CN110003809A - Heatproof can laser marking film - Google Patents

Heatproof can laser marking film Download PDF

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Publication number
CN110003809A
CN110003809A CN201811553625.5A CN201811553625A CN110003809A CN 110003809 A CN110003809 A CN 110003809A CN 201811553625 A CN201811553625 A CN 201811553625A CN 110003809 A CN110003809 A CN 110003809A
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CN
China
Prior art keywords
weight
melting
laser marking
film
marking film
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Pending
Application number
CN201811553625.5A
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Chinese (zh)
Inventor
S.格伦德
M.塞伯特
G.德罗顿
T.尼迈耶
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Tesa SE
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Tesa SE
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Publication of CN110003809A publication Critical patent/CN110003809A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/43—Marking by removal of material
    • B42D25/435—Marking by removal of material using electromagnetic radiation, e.g. laser
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • 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
    • 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
    • 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
    • B41M5/24—Ablative recording, e.g. by burning marks; Spark recording
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/006—Presence of (meth)acrylic polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2471/00—Presence of polyether
    • C09J2471/006—Presence of polyether in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane in the substrate

Abstract

The present invention relates to good long-term temperature tolerance, good chemical resistance and height anti-counterfeiting performance can laser marking film, it includes equivalent beds based on cured acrylate coating composition and the carving layer being arranged in above equivalent beds, the film further has the potential reaction gluing oxidant layer being arranged in below equivalent beds, it includes the melting temperature T (melting) with 35 DEG C≤T (melting)≤90 DEG C and includes the thermoplastic component for the functional group that can be reacted with isocyanates and with being in granular form, it is particularly dispersed in fine particulate in thermoplastic component and is closed, microencapsulation or the component containing isocyanates inactivated substantially in the region of particle surface, wherein particle has the initial temperature T (starting) of 40 DEG C≤T (starting)≤120 DEG C, and wherein T (starting) >=T (melting ).

Description

Heatproof can laser marking film
Technical field
The present invention relates to it is a kind of can laser marking (laserbeschriftbare) film comprising be based on cured third The equivalent beds of olefin(e) acid ester paint composition (coating compositions), wherein the cured acrylate coating composition be based on include with The composition of lower component: the trifunctional monomer B of trifunctional the oligomer A, 0 to 20 weight % of 30 to 80 weight %, 1 to 30 weight Measure the coloring pigment of the bifunctional monomer weight of C and 2 to 40 % of %；With the carving layer being arranged in above the equivalent beds, with And be related to made of the film can laser marking label.The invention further relates to preparation can laser marking film method and The film of preparation and the purposes of label.
Background technique
The label of object becomes more and more important.For example, in the automotive industry, traditional printed label is by can laser The label of mark replaces.By means of can laser marking label, the information of such as tire pressure or fuel type and instruction are set to In in the various parts of motor vehicles.Other than these instructions, can the label of laser marking may also include security information for example Chassis and identification of the vehicle.Corresponding label permission is obtained in the case where theft or accident about in vehicle and its manufacturing process Fabrication stage conclusion.Such as hologram, lasting UV trace (foot are used on the substrate of adhesive label thereon Print specific safety feature) and purposefully selection can the material of label of laser marking on the one hand make it difficult to copy Material and another aspect show and distort trial (Manipulationsversuche).
From the prior art it is known can laser marking label, can rapidly be write, the height for allowing to be written character is right Than degree and ensure heat-resisting quantity in a short time.81 30 861 U1 of DE discloses multilayer labels, and it includes thin and thick Paint layer and high temperature is born in a short time.101 42 638 A1 of DE 100 48 665 A1 and DE is described can laser marking Label, equally bear high temperature in a short time.
However, the label of the prior art will appear a layer or more in the case where long-term temperature influences A layer of contraction (" shrinkage ").It is assumed that this contraction is caused by variation as a layer or multiple layers of area expansion.? The performance of the contraction of one or more layers in known label is removing of the label in its fringe region.At sensitive data such as bottom In the case that disk is numbered, inherently there is safety problem in this removing, because label may be with undamaged and noresidue Mode is completely removed.On the other hand, when the expansion behavior of the different layers in label with temperature increase and it is different or When chemical process leads to the shrinkage in layer, the tension in label can lead to by the contraction.This can for example pass through ageing process (such as cross-linking reaction) causes.It in the case where such tension, cracks in label, thus one side aesthetic requirement is not It is fully considered, on the other hand may mistakenly suspect and distort trial.
To can need under the background that is continuously improved of durothermic requirement of the label within a longer period of time of laser marking It is improved be used as accordingly can laser marking label starting material film.From it is known in the art it is all can laser marking Label and film only limitedly meet to anti-distort and high durothermic growing requirement.Particularly at high temperature, The label known occur the loss (this show as shrink or " shrinkage ") of a layer or multiple layers of dimensional stability and occur with Relevant label edges tilt (Kantenabheben) and crack.
2011080803 A1 of DE disclose in this context can laser marking film, can be used as manufacture dimensionally stable Can laser marking label starting material, and wherein keep compared with the label of the prior art or improve chemical resistant Property.This film has the equivalent beds based on cured acrylate coating composition, and the acrylate coating composition is based on Composition including following components: the trifunctional monomer B of trifunctional the oligomer A, 0 to 20 weight % of 30 to 80 weight %, 1 to The coloring pigment of the bifunctional monomer weight of C and 2 to 40 % of 30 weight %.
Application for film or label prepared therefrom, can laser marking film below equivalent beds have pressure-sensitive adhesive Layer.In this case, owning with high cohesive force (adhesion strength) and high touch sticky (Anfassklebrigkeit) Typical binders, particularly acrylate adhesive, such as resin modified acrylate adhesive, natural rubber adhesive and Synthetic rubber adhesive is all defined as suitable pressure-sensitive adhesive.
It has now been found that the adhesive according to the prior art for film and label is not suitable for reliably and durably unfortunately Bond them.(it must wherein apply relatively thick gluing oxidant layer in particular for structured substrate to obtain bonding good enough Power), it has been found that, it, can be without passing through cutting gluing oxidant layer in the case where destroying film or label due to the thickness of gluing oxidant layer To remove striping or label.It is thus impossible to guarantee anti-forgery security.In addition, the film of the prior art is not met by auto industry About durothermic long-term requirement.
Summary of the invention
Therefore, the purpose of the present invention is to provide it is a kind of following can laser marking film, can be easily and safely (reliable Ground) adhere in different substrates, wherein the film be anti-tamper security and can not in the case where no damage again from Substrate removing.The film must also meet requirement of the automobile industry to long-term temperature stability (150 DEG C, 1,600 week) and It in this case is chemical resistance, particularly to liquid such as gasoline or brake fluid common in automobile industry.
The purpose realizes that the film further comprises being arranged in below equivalent beds by the film for the type being initially mentioned At least one, preferably just what a gluing oxidant layer (or adhesive layer), wherein the adhesive layer is potential reaction adhesive Layer comprising the melting temperature T (melting) with 35 DEG C≤T (melting)≤90 DEG C and include the official that can be reacted with isocyanates The thermoplastic component that can be rolled into a ball, and the mode to be in granular form, being particularly dispersed in thermoplastic component to fine particulate exist And it is closed, microencapsulation or the component containing isocyanates inactivated substantially in the region of particle surface, wherein particle has There is 40 DEG C≤T (starting)≤120 DEG C of initial temperature T (starting), and wherein T (starting) >=T (melting).Fine particulate This means with d50< 50 μm of particle size distribution (i.e. size distribution), wherein the particle size distribution is preferably < 15 μm.
This film meets the requirement to high anti-forgery security, because can not nondestructively remove from substrate；It meets to length Phase durothermic requirement, that is to say, that even if 150 DEG C at a temperature of continue 1600 weeks without discovery removing, shrink, crack Deng；And meet requirement to chemical resistance.Therefore, the film is highly suitable as in various fields, particularly in vapour Anti-tamper security in turner industry, can laser marking film.
Chemical resistance in the sense that refers to for example to the hydro carbons such as fuel for motor vehicle that can contact with label and molten The tolerance of agent.
For purposes of this application, T (melting) is the melting temperature of thermoplastic component, and T (starting) is dispersed in thermoplasticity The isocyanate groups of particle in component can be with the functional group reactions of thermoplastic polyurethane (such as because they and thermoplasticity Polyurethane is distributed in matrix together) temperature.In the case where closed isocyanate groups, T (starting) is deblocking temperature (Deblockierungstemperatur), in the case where microencapsulation, (such as pass through for isocyanates from microcapsules release The thawing of microcapsule shell) temperature, and in the case where being the isocyanates inactivated in the surface region of isocyanate particles, For the temperature of isocyanate particles fusing.For purposes of the present invention, it is contemplated that with good grounds satisfaction known in the art close In being closed of information of T (starting), microencapsulation or the system containing isocyanates inactivated in the region of particle surface.Heat Plastic polyurethane and component containing isocyanates preferably it is dispersible in an aqueous medium or dispersion in an aqueous medium.
Melting temperature is measured by differential scanning calorimetry (DDK, DSC) according to DIN 53765-B-10 (1994).T (rises Begin) measurement also by differential scanning calorimetry (DDK, DSC) carry out.Here, to first under the 10K/ minutes rates of heat addition Heat release signal in the thermogram of heating curves is assessed, this corresponds to the reaction of isocyanate groups.The signal rises Beginning temperature is used as T (starting).
In a preferred embodiment of the invention, the composition that acrylate coating composition is based on includes 50 To 60 weight %, trifunctional the oligomer A, 5 to 15 weight % of preferably 52 to 58 weight %, preferably 8 to 12 weight % The bifunctional monomer C of the trifunctional monomer weight of B and 5 to 15 %, preferably 8 to 12 weight.The propylene of preferred embodiment The amount of coloring pigment in acid esters coating composition depends on the type of material therefor.The case where carbon black is as coloring pigment Under, for example, it is preferred to using 2 to 7 weight %, and in TiO2In the case where, it is preferred to use 15 to 40 weight %, particularly preferably 22 to 28 weight % of ground.Trifunctional oligomer A, trifunctional monomer B and bifunctional monomer C are hereinafter also referred to as component A, component B or component C.Astoundingly it has been found that spy can be obtained in the composition of the coloring pigment comprising component A, B and C and the amount The cured acrylate coating composition of other heatproof.
Carving layer is arranged on the layer above equivalent beds, can come by means of single laser beam or by means of multiple laser beams Mark.During the mark, carving layer is ablated at the position that the laser beam with energy appropriate is aligned (site). Under enough energy inputs, carving layer is fully removed by part, so that it is light transmission (transparent) at these locations. It is also contemplated that carving layer at some positions only by partly ablation so that at these locations generate carving layer not Transparent appearance.Carving layer is preferably coating (paint) layer, can be applied by printing technology.Corresponding printing coatings (paint) layer Preferred example includes the printing coatings (paint) based on the curable acrylate paint of electron beam curable or UV (paint).At this In the alternative embodiment of invention, carving layer is made of thin metal layer.Carving layer preferably have 1 to 30 μm, preferably 1 to 20 μm of ground, particularly preferably 1 to 10 μm of thickness.If the thickness of carving layer moves in the range, can provide especially Heatproof can laser marking film.With preferably have 20 to 300 μm, preferably 40 to 200 μm, particularly preferably 60 to 150 μ The equivalent beds of the thickness of m compare, and the thickness of carving layer is preferably the 10% or smaller of such as equivalent beds' thickness.
The equivalent beds of film of the invention include cured acrylate coating composition, based on the group including following components Close object: the trifunctional oligomer A of 30 to 80 weight %, preferably 50 to 60 weight %, particularly preferably 52 to 58 weight %, 0 To the trifunctional oligomer B of 20 weight %, preferably 5 to 15 weight %, particularly preferably 8 to 12 weight %, 1 to 30 weight The bifunctional monomer weight of C and 2 to 40 % of amount %, preferably 5 to 15 weight %, particularly preferably 8 to 12 weight % Color pigment.The equivalent beds of film of the invention can be provided by solidifying the composition including component A, B and C and coloring pigment. For this purpose, the composition is radiated by UV, electronic beam curing (hereinafter referred to as ESH) is crosslinked or heat cross-linking.Crosslinking preferably passes through ESH It carries out.
The equivalent beds of film according to the present invention include at least one coloring pigment.In the context of the present invention, face is coloured Material includes but is not limited to all coloring face that can be used as painting (Farben) and dyestuff and/or brightening agent in varnish (Lacken) Material.The example of coloring pigment is rutile titanium dioxide (" TiO2", such as the rutile-type from Kronos company), carbon black (such as Printex type from Evonik company) or other coloring pigments well known by persons skilled in the art, such as in religion section Book Lacke und Beschichtungen Bd.5 (Hans Kittel und J ü rgen Spille, Hirzel Verlag (Stuttgart), 2003) those of mentioned.Coloring pigment is preferably as weather-proof as possible (witterungsstabile's) Pigment.For equivalent beds, particularly preferably rutile titanium dioxide.Vital for the present invention is not pigment or right Than the color of layer itself, but the color difference or contrast obtained compared with carving layer.The pigment that the present invention uses is used herein to adjust It saves after film mark, i.e., the contrast generated between equivalent beds and carving layer after through laser ablation carving layer.
Trifunctional oligomer A is per molecule tool there are three the oligomer of unsaturated (methyl) acrylic ester unit, and number is equal Molecular weight Mn (being measured by GPC, calibrated with polystyrene standards) preferably between 1000 and 5000g/mol, preferably Between 1400 and 3600g/mol, preferably between 1800 and 2200g/mol, be particularly preferred in 1900 and 2100g/ Between mol.If molecular weight Mn, in the range, this has the long-term temperature tolerance of cured acrylate coating composition There is positive influence, to can get the equivalent beds of special dimensionally stable.
In a preferred embodiment, trifunctional oligomer A is selected from (methyl) acrylate of polyurethane three and polyester Three (methyl) acrylate, wherein particularly preferred polyurethane three (methyl) acrylate.Term " (methyl) acrylate " packet Include acrylate, methacrylate and its mixture.Trifunctional oligomer A is preferably polyurethane three (methyl) acrylic acid Ester, more preferably urethane triacrylate.Polyurethane three (methyl) acrylate is that per molecule has each three unsaturations The oligomer of (methyl) acrylate group and multiple (that is, at least two) urethane units.Preferred polyurethane three The example of acrylate is the aliphatic urethane triacrylate of Sartomer CompanyWithWherein it is particularly preferably
Trifunctional monomer B per molecule is comprising three unsaturation (methyl) acrylic ester units and excellent in one kind of the invention In the embodiment of choosing have 300 to 1000g/mol, preferably 350 to 800g/mol, preferably 350 to 600g/mol, especially Preferably 400 to 450g/mol molecular weight.Component B is preferably chosen from the propoxylation of logical formula (I) and three hydroxyls of ethoxylation (methyl) acrylate of methylpropane three and propoxylation and (methyl) acrylate of the glycerol of ethoxylation three or its mixing Object:
Wherein the R in Formulas I represents hydrogen or methyl；A is hydrogen or ethyl；X, Y and Z each independently represents propylene or ethylene list Member；And a, b and c are each independently 1 to 4, preferably integer of 1 to 3, and a+b+c is 3 to 12, preferably 3 to 9 Number.In particularly preferred embodiment of the invention, X, Y and Z are propylene units.It is particularly preferred that trifunctional monomer is Propenoxylated glycerol tri-acrylate.If selection trifunctional monomer B falls molecular weight within the above range and/or monomer B is fallen into above-mentioned Formulas I, then component B also to the temperature tolerance of equivalent beds and therefore to can laser marking film temperature tolerance generate product The influence of pole.
Bifunctional monomer C is that there are two the monomers of unsaturated acrylic ester unit for per molecule tool.Component C preferably has 100 to 1000g/mol, preferably 180 to 350g/mol, particularly preferably 220 to 280g/mol molecular weight, and preferably Glycol diacrylate selected from logical formula (II):
With the propylene glycol diacrylate of logical formula (III):
Or mixtures thereof, wherein the n in Formula II and III is each independently 1 to 15, preferably 1 to 9, particularly preferably 2 To 6 integer, and most preferably 3 or 4.In particularly preferred embodiment of the invention, bifunctional monomer C is triethylene glycol Diacrylate.If selection bifunctional monomer C make molecular weight within the above range and/or monomer C fall into above-mentioned Formula II or In III, then component C also to the temperature tolerance of equivalent beds and therefore to can laser marking film temperature tolerance generate positive influence.
In particularly preferred embodiment of the invention, equivalent beds are based on a kind of composition, and the composition includes at least one Plant urethane triacrylate, preferably from Sartomer CompanyOrAs Component A, the propenoxylated glycerol tri-acrylate of Formulas I given above is as component B, triethylene glycol diacrylate conduct The titanium dioxide of component C and pigment such as rutile-type.
Potential reaction gluing oxidant layer is based preferably on so-called 1K potential reaction polyurethane, by aqueous polyurethane point Granular media, preferably Bayer AG companyIt obtains.Potential reaction adhesive film includes having melting temperature T (melting) and include the functional group that can be reacted with isocyanates thermoplastic component and be in granular form ground, particularly thin The mode being dispersed in the thermoplastic component granularly exists and what is inactivated substantially in the region of particle surface contains isocyanide The component of acid esters.Mean herein with d to fine particulate50< 50 μm of particle size distribution, wherein the particle size distribution is preferred Ground is < 15 μm.
Particle has initial temperature T (starting), wherein being applicable in T (melting)≤T (starting).T (melting) is in 35 DEG C and 90 DEG C Between, preferably between 40 DEG C and 60 DEG C.T (starting) between 40 DEG C and 120 DEG C, be preferably lower than 100 DEG C, be most especially excellent Selection of land is lower than 90 DEG C.As lower limit, it is therefore preferable to 50 DEG C and particularly preferably 60 DEG C.Potential reaction adhesive film is in room temperature Under be not pressure sensitive glueyness, thus heat cause and start bonding adhesion strength building before ensure it is good can (weight Newly) polarization.
T (melting) < T (starting) is particularly preferred, because of that can reliably avoid in the glue for preparing breadth form Cross-linking reaction is unintentionally triggered when stick product.
As thermoplastic component, it is preferred to use use OH group and/or NH2Those of group functionalization compound.Thermoplastic Property component is most preferably at least one semicrystalline polyester polyurethane.
Potential reaction gluing oxidant layer preferably includes anionic, high molecular weight dispersions of polyurethanes conduct herein Thermoplastic component, with 35 DEG C≤T (melting)≤90 DEG C, particularly 40 DEG C≤T (melting)≤60 DEG C of melting temperature T (melts Melt) (in a dried form) and include the functional group that can be reacted with isocyanates, such as to come from above-mentioned Dispercoll U system The form of the commercial product of column；Such as Dispercoll U53, Dispercoll U54, Dispercoll U56, Dispercoll U 8755、Dispercoll U XP 2815、Dispercoll VP KA 8758、Dispercoll U XP 2682、 Dispercoll U 2824 XP、Dispercoll U XP 2701、Dispercoll U XP 2702、Dispercoll U XP 2710 and/or Dispercoll BL XP 2578 (registered trademark that Dispercoll is Bayer AG).
In addition, potential reaction gluing oxidant layer preferably includes toluylene (toluene (Toluylen)) diisocyanate Compound (TDI compound) such as Dispercoll BL XP 2514 (TDI dimer) and/or the Aqualink U (TDI of sealing end The dispersion of dimer) and/or isophorone diisocyanate (IPDI) such as Aqualink D (point of the IPDI tripolymer of sealing end Granular media) as the component containing isocyanates, the side in thermoplastic component is dispersed in be in granular form, particularly fine particulate Formula exists and is closed, microencapsulation or inactivates substantially in particle surface region.Diisocyanate is for example with corresponding potential The form of the aqueous suspension of reactive solid isocyanates uses.Aqualink is provided by Aquaspersions company.Especially Ground with as thermoplastic component anionic high molecular weight dispersions of polyurethanes (such as above-mentioned Dispercoll U produce Product) it is combined, above-mentioned diisocyanate product can be used as crosslinker component.It can be used other isocyanates, including monomer and low Polyacetylene compound and polyisocyanates.
In addition, potential reaction gluing oxidant layer may include other formulation ingredients.These include thickener, wetting agent, disappear Infusion, filler (such as heat filling), pigment, catalyst, age resister, light stabilizer and for setting specific adhesive property Other polymer.For example, passing through mixing amorphous polymer (such as poly(ether-urethane) (polyether polyurethane) or polyacrylic acid Ester) water-borne dispersions and/or by mixing aqueous resin dispersion (in particular upon rosin ester) or liquid resin, be adjusted Specific adhesive property.
Preferably, potential reaction gluing oxidant layer is not pressure sensitive glueyness at room temperature.
According to the present invention, at least one potential reaction gluing oxidant layer have at least 10 μm at most 500 μm, preferably extremely Few 15 μm at most 250 μm and most particularly preferably 20 μm at most 35 μm of thickness degree.
The invention further relates to made of the film can laser marking label.This is completed in cutting or punching course 's.Due to it is according to the present invention can laser marking film have gluing oxidant layer, can be marked by being stamped or cut out step Label, the label can be applied directly in different substrates without the (in the form of batch as former state Konfektionierter Form) carry out further coating step.
It is according to the present invention can the film of laser marking can manufacture in various ways.However, in a preferred embodiment, this Invention be related to manufacture can laser marking label method, comprising the following steps:
I) support membrane (backing film) is provided；
Ii) carving layer is applied on support membrane；
Iii the acrylate coating composition including component A, optionally B, C and coloring pigment) is applied to carving layer On；
Iv solidify the acrylate coating composition) to obtain equivalent beds；
V) potential reaction gluing oxidant layer is applied to equivalent beds and goes up and use peeling paper or similar release liner rubber cover Stick；
Vi) and remove support membrane.
In the method, the conventional film based on a variety of materials such as polyethylene terephthalate (PET) can be used to make For support membrane, it is also referred to as technique liner.Carving layer is applied on support membrane and applies acrylate coating composition Being added on carving layer can all be completed by conventional printing and paint-on technique.In the preferred embodiments of the present invention by Apply acrylate coating composition in comma stick (Kommarakel).
Preferably, gluing oxidant layer is laminated in membrane form on the film being made of carving layer and equivalent beds.Gluing oxidant layer Film preferably has 10g/m2To 100g/m2, preferably 15g/m2To 75g/m2, particularly preferably 20g/m2To 60g/m2And it is special Other ground 25g/m2To 50g/m2Weight per unit area.
Finally, the purposes the present invention relates to the film of preparation and label in the automotive industry.
Surprisingly it was found that can be prepared by the method compared with the known film and label of the prior art And including the equivalent beds based on the acrylate coating composition according to the present invention can laser marking film have improve Long-term temperature tolerance.Therefore, film of the invention particularly meet GB standard GB/T 25978 to long-term temperature tolerance (150 DEG C, 1, 600 weeks) requirement.The long-term temperature tolerance of this raising show by adhesive be applied to film in substrate and label through pressing down The edge of system tilts aspect, and under the bond state to substrate under the influence of long-term temperature reduction tearing tendency.It enables People in surprise, there is improved durothermic film according to the present invention and label also to show excellent tamper-resistance properties, because, to the greatest extent Them are managed with temperature stability, but in the case where distorting trial, they are broken in the region of equivalent beds, such as are bonding During being attempted under state from the removing of substrate.This fracture is presented as externally visible with obvious identifiable cracking forms.Knot Fruit, when also being attempted accordingly, label according to the present invention then only attempt by tamper-indicating.
The present invention is explained in greater detail below with reference to embodiment.Unless otherwise stated, the institute in following embodiment The numerical value for the amount of having is the parts by weight based on total composition.
Specific embodiment
The preparation of sample
In order to prepare can laser marking film sample, in following Examples 1 and 2, first will as support carrier The polyester film of 50 μ m-thicks of film is in the UV flexographic presses of SMB company to be used to make in web speed printing in 15m/ minutes The Flexocure Gemini (black) from Flint company of standby carving layer, so that printing height is between 2 and 4 μm.With Afterwards, using the Hg radiant tube of E 70-2 (4) x1 BLK-2-SLC type from IST Metz GmbH company by thus obtained painting Layer UV solidification is to prepare carving layer.The radiant power of radiant tube is 80W/cm.
To prepare equivalent beds, by following components:
(VMA is come from the Dispermaten with water cooling dispersion cup (volume capacity 11) and 60mm dissolvers disk The dissolvers CN10 of Getzmann company) in merge, and 40 DEG C at a temperature of with 8000U/ minute homogenizing 20 minutes.By scraping Thus obtained composition is applied on carving layer by knife with 100 μm of thickness degree, and by electronic beam curing in 80kGy and Crosslinking is under 240kV to obtain equivalent beds.
Embodiment 1: before removing polyester support carrier film, by thus obtained by support carrier film/carving layer/comparison The compound of layer composition is applied to side equipped with the Acrylic Pressure Sensitive Adhesive (see below) of 40 μ m-thicks of release liner On；
Embodiment 2: the thus obtained composite layer being made of support carrier film/carving layer/equivalent beds is pressed in potential On reactive adhesive film.
By means of laser technology using the Nd:YAG solid state laser 50D from Rofin company to test lettering (Testschriftzug) and bar code carries out mark to the film so obtained, and is used in the same manner the laser and is cut to The label of 3 × 8cm size.
The preparation of the Acrylic Pressure Sensitive Adhesive of embodiment 1:
The pressure-sensitive adhesive used is resin modified acrylate adhesive, by propylene in the degree of 80 weight % It acid ester copolymer and is made of in the degree of 20 weight % terpene phenolic resin.The copolymer passes through 47.5 weight % propylene Sour N-butyl, 47.5 weight % 2-EHAs, 2 weight % glycidyl methacrylate and 1 weight % propylene The polymerization of acid obtains.
The preparation of the potential reaction adhesive film of embodiment 2:
By 100 parts of Dispercoll U53 (Bayer AG company), 10 parts of 2514 (Bayer of Dispercoll BL XP AG company) and 1.5 parts of Borchigel 0625 (OMG Borchers company) preparation potential reaction adhesive films.By formulation Ingredient uses anchor agitator to mix 15 minutes at room temperature with 60 1/min (rpm) as the water-borne dispersions in charging basket. Solid content is adjusted to 46 weight % by addition demineralized water.
By means of breadth coating apparatus, by means of scraper on temporary carrier with single side pretreated polyester film (50 μ m-thicks PET, the Hostaphan GN4600A type from Mitsubishi company) form prepares coating.
Then it is dehydrated in 40 DEG C of dry baking tunnel 15 minutes.By obtained bale packing (Ballen) be cut into 50mm wide and The volume of 100m long.Sample has 40 μm of potential reaction adhesive thicknesses of layers.
Test method
In order to determine temperature tolerance and anti-distort, each five labels of the sample obtained according to embodiment 1 to 4 are had detected. Program is as follows.
Temperature tolerance:
On the steel plate that laser tag is pasted to 1mm thickness in a manner of bubble-free, which is comprehensively coated with Kansai The solvent-type acrylic ester varnish (clear coat) (KINO 1210TW-2) of Paint company.It waits at room temperature about 24 hours Afterwards, sample is stored 2300 hours at 150 DEG C.
At the end of Storage period, check that the edge of sample tilts the (removing of label edges and substrate, in terms of mm-from label Edge metering) and label in crack quantity.In addition, the shrinking percentage of measurement sample (in terms of the % of original bond area).
As a result it is defined as the average value of five kinds of samples, and with 1 to 6 grade classification.Here, value 1-6 is respectively intended to mean:
1 edge, which tilts, is less than 0.1mm, and shrinking percentage is less than 0.5%；In addition, without visible crack；
2 edges, which tilt, is less than 0.5mm, and shrinking percentage is less than 2%；In addition, without visible crack；However, edge is tilted, is received Shrinkage and/or cracking are so obvious, so that the value of not up to " 1 "；
3 edges, which tilt, is less than 2.0mm and shrinking percentage less than 5%；In addition, most visible 2 cracks；However, edge is stuck up Rise, shrinking percentage and/or cracking it is so obvious so that not up to " 2 " value；
4 edges, which tilt, is less than 5.0mm and shrinking percentage less than 10%；In addition, most visible 5 cracks；However, edge is stuck up Rise, shrinking percentage and/or cracking it is so obvious so that not up to " 3 " value；
5 labels be completely exfoliated from substrate (" full side tilt () ") and shrinking percentage Kantenabheben It is 10% or higher；In addition, most visible 10 cracks；
(" full side tilting ") is completely exfoliated from substrate for 6 labels and shrinking percentage is 10% or higher；Furthermore, it is seen that be more than 10 A crack.
Anti-distort
In anti-distort (" distorting evidence (tamper evidence) ") test, test sample is with the side of bubble-free Formula affix on the steel plate of 1mm thickness after brittleness, the steel plate comprehensively paints the Clear for having Kansai Paint company Coat(KNIO 1210TW-2).For this purpose, it is intended to will after waiting 24 hours after being bonded to steel plate in a manner of bubble-free Sample is pulled away from from substrate.The anti-distort of laser tag material is with four evaluation grades (" 1 " to " 4 ") scoring.Detect safety post Label can be removed from substrate without damage with which supplementary means.In this case, " destruction " refers to the rupture and comparison of label The formation in the crack in layer.Here, value 4-1 is respectively intended to mean:
4 labels can be removed by hand without damage without additional auxiliary tool；For this respect, anti-distort is not Foot；
3 labels can not be removed by hand without damage but can be removed by sharp metal blade；It is anti-to usurp for this respect It is modified same insufficient；
2 can not also mark even with sharp metal blade as uniquely additional auxiliary tool without devastatingly removing Label；However, isopropanol is used to combine the removing that can carry out no destruction with sharp metal blade as solvent；Anti-distort is commented Grade is enough；
1 can not remove without damage using isopropanol to combine as solvent with sharp metal blade；This In the case of, tamper-resistance properties are rated well.
As a result
Test method Embodiment 1 Embodiment 2
Temperature tolerance 2 1
Tamper-resistance properties 3 1
Sample (embodiment 2) according to the present invention shows excellent tamper-resistance properties and simultaneously improved long-term temperature tolerance. In contrast, lead to insufficient tamper-resistance properties and poor simultaneously resistance to herein using the conventional label with pressure-sensitive adhesive Warm nature (embodiment 1).

Claims (11)

1. can laser marking film, including
Based on the equivalent beds of cured acrylate coating composition, wherein the cured acrylate coating composition base In the composition including following components:
The trifunctional oligomer A of 30 to 80 weight % of ο；
The trifunctional monomer B of 0 to 20 weight % of ο；
The bifunctional monomer C of 1 to 30 weight % of ο；
The coloring pigment of the weight of ο and 2 to 40 %；
The carving layer being arranged in above the equivalent beds, which is characterized in that the film is further
There is at least one the gluing oxidant layer being arranged in below the equivalent beds, wherein the adhesive layer is potential reaction Gluing oxidant layer, the gluing oxidant layer include the melting temperature T (melting) with 35 DEG C≤T (melting)≤90 DEG C and include can be with Isocyanates reaction functional group thermoplastic component and be in granular form ground, be particularly dispersed in fine particulate the thermoplastic Property component in mode exist and be closed, microencapsulation or inactivated substantially in the region of particle surface containing isocyanates Component, wherein particle has the initial temperature T (starting) of 40 DEG C≤T (starting)≤120 DEG C, and wherein T (starting) >=T (melting).
2. it is according to claim 1 can laser marking film, which is characterized in that the trifunctional oligomer A be selected from poly- ammonia (methyl) acrylate of ester three and polyester three (methyl) acrylate.
3. it is according to claim 1 or 2 can laser marking film, which is characterized in that the trifunctional monomer B be selected from general formula (I) or mixtures thereof glycerol three (methyl) acrylate of propoxylation and ethoxylation:
Formula (I)
Wherein the R in Formulas I represents hydrogen or methyl；A is hydrogen or ethyl；X, Y and Z each independently represents propylene or ethylene unit； And a, b and c are each independently 1 to 4 integer, and the number that a+b+c is 3 to 12.
4. according to one of preceding claims can laser marking film, which is characterized in that the bifunctional monomer C is selected from The glycol diacrylate of logical formula (II):
Formula II
With the propylene glycol diacrylate of logical formula (III):
Formula III
Or mixtures thereof, wherein the n in formula (II) and (III) is each independently 1 to 15 integer.
5. according to one of preceding claims can laser marking film, which is characterized in that the acrylate paint group Close the trifunctional monomer B of trifunctional oligomer A, 5 to 15 weight % that the composition that is based on of object includes 50 to 60 weight % with And 5 to 15 weight % bifunctional monomer C.
6. it is according to one of claims 1 to 5 can laser marking film, which is characterized in that the trifunctional oligomer A is There are three the oligomer of unsaturated (methyl) acrylic ester unit and 1000 to 5000g/mol number-average molecular weight Mn for tool；Wherein The trifunctional monomer B is that there are three the lists of unsaturated (methyl) acrylic ester unit and 300 to 1000g/mol molecular weight for tool Body；And wherein the bifunctional monomer C is with per molecule two unsaturated acrylic ester units and 100 to 1000g/mol Molecular weight monomer.
7. it is according to one of claims 1 to 6, can laser marking film, which is characterized in that particle initial temperature T (rise Begin)≤100 DEG C, particularly≤90 DEG C, preferably >=50 DEG C, particularly >=60 DEG C.
8. according to claim 1 to described in one of 7 can laser marking film, which is characterized in that for the thermoplastic component Melting temperature T (melting): 40 DEG C≤T (melting)≤60 DEG C.
9. according to claim 1 to described in one of 8 can laser marking film, which is characterized in that the film is in the form of a label In the presence of.
10. according to claim 1 to described in one of 8 can laser marking film or according to claim 9 label in automobile Purposes in industry.
11. preparation can laser marking film method, comprising the following steps:
I) support membrane is provided；
Ii) carving layer is applied on the support membrane；
Iii) apply the acrylate coating composition including following components:
The trifunctional oligomer A of 30 to 80 weight % of ο；
The trifunctional monomer B of 0 to 20 weight % of ο；
The bifunctional monomer C of 1 to 30 weight % of ο；
The coloring pigment of the weight of ο and 2 to 40 %；
Iv solidify the acrylate coating composition) to obtain equivalent beds；
V) potential reaction gluing oxidant layer is applied on above-mentioned equivalent beds and is covered with peeling paper or similar release liner Adhesive, the potential reaction gluing oxidant layer include the melting temperature T (melting) with 35 DEG C≤T (melting)≤90 DEG C and Comprising the thermoplastic component of functional group that can be reacted with isocyanates and to be in granular form ground, be particularly dispersed in fine particulate Mode in the thermoplastic component exists and is closed, microencapsulation or what is inactivated substantially in the region of particle surface contain The component of isocyanates, wherein particle has the initial temperature T (starting) of 40 DEG C≤T (starting)≤120 DEG C, and wherein T ( Begin) >=T (melting)；
Vi) and remove support membrane.
CN201811553625.5A 2017-12-20 2018-12-19 Heatproof can laser marking film Pending CN110003809A (en)

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