered on the sheet of coating melamine, makes sample.Described sample places and is set in 65 ℃, a week in the baking oven of 95%RH.Then, check the edge of described film, determine whether it rolls.If do not roll, judge that then described film has good moisture-proof gas at this condition lower limb.Use adheres to resin film the adhesive pressure sensitive acrylic adhesive normally on the sheet of coating melamine.Perhaps, also can use to be actually used in Marking film is adhered to adhesive on the adhesion.The moisture-proof gas of evaluation mark film in the same manner described above.
Polyurethane as anti-Petropols is raw material and the prepared polymer of vulcabond that polymerization comprises above-mentioned polyalcohol (polycarbonate polyol and/or PCL polyalcohol).Described raw material can comprise the short-chain diol as cahin extension agent, as neopentyl glycol, ethylene glycol, propane diols etc.The example of described vulcabond comprises the MDI, 1 of IPDI (IPDI), methyl diphenylene diisocyanate (MDI), hydrogenation, 6-hexylene glycol vulcabond, toluene di-isocyanate(TDI) (TDI), tetramethyl eylylene diisocyanate (TMXDI) etc.Described raw material can comprise one or more polyalcohols and one or more diisocyanates.
Select the chemical constitution of vulcabond in the described raw material and the ratio of short-chain diol (optional is polyalcohol), the described character (for example, glass transition temperature, compound dynamic viscosity and Vicat softening point) that comprises the thermoplastic resin membrane of polyurethane is all dropped in the optimum range.
The thermoplastic resin membrane's of described receptive layers glass transition temperature is generally 0-100 ℃.When the glass transition temperature of described receptive layers was too high, the toner transfer printing variation of described receptive layers can not form distinct image.In addition, when glass transition temperature was too high, the pliability of described Marking film is whole to be reduced.When glass transition temperature during less than 0 ℃, the resistance to petroleum variation.And, the glass transition temperature of described receptive layers be preferably 0 ℃ or more than, accept surface viscosity at room temperature to reduce colouring agent effectively.When described receptive layers has such glass transition temperature, before covering, can prevent the adhesion of Marking film precursor or acceptor sheet effectively with protective film.Therefore, after with the web-like storage, described Marking film precursor or acceptor sheet are easily by the formal expansion of rolling up.
The glass transition temperature of described receptive layers is preferably 10-90 ℃, is more preferably to be 20-80 ℃, improves above effect effectively with good balance, promptly improves resistance to petroleum and toner transfer printing, reduces the pliability of room temperature viscosity and raising film.
The thermoplastic resin membrane's of described receptive layers glass transition temperature (Tg), and is fixed on this sample among the DSC (differential scanning calorimetry (DSC)) and measures as sample by the film that thickness is provided is about 10 microns (usually 8-20 microns).In measurement, described temperature rises to 120 ℃ (for the first time scanning) from-50 ℃, then, is reading glass transition temperature from the flex point of corresponding second inversion point in the scanning for the first time.
Except glass transition temperature, the Vicat softening point that the character that described thermoplastic resin membrane will note is the thermoplastic resin membrane uses the viscoplasticity spectrophotometer measurement down at 25 ℃.Described thermoplastic resin membrane's Vicat softening point is generally 30-95 ℃, better is 40-93 ℃.When described Vicat softening point is too high, be difficult to toner is transferred on the resin film.When the Vicat softening point was too low, the mechanical strength of described resin film reduced, and made the durability degree variation of Marking film.
Described Vicat softening point is the softening point that records according to the K of Japanese Industrial Standards (JIS) 7206: with the temperature of constant speed rising sample, simultaneously concrete heavy burden is applied on the needle-like penetrant, its keeps vertical with sample (thermoplastic resin membrane), and the temperature of measurement penetrant when penetrating sample 1mm.
Described especially preferred polyurethane is the polyurethane that has the polyol unit of being derived by polycarbonate polyol in the molecule (polycarbonate polyurethane).Described polycarbonate polyurethane has good weatherability and moisture-proof gas, therefore can prevent to comprise its film variation or variable color effectively.The variable color of described protective film or receptor film causes fading of image.Therefore, describedly do not allow allochroic receptor film and protective film to help element as the Marking film of outdoor application, especially for motor vehicle Marking film.
The carbon number of alkylidene is preferably 5-7 in the polyalcohol main chain.When carbon number surpasses 7, described thermoplastic resin membrane's resistance to petroleum variation.When carbon number less than 5 the time, the hot transfer printing degradation of described toner.
The molecular weight of described polyurethane does not have any restriction, and its weight average molecular weight is generally 20000-1000000.
Phenoxy resin also has high resistance to petroleum and moisture-proof gas.This is because have by the bis-phenol repeat units derived in the molecule of phenoxy resin.Can use phenoxy resin, as be usually used in coating those.The object lesson of commercially available phenoxy resin comprises " YP 50S " (trade name, from TOTO Chemical Co., Ltd. buys), " PKHH " (trade name is buied from Phenoxy Specialties) etc.The molecular weight of described phenoxy resin does not have any restriction, and enough tough as long as it has, weight average molecular weight is generally 20000-1000000.
Described phenoxy resin helps improving the toughness of receptor film, and this is because its fracture strength is higher than polyurethane.When peeling off Marking film in order to reuse, the toughness that improves described receptor film can prevent that Marking film from splitting, and reduces the workload of peeling off effectively.
When using phenoxy resin, better and polyurethane is used in combination, and this is because the flexibility and the toughness of receptor film improve easily, and has good balance.In this case, polyurethane with the mixture of phenoxy resin in percetage by weight be at least 60% usually, better be at least 65%, be more preferably at least 70%.The polyurethanes that mixing is used with phenoxy resin is polycarbonate polyurethane or PCL polyurethane normally.When the percentage of polyurethane is 70% or when following, can use other polyurethanes.
Also can use as soft component copolymer (it comprises at least a alkyl acrylate that has 1-8 carbon atom in the alkyl) and as the methyl methacrylate of hard component.This alkyl acrylate has reduced the glass transition temperature of copolymer.Described copolymer can also comprise at least a other comonomer, as methyl acrylic ester (except methyl methacrylate), styrene etc.The glass transition temperature of described copolymer is generally 0-100 ℃, better is 20-90 ℃, is more preferably 30-80 ℃.In the weight of described copolymer, the amount of described alkyl acrylate better is at least 20 weight %, but is not limited to this scope.
In copolymer, especially preferably include the copolymer of butyl acrylate and methyl methacrylate.When using this acrylic copolymer as anti-Petropols, described receptor film is a single thin film.
The resin Composition that constitutes receptive layers (and basic unit) can comprise other resin, as long as to not infringement of effect of the present invention.An example of described other resin is exactly an acrylic resin.Described acrylic resin is the polymer by the preparation of polymerization (methyl) acrylic monomers mixture.Described (methyl) acrylic monomers mixture comprises (methyl) that have 1-10 carbon atom in the alkyl but the monomer of acrylate and other copolymerization usually.But the monomer of described other copolymerization better is a hydrophilic monomer, as hydroxyl (methyl) acrylate, alkyl diol diacrylate, acrylic acid, methacrylic acid etc., improves resistance to petroleum.Described acrylic resin can come this monomer mixture of polymerization to make by conventional polymerization such as solution polymerization.Better select the ratio of described monomer, make thermoplastic resin membrane's glass transition temperature and other character in the scope of the best.The molecular weight of described acrylic resin does not have any restriction, and its weight average molecular weight is generally 20000-1000000.
In the whole resin Composition contained as the thermoplastic resin membrane of receptive layers or basic unit, the amount of the resin of anti-oil is at least 70 weight % usually.In order further to improve the resistance to petroleum of film, the amount of described anti-Petropols in whole resin Composition better is at least 80 weight %, especially at least 90 weight %.
Described acceptor sheet can as described belowly make:
Make the thermoplastic resin membrane who forms receptive layers by conventional film build method.For example, the coating that will comprise resin Composition is applied on the stripper surface of liner, and is solidified into the thermoplastic resin membrane.As for applying equipment, can use conventional spreader, be coated with device, blade coating device, roller coat device, die orifice spreader etc. as rod.Described curing is included in the resin Composition etc. that carries out drying, cooling fusion under the situation that comprises volatile solvent.Perhaps, described thermoplastic resin membrane can form by melt extruding method.
When described acceptor sheet comprised basic unit and receptive layers, it can make (though described manufacture method is not limited to this) by the following method:
At first, on liner, form receptive layers, then, will comprise basic unit and be applied on the receptive layers with liner, and solidify with the coating of resin Composition.Make the receptor film that comprises the thin layer compressing tablet thus.Between receptive layers and adhesive phase, can form another the layer as prime coat or adhesive phase, however can damage effect of the present invention.
Then, adhesive phase is applied on the rear surface of receptor film, it makes as mentioned above.
Be applied to by the coating liquid that will comprise adhesive on the stripper surface of liner, and dry make adhesive phase, will have the adhesive phase lamination of liner then and adhere on the receptor film, make described adhesive phase thus with liner.So just finished acceptor sheet of the present invention.
The integral thickness of receptor film is generally the 20-150 micron, better is the 30-100 micron.When thickness too hour, the mechanical strength of described film reduces, therefore after Marking film adheres on the adhesion when adhesion is peeled off, described acceptor sheet ruptures.When thickness was too big, the described pliability of the Marking film of acceptor sheet that comprises can reduce.
Bonding sheet
Bonding sheet for Marking film (or receptor film) being adhered on the adhesion forms above-mentioned irregular adhesive phase.In order to form irregular adhesive phase, can use any method of in above prior art, announcing.An example of this method below has been described:
The liner of the stripper surface with special construction at first, is provided.On the stripper surface of liner, apply and comprise from the polymer of adhering (adhesive composition is used to form the adhesive phase of bonding sheet), and the dry adhesive phase that forms.Thus gasket construction (negative) is transferred on the surface of adhesive phase, described adhesive phase contacts (adhesive surface that this surface has formed bonding sheet) with liner, has formed the adhesive surface of the band structure with special construction so thereon.Design the structure on the described adhesive surface, make it comprise groove, when projection contacts with adhesion, form conduit.
On adhesive surface, can form the groove of adhesive phase, arrange groove, perhaps arrange at random and have erose groove, as long as when the usage flag film, can prevent residual bubble with special shape with form clocklike.When arranging many grooves in substantially parallel mode, the distance between the groove is preferably the 10-2000 micron.The degree of depth of groove (along the distance of direction from the adhesive surface to the bottom portion of groove towards receptor film) is generally the 10-100 micron.The shape of described groove without limits, only otherwise can damage effect of the present invention.For example, the cross section perpendicular to the groove of adhesive surface can be rectangle (comprising trapezoidal), semicircle, half elliptic etc.
Described liner is made by the scraps of paper or plastic sheeting usually.Described paper gasket pad is laminated to as polyethylene coating, silicone coating etc. on the surface of the scraps of paper by lamination release coating (peel ply) usually and makes.When lamination silicone release coating, common lamination bottom such as clay coating, polyethylene coating etc., the described release coating of lamination then.After the lamination release coating,, stripper surface forms gasket construction by being expressed on the instrument that is used for transfer organization.
Described adhesive phase can be formed by the adhesive coated thin film that comprises from the polymer of adhering.Adhesive comprises from polymer and the crosslinking agent that is used for the crosslinked polymer of adhering certainly of adhering preferably.In this article, the described polymer of adhering certainly is meant the polymer that has viscosity under room temperature (about 25 ℃).This example from the polymer of adhering comprises acrylate copolymer, polyurethane, polyolefin, polyester etc.
Illustrate that with reference to acrylate copolymer self-adhesion the synthetic example of polymer.
As first monomer, provide acrylic acid unsaturated acids (for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid etc.) or polarity (methyl) acrylic monomers (for example, acrylonitrile etc.).Described first monomer and mix as the acrylic monomers of second monomer makes monomer mixture.As for second monomer, can use alkyl-acrylates, as Isooctyl acrylate monomer, butyl acrylate, acrylic acid 2-methyl butyl ester, acrylic acid 2-ethyl ester, acrylic acid ester in the different ninth of the ten Heavenly Stems etc.
Described monomer mixture can be by routine polymerisation such as solution polymerization, emulsion polymerization, bulk polymerization wait the synthetic polymer of adhesion certainly with concrete molecular weight.
When using crosslinking agent crosslinked described when adhering polymer, in the polymer of adhesion certainly of per 100 weight portions, the amount of crosslinking agent is generally the 0.02-2 weight portion, better is the 0.03-1 weight portion, though this depends on the kind of crosslinking agent.The example of crosslinking agent comprises isocyanate compound, melamine compound, poly-(methyl) acrylate compounds, epoxy compounds, amide compound, bisamide compound (for example, binary acid as phenodiazine third piperidine derivatives of a benzoyl two (2-methylaziridine) etc.).
The glass transition temperature of described adhesive phase (Tg) is preferably-50 ℃ to-10 ℃, especially better is-40 ℃ to-5 ℃.When the Tg of adhesive phase is too high, the viscosity variation between adhesion and the Marking film.When Tg was too low, adhesive can be extruded from the edge of Marking film volume, when storing described Marking film with roll form; Therefore can not prevent the part bonding lanigerous of Marking film.
Here, the Tg of adhesive phase is calculated by the tan δ that uses the dynamic viscosity instrumentation to get.Described measuring condition comprises that shear rate is the torsional mode of 1 radian per second ,-60 to 100 ℃ heating-up temperature scope and 5 ℃/second firing rate.Sample thickness is generally 1-2mm.
The thickness of described adhesive phase is generally the 20-100 micron, better is the 25-80 micron.Described pressure sensitive adhesive layer can comprise various additives, as the microballoon of tackifier, elastic microsphere, sticky polymers, crystalline polymer, inorganic powder, ultra-violet absorber etc.
Protective film
Described protective film integral body has light transmission.The light transmittance of described protective film is at least 60% usually, better is at least 70%, especially better is at least 80%.Here, described light transmittance is the total light transmittance of measuring with spectrophotometer or color meter, above-mentioned color meter under the wavelength of 550nm as photometer.
Described protective film better comprises the resin film that transparency is high.The resin examples of described resin film comprises fluororesin, phthalic acid ester group polyesters (for example, PET, PEN etc.), acrylic resin and above anti-Petropols etc.Described fluororesin is to be made by at least a monomer that comprises fluorine of polymerization.The examples of monomers that comprises fluorine comprises the vinyl monomer that comprises fluorine, as vinylidene fluoride, hexafluoropropene, tetrafluoroethene, CTFE etc.In addition, can with one or more can and the monomer of fluorochemical monomer copolymerization such as methacrylate (for example, methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate etc.) and acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate etc.) mix with fluorochemical monomer.Except fluorochemical monomer, but described raw material monomer can comprise the monomer of other copolymerization, as acrylic monomers (for example, methyl methacrylate, EMA etc.).And described protective film can be made by the resin combination that comprises fluororesin and acrylic resin.
When Marking film of the present invention during as the Marking film of the vehicle that relies on petroleum fuel to drive as the energy, the resin of protective film better is the resin of fluororesin or anti-oil.In this case, the percentage of fluororesin or anti-Petropols is at least 70 weight % usually in the resin Composition of formation protective film, better is to be at least 80 weight %, especially better is at least 90 weight %.When protective film comprises fluororesin and anti-Petropols, in the more above-mentioned scope of the total amount of described two kinds of resins.
The thickness of described protective film is generally the 5-120 micron, better is the 10-100 micron.When adhesive phase was used for adhering to protective film on the receptor film, its thickness was generally the 2-100 micron, better was the 25-80 micron.
Form image
Described colouring agent is toner or printing ink normally.For example, when when toner being transferred to receptive layers forming image, can use conventional Method of printing such as electrostatic printing method that toner is transferred on the rear surface of protective film.Described electrostatic printing method comprises method of direct printing (wherein, image directly prints to the rear surface of protective film) and transfer printing (wherein, image is printed on the temporary support thing, transfers on the protective film then).In printing transferring method, described image is formed directly on the temporary support thing (this can be called offset medium), is transferred on the rear surface of protective film by the heating pressurization then, makes the protective film with print image.
The described toner that is used to form image comprises resin glue and the pigment that is dispersed in the resin glue.Described resin glue can be the resin that is selected from acrylic resin and mylar and their mixtures.The details of described electrostatic printing method is as described in JP-A-4-216562, the JP-A-11-513818 etc.
Embodiment
Embodiment 1
The acceptor sheet of manufacturing present embodiment as described below:
Weight ratio mixed polycarbonate polyurethane and phenoxy resin with 70: 30 are dissolved in it in toluene then, make the coating that is used for receptive layers.Described polyurethane comprises 1 by polymerization, and the raw material of 6-hexylene glycol carbonate polyol and hexamethylene diisocyanate makes.Described phenoxy resin is " PKHH " (trade name, from PhenoxySpecialties, USA buys).
This coating is applied on the polyester support (thickness with peel ply is 50 microns polyester film liner), and it does thick is 10 microns, the dry then receptive layers that comprises clear thermoplastic resin membrane that makes.The Tg of described receptive layers (thermoplastic resin membrane) is 24 ℃.The Tg of described polyurethane is 34 ℃, and the Tg of described phenoxy resin is 72 ℃.
On the rear surface of described receptive layers (effect that colouring agent is accepted the surface is played on the surface that contacts with carrier), apply solution (the REZAMINO NE310 of polyester-polyurethane, from DAINICHI SEIKA Co., Ltd. buy), be 33 microns to doing thick, and the dry basic unit that forms.Make the receptor film that constitutes by receptive layers and basic unit thus.
The coating that will be used for adhesive phase with the blade coating device is applied to the stripper surface of liner separately, is 40 microns to doing thick, and 90 ℃ dry 5 minutes down, above-mentioned liner has the uneven surface of the pattern of rule on peel ply.This coating prepares in ethyl acetate and toluene mixed solvent by mixing from adhere acrylate copolymer, crystallization polyurethane and bisamide crosslinking agent.From the adhesion polymer: crystallization polyurethane: the weight ratio of crosslinking agent is 90: 10: 0.2 (ratio of nonvolatile element).
Described acrylic acid is that to comprise weight ratio by polymerisation in solution be the copolymer that 93: 3: 4 butyl acrylate, acrylonitrile and acrylic acid monomer mixture makes from the polymer of adhering.Described weight average molecular weight from the polymer of adhering is 460000, and Tg is-21 ℃.
Described crystalline polymer is by polymerization IPDI (IPDI) and PCL (PLACSEL in toluene
220, from DAICEL Chemical Industries, Ltd. buys, weight average molecular weight=6000, weight-average molecular weight/number-average molecular weight=1.8) prepare.The mol ratio of PCL and IPDI is 2: 1.The weight average molecular weight of described polyurethane is 13000, weight-average molecular weight/number-average molecular weight=2.2.
On the peel ply of above-mentioned liner, form many ridges continuously along cross spider, it is corresponding to the groove of transferring on the adhesive phase, and described ridge intersects mutually.The height of described ridge is 19.5 microns.Therefore, the depth capacity of described adhesive surface upper groove is 19.5 microns.Ultimate range between the adjacent ridge (distance between the ridge bottom) is 12mm, and the width of ridge is 55 microns.Described ridge vertical cross-section is trapezoidal.Correspondingly, the groove vertical cross-section on the adhesive layer also is trapezoidal.
The adhesive phase with liner that makes more than the dry-pressing on the rear surface of acceptor sheet basic unit, described then polyester support is removed from the surface of receptive layers, makes the acceptor sheet of this embodiment.
Use prepared acceptor sheet, the Marking film that makes this embodiment as described below:
With (the Scotchprint of static dump system
9512, make by 3M) at offset medium (TRIDENT
, make by 3M) on be formed for the digital picture of transfer printing.Then, the offset medium that will have print image is rolled into web-like, makes media roll.
Then, acceptor sheet and media roll are fixed on the laminating machine (ORCA III is made by 3M), described laminating machine is operated under the following conditions, and the image of described colouring is transferred on the acceptor sheet, makes the volume mark film of this embodiment:
The image transfer ribbon part
-last roll temperature: 130 ℃
-following roll temperature: 50 ℃
-coiled material transfer rate: 70cm/ minute
-pressure: about 410kPa (60psi)
With the Marking film of this embodiment, the image that sees through protective film is clearly.
As described belowly carry out described toner viscosity test:
On toner image, form 100 intersection otch (sizes of each section: about 1mm * about 1mm), then adhesive tape (#610 is available from 3M) is adhered on the toner image.Peel off described adhesive tape rapidly.Observing does not have toner to be transferred on the adhesive tape, and the viscosity between this proof toner and the receptive layers is good.
With adhesive separately clearly protective film adhere on the toner image on the Marking film (colouring agent is accepted the surface), make Marking film with protective film.Used protective film is the protective film that comprises fluororesin, and it has adhesive phase (Overlaminate film SP 4114 is available from Sumitomo 3M Ltd.).
The described resistance to petroleum of evaluation as described below with Marking film of protective film:
Provide length to be about 50mm, width is about two rectangle marked diaphragms of 30mm.A slice adheres on the sheet (obtaining from PALTEC) of the coating melamine of baking with the Marking film adhesive phase with out-of-flatness bonding surface, and other sheet also adheres on the coated sheets with adhesive phase, and it and a slice are overlapped, and make test specimen.Described overlapping border width is about 10mm.Under this overlapping situation, petroleum fuel from the edge infiltration adhesive phase and the slit between the coated sheets of film, is carrying out described test easily relatively under the exacting terms.
Fixing described test specimen, the longitudinal edge portions that makes the width of two Marking films be about 10mm is immersed in the diesel oil (from Mobil Oil Co., Ltd. buys), and leaves standstill 8 hours.Afterwards, described sample at room temperature dried in the shade 16 hours, and its outward appearance then detects by an unaided eye.At any part place of two Marking films, do not find that interface peel, layer as peeling off between the receptive layers, also do not find wrinkle, and outward appearance keep well.
The moisture-proof gas of evaluation mark film as mentioned above.The edge of described Marking film is not rolled from adhesion (sheet of the coating melamine of baking).Like this, moisture-proof gas is chosen as well.
Embodiment 2
Except receptive layers is only formed by polycarbonate polyurethane and uses the receptor film of being made up of this receptive layers, make the acceptor sheet of this embodiment as same way as described in the embodiment 1.The thickness of described acceptor sheet is 33 microns.
With the Marking film of this embodiment, the image that sees through the protective film observation is clearly.The viscosity of described toner is good, does not observe toner and is transferred on the adhesive tape.
Resistance to petroleum as mode evaluation mark film identical as described in the embodiment 1: do not find that interface peel, layer as peeling off between the receptive layers, also do not find wrinkle, and outward appearance keep well.
Moisture-proof gas as mode evaluation mark film identical as described in the embodiment 1.The edge of described Marking film is not rolled.
Embodiment 3
Except using PCL polyurethane, make the acceptor sheet of this embodiment as same way as described in the embodiment 2 as the polyurethane.The used polyurethane of this embodiment is to prepare by PCL, MDI and the neopentyl glycol of polymerization as raw material.The Tg of described receptive layers (thermoplastic resin membrane) is 0 ℃.
With the Marking film of this embodiment, the image that sees through the protective film observation is clearly.The viscosity of described toner is good, does not observe toner and is transferred on the adhesive tape.
Resistance to petroleum as mode evaluation mark film identical as described in the embodiment 1: do not find that interface peel, layer as peeling off between the receptive layers, also do not find wrinkle, and outward appearance keep well.
Moisture-proof gas as mode evaluation mark film identical as described in the embodiment 1.The edge of described Marking film is not rolled.
Embodiment 4
Except the acceptor sheet is only formed by phenoxy resin, make the acceptor sheet of this embodiment as same way as described in the embodiment 2.
Except the acceptor sheet that uses this embodiment, make a volume mark film as identical mode as described in the embodiment 1.
With the Marking film of this embodiment, the image that sees through the protective film observation is clearly.The viscosity of described toner is good, does not observe toner and is transferred on the adhesive tape.
Resistance to petroleum as mode evaluation mark film identical as described in the embodiment 1: do not find that interface peel, layer as peeling off between the receptive layers, also do not find wrinkle, and outward appearance keep well.
Moisture-proof gas as mode evaluation mark film identical as described in the embodiment 1.The edge of described Marking film is not rolled.
Comparative Examples 1
Except with thickness being 50 microns ionomer films (HIMIRAN
1601, available from MITSUI DUPONT Co.,, make the Marking film of this Comparative Examples as same way as described in the embodiment 2 Ltd.) as beyond the receptive layers.
With the Marking film of this embodiment, the image that sees through the protective film observation is clearly.The viscosity of described toner is good, does not observe toner and is transferred on the adhesive tape.
Resistance to petroleum as mode evaluation mark film identical as described in the embodiment 1: as described in the receptive layers swelling, described Marking film is peeled off from adhesion.
Comparative Examples 2
Except receptive layers is only formed by following polyester-polyurethane, make the acceptor sheet of this Comparative Examples as same way as described in the embodiment 2.
The used polyurethane of this Comparative Examples is to comprise 1 by polymerization, 6-hexylene glycol, 1, and the raw material of 4-butanediol, adipic acid, IPDI and hydrogenation MDI prepares.
The toner transfer printing performance of the Marking film of this Comparative Examples is low, makes the definition of image be not so good as the image of embodiment 1-4.When estimating the moisture-proof gas of described Marking film with embodiment 1 described same way as, the edge of described film is rolled.Like this, described moisture-proof gas is obviously not as embodiment 1-4.
Embodiment 5
Forming thickness by the composition that comprises methyl methacrylate (MMA)-butyl acrylate (BA)-methyl acrylate (MA)-styrene (St) copolymer (MMA: BA: MA: St=69: 23: 3: 5, weight meter) and titanium dioxide is 80 microns individual layer white film.The glass transition temperature Tg of described receptive layers is 56 ℃.
Described film cuts into 25mm, uses cupping machine to measure its percentage elongation down at 20 ℃, and clamp distance is 100mm, and pulling speed is 300mm/ minute.Percentage elongation is 55%.
To be used for the stripper surface of the independent paint liner of coating of adhesive phase in embodiment 1 described identical mode, and the dry adhesive phase with liner that makes.Then, the receptive layers film dry-pressing that step is before made makes the described acceptor sheet of this embodiment in adhesive phase.
Be formed for the digital figure of transfer printing in embodiment 1 described identical mode.Then, except the temperature of top roll is 135 ℃,, make the Marking film of this embodiment under the condition identical as described in embodiment 1 image of colouring being transferred on the above-mentioned acceptor sheet.With TRIDENT
Paper carrier peel off.Described perusal confirms the complete transfer printing of described toner image.
Described toner-viscosity test carries out in embodiment 1 described identical mode.Observing does not have toner to be transferred on the adhesive tape, confirms that the viscosity between toner and the receptive layers is good.
Identical transparent protective film used among the embodiment 1 adheres on the toner image on Marking film (painted acceptance surface) with adhesive, makes on the Marking film of protective film.
Evaluation as described below has the resistance to petroleum of the Marking film of protective film:
Described Marking film is cut into 50 square millimeters sheet, and adhere to the adhesive phase of Marking film on the sheet (obtaining) of coating baking melamine, make test specimen from PALTEC.Fixing described test specimen makes the width of Marking film be about being immersed in the diesel oil (from Mobil Oil Co., Ltd. buys) than low edge of 10mm, and left standstill 8 hours.Afterwards, described sample at room temperature dried in the shade 16 hours, and its outward appearance then detects by an unaided eye.Any part place at Marking film does not find swelling, does not find that film peels off yet, and outward appearance keeps good.
Comparative Examples 3
Except used thickness is that 80 microns polymethyl methacrylate replaces the MMA-BA-MA-St copolymer, make the acceptor sheet of this Comparative Examples in embodiment 5 described identical modes.The percentage elongation of this methyl methacrylate film is 5%, when the same terms as described in embodiment 5 is measured.This percentage elongation is meant that the percentage elongation of this film is little, makes Marking film not enough to the adaptability on complete surface.
Except using the acceptor sheet that above-mentioned steps makes, make Marking film as identical mode as described in the embodiment 5.But a part of toner is stayed on the paper carrier, so the transfer printing of toner can not be satisfactory.However, but the toner of primary transfer can not be transferred on the adhesive tape in toner-viscosity test, and has good cementing property.
In embodiment 5 described identical modes, protective film is adhered on the toner image of Marking film, make on the Marking film with protective film, it carries out the resistance to petroleum test.Do not observe swelling, do not have film to peel off yet.
Comparative Examples 4
Except used thickness is that 50 microns acrylic resin film (comprising 90 weight portion BA and 10 parts by weight of acrylic acid) replaces the MMA-BA-MA-St copolymer, make acceptor sheet in the Comparative Examples as same way as described in the embodiment 5.The Tg of this film is-50 ℃.The surface of this film has viscosity, so it is unsuitable for the receptive layers as Marking film.
Claims (8)
1. Marking film, described film comprises:
(a) receptor film, it has as colouring agent accepts the front surface on surface and the back of the body surface relative with described front surface,
(b) colouring agent of on the front surface of described receptor film, accepting and
(c) be fixed on the described lip-deep adhesive phase of thin film back of accepting, it comprises the described film of accepting is adhered to adhesive on the adhesion,
Wherein, described adhesive phase has projection and the sunk part around described projection that comprises described adhesive, above-mentioned convexing to form on the bonding surface that will be adhered on the described adhesion, when described adhesive phase adheres on the described adhesion, form conduit between the described bonding surface that is recessed in described adhesion surface and adhesive phase, be used for being communicated with atmosphere, it is characterized in that, described receptor film comprises the receptive layers that is formed by the thermoplastic resin membrane, has the surface of accepting the surface as colouring agent; Described thermoplastic resin membrane comprises the resinite component, it comprises the resin of at least a anti-oil, is selected from the polyurethane that comprises the polyol unit of being derived by polycarbonate polyol, comprises polyurethane and phenoxy resin by the polyol unit of PCL polyol derivative.
2. Marking film as claimed in claim 1 is characterized in that described thermoplastic resin membrane comprises polyurethane and phenoxy resin.
3. Marking film as claimed in claim 1 is characterized in that described receptor film is made up of described receptive layers basically.
4. acceptor sheet, it is printed by the static toner and is used to make the described Marking film of claim 1, described acceptor sheet comprises described receptor film and the described adhesive phase that is fixed on the described receptor film rear surface, described receptor film comprises the receptive layers that is formed by the thermoplastic resin membrane, has as colouring agent to accept the surface that surperficial toner is transferred to; Wherein, described thermoplastic resin membrane comprises the resinite component, it comprises the resin of at least a anti-oil, be selected from the polyurethane that comprises the polyol unit of deriving, comprise polyurethane and phenoxy resin, and the glass transition temperature of described receptive layers is 0-100 ℃ by the polyol unit of PCL polyol derivative by polycarbonate polyol.
5. Marking film, described film comprises:
(a) receptor film, it has as colouring agent accepts the front surface on surface and the back of the body surface relative with described front surface,
(b) colouring agent of on the front surface of described receptor film, accepting and
(c) be fixed on the described lip-deep adhesive phase of thin film back of accepting, it comprises the described film of accepting is adhered to adhesive on the adhesion,
Wherein, described adhesive phase has projection (being formed on the bonding surface that will be adhered on the described adhesion) and the sunk part around described projection that comprises described adhesive, when described adhesive phase adheres on the described adhesion, form conduit between the described bonding surface that is recessed in adhesion surface and adhesive phase, be used for being communicated with atmosphere, it is characterized in that, described receptor film is the film of anti-Petropols that comprises copolymer, and described copolymer comprises at least a acrylic acid C1-C8 alkane ester and methyl methacrylate.
6. acceptor sheet, it is printed by the static toner and is used to make the described Marking film of claim 5, described acceptor sheet comprises described receptor film and the described adhesive phase that is fixed on the described receptor film rear surface, wherein, described receptor film is the film of anti-Petropols that comprises copolymer, described copolymer comprises at least a acrylic acid C1-C8 alkane ester and methyl methacrylate, and the glass transition temperature of described film is 0-100 ℃.
7. as claim 1 or 5 described Marking films, it also comprises the printing opacity protective film that covers the receptor film front surface of accepting described colouring agent, it is characterized in that described protective film comprises fluororesin.
8. Marking film that is used for vehicle, it comprises claim 1 or 5 described Marking films, it adheres to uses on the carbody surface of petroleum fuel as driven by energy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP363963/2002 | 2002-12-16 | ||
| JP2002363963A JP2003326629A (en) | 2002-03-05 | 2002-12-16 | Marking film, receptor sheet and marking film for vehicle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1726137A true CN1726137A (en) | 2006-01-25 |
Family
ID=32708098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200380106126 Pending CN1726137A (en) | 2002-12-16 | 2003-12-09 | Marking film, receptor sheet and marking film for vehicles |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1572466A1 (en) |
| CN (1) | CN1726137A (en) |
| AU (1) | AU2003296458A1 (en) |
| WO (1) | WO2004060688A1 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6349590A (en) | 1986-08-19 | 1988-03-02 | Bridgestone Corp | Rubber crawler |
| JP2503717Y2 (en) | 1992-04-03 | 1996-07-03 | 日栄化工株式会社 | Adhesive sheet |
| US5468532A (en) * | 1992-12-10 | 1995-11-21 | Minnesota Mining And Manufacturing Company | Multilayer graphic article with color layer |
| US6197397B1 (en) | 1996-12-31 | 2001-03-06 | 3M Innovative Properties Company | Adhesives having a microreplicated topography and methods of making and using same |
| US6203885B1 (en) | 1998-06-18 | 2001-03-20 | 3M Innovative Properties Company | Cling films having a microreplicated topography and methods of making and using same |
| DE19834218A1 (en) | 1998-07-29 | 2000-02-03 | Heuft Systemtechnik Gmbh | Procedure for checking closed containers |
| CA2368811A1 (en) * | 1999-03-30 | 2000-10-05 | Minnesota Mining And Manufacturing Company | Adhesion-enhancing surfaces for marking materials |
| JP2001341420A (en) * | 2000-06-05 | 2001-12-11 | Three M Innovative Properties Co | Image recording medium |
| JP2002019303A (en) | 2000-07-10 | 2002-01-23 | Harima Chem Inc | Thermosensitive recording medium |
-
2003
- 2003-12-09 AU AU2003296458A patent/AU2003296458A1/en not_active Abandoned
- 2003-12-09 WO PCT/US2003/039284 patent/WO2004060688A1/en not_active Application Discontinuation
- 2003-12-09 CN CN 200380106126 patent/CN1726137A/en active Pending
- 2003-12-09 EP EP03814702A patent/EP1572466A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004060688A1 (en) | 2004-07-22 |
| AU2003296458A1 (en) | 2004-07-29 |
| EP1572466A1 (en) | 2005-09-14 |
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