CN104936776A - Multilayer film having pressure sensitive adhesive layer - Google Patents

Multilayer film having pressure sensitive adhesive layer Download PDF

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Publication number
CN104936776A
CN104936776A CN201280078163.0A CN201280078163A CN104936776A CN 104936776 A CN104936776 A CN 104936776A CN 201280078163 A CN201280078163 A CN 201280078163A CN 104936776 A CN104936776 A CN 104936776A
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sensitive adhesive
base material
polymer
film
combination
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CN201280078163.0A
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CN104936776B (en
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X·刘
J·肯普斯基
M·J·齐瓦尼斯
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Saint Gobain Performance Plastics Corp
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Saint Gobain Performance Plastics Corp
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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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • 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
    • C09J2407/00—Presence of natural rubber
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/005—Presence of polyolefin in the release coating
    • 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
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/005—Presence of halogenated polymer in the release coating
    • 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
    • C09J2451/00—Presence of graft 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
    • C09J2475/00—Presence of polyurethane
    • 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
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Abstract

A multilayer film includes a substrate film having first and second major surfaces and a pressure sensitive adhesive layer disposed on the first major surface of the substrate film. The pressure sensitive adhesive layer includes a curable composition. The multilayer film further includes a release layer disposed on the pressure sensitive adhesive layer opposite the substrate film. The release layer includes a release material and a catalyst to cure the curable composition.

Description

There is the multilayer film of pressure sensitive adhesive layer
Technical field
The disclosure is usually directed to the multilayer stripping film with pressure sensitive adhesive layer, and for the preparation of the method for this film.
Background technology
Multilayer film has the purposes day by day increased in the industry.Such as, film can be used as protection shaft coupling, mask, label, interim safety device, or their any combination.Hyaline membrane is used as the protection coating on display equipment (as mobile telephone display, handheld game device or even TV).Film is also used as the protection coating on parts, swipes to reduce and protects color.
Many this films use adhesive and adhere to surface.Especially, film can comprise contact adhesive.But the required adherence obtaining the contact adhesive coated on multilayer film is process consuming time, needs high temperature in some cases.
Unsuitable solidification can cause the adhesion of the difference of multilayer film, or can cause undesirable excessive adhesion power, particularly can remove in film.In many cases, catalyst is added in pressure-sensitive adhesion agent prescription to control solidification.But, too much catalyst is added in pressure-sensitive adhesion agent prescription and can causes significantly reduced storage life and unacceptably high viscosity.
Like this, the multilayer film with contact adhesive of improvement is required.
Accompanying drawing explanation
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 comprise the diagram of exemplary multiple layer film.
Fig. 5 comprises the diagram of an illustrative methods for the formation of multilayer film.
Detailed description of the invention
In a particular embodiment, multilayer film comprise base material film, on cover the pressure sensitive adhesive layer of described base material film, and the peel ply contacted with described pressure sensitive adhesive layer or coating.Peel ply or coating comprise release liner and the activated reagent of component tool to pressure sensitive adhesive layer.Base material can comprise polymer film, and can comprise the antistatic layer being arranged between polymer film with pressure sensitive adhesive layer or being arranged on the surface relative with pressure sensitive adhesive layer of polymer film.In another example, can lining form be applied on release coating, to be conducive to removing release coating from pressure sensitive adhesive layer when final utilization.In a particular instance, multilayer film can distribute from roller.
In a further exemplary embodiment, the method forming multilayer film comprises distribution base material film, is coated on described base material film by contact adhesive composition, and is coated on described contact adhesive composition by release coating.Release coating comprises release liner and the activated reagent of component tool to contact adhesive composition.Optionally, lining form can be applied on release coating.Or release coating can be applied on the apparent surface of base material film relative to pressure sensitive adhesive layer, thus when multilayer film is rolled into volume, release coating contact contact adhesive composition.In another example, base material film can comprise antistatic layer.Or, the first type surface that antistatic layer can coat polymer film solidifies.
Fig. 1 comprises the diagram of an exemplary multiple layer film 100.Such as, multilayer film 100 comprises base material film 102, pressure sensitive adhesive layer 104 and release coating 108.Release coating 108 is in order to contact pressure sensitive adhesive layer 104.Pressure sensitive adhesive layer 104 directly can contact with the first type surface 110 of base material film 102, or can there is intermediate layer between base material film 102 and pressure sensitive adhesive layer 104.As shown, the second first type surface 112 of base material film 102 can form the skin of multilayer film 100.
In an example, base material film 102 comprises one or more layers of polymeric material.Such as, polymeric material can be thermoplastic, polymeric materials.In another example, polymeric layer can be thermosets.In a particular instance, polymeric layer is extruding layer.Extruding layer can comprise other coating.In an example, polymeric material comprises polyolefin, acetate polymer, acrylic polymer, PAEK, polyester, Merlon, polyvinyl chloride, polyethers, polyamide, polyimides, thermoplastic elastomer (TPE), liquid crystal polymer, fluoropolymer, or their any combination.
A kind of exemplary polyolefins comprises polyolefin homopolymer (as polyethylene, polypropylene, polybutene, polypenthylene or polymethylpentene), polyolefin copolymer (as ethylene-propylene copolymer, ethylene-butene copolymer, or ethylene-octene copolymer), or their any blend or combination.An exemplary polyethylene comprises high density polyethylene (HDPE) (HDPE), Medium Density Polyethylene (MDPE), low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene, or their any combination.An exemplary polyamide comprises nylon 6, nylon 6,6, nylon 11, nylon 12, or their any combination.A specific vinyl acetate comprises ethylene vinyl acetate (EVA).An exemplary PAEK can comprise polyether-ketone, polyether-ether-ketone, polyether ether ketone ketone, or their any combination.In a particular instance, PAEK can comprise polyether-ether-ketone (PEEK).
An exemplary fluoropolymer comprises PEP (FEP), polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), perfluoro alkoxy (PFA), the terpolymer (THV) of tetrafluoroethene, hexafluoropropene and vinylidene, polychlorotrifluoroethylene (PCTFE), ethylene tetrafluoroethylene copolymer (ETFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), the terpolymer of ethene, hexafluoropropene and tetrafluoroethene, or their any combination.
Acrylic polymer can comprise polyacrylate, polymethyl methacrylate, polymethacrylates or any combination, and can be such as lashing stage or through impact modified acrylic compounds.The comonomer of the monomer of acrylic monomer and the suitable of effective dose or the copolymer of graft is generally included, to produce required elastic modelling quantity and resistance to impact through impact modified acrylic polymer.Acrylic elastomer can be used, it is sometimes referred to as ACM, lactoprene, polyacrylic elastomer or " ACM ", it is the mixture based on the mixture of polyacrylate and polymethacrylates, polyacrylate and ethylene methyl acrylate copolymer (" EMAC ") (as Chevron Chemicals EMAC 2260), or the composition of the mixture of polyacrylate and ethylene butyl acrylate (" EBAC ").Or, the thermoplastic blend that can be transparent glassy acrylic polymer (as the plastic copolymer of ethene and carboxylic acid compound, described carboxylic acid compound is selected from acrylic acid, methacrylic acid and their mixture) and elastomeric component through impact modified acrylic polymer.
An exemplary thermoplastic elastomer (TPE) can comprise the blend of polyolefin and elastomer vulcanizate.Such as, thermoplastic elastomer (TPE) can comprise polyolefin and be scattered in the elastomer in polyolefin.A kind of exemplary elastomer can comprise diene elastomer.Diene elastomer is the cross-linkable copolymers comprising diene monomers, and described diene monomers is ethylene propylene diene monomer (EPDM), ABS such as, or their any combination.Other exemplary elastomers can comprise the elastomer blend (being commonly referred to thermoplastic olefin (TPO)) of alkene.
In another example, polymer is polyester, as PETG.In another example, polyester is liquid crystal polymer.An exemplary liquid crystal polymer comprises aromatic polyester polymer, as can with trade name (Amoco (Amoco)), (Hirst Celanese Corp. (Hoechst Celanese)), SUMIKOSUPERTM (sumitomo chemical company (SumitomoChemical)), EKONOL tM(company of Saint-Gobain (Saint-Gobain)), DuPont HX tMor DuPont ZENITE tM(E.I.Du Pont Company (E.I.DuPont de Nemours)), RODRUN tM(You Niji can company (Unitika)), GRANLAR tM(Ge Langmeng company (Grandmont)) obtain those, or their any combination.Liquid crystal polymer comprises thermic (melt processible) liquid crystal polymer, and wherein limited microbedding degree of crystallinity can be particularly advantageous.
Be back to Fig. 1, base material film 102 can have in the scope of 0.5 mil to 10 mil, in the scope as 0.5 mil to 5.0 mil, in the scope of 1 mil to 5.0 mil, or the thickness in the scope of even 1 mil to 3 mil.
Pressure sensitive adhesive layer 104 can be formed by curable pressure-sensitive adhesive composition.Contact adhesive is a kind of adhesive, and its combination degree is subject to the impact of the amount of the pressure for adhesive being applied to surface.Such as, contact adhesive composition can comprise natural rubber, styrene block copolymer, acrylate, polyurethane, organosilicon, polydiorganosiloxanepolyurea polyurea copolymer, or their any combination.An exemplary styrene block copolymer comprises styrene-butadiene-copolymer (SBR), styrene/isoprene/styrene block copolymer (SIS), acrylonitrile/styrene block copolymer, or their any combination.
Acrylic polymer can derived from monomer, as (methyl) alkyl acrylate, alkyl acrylate, or alkyl methacrylate.The example of (methyl) alkyl acrylate comprises (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) acrylic acid peopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid 11 ester, (methyl) dodecyl acrylate, or their any combination.Especially, acrylic polymer can be poly-(methyl) methyl acrylate.
In another example, acrylic polymer can be the copolymer derived from least one acrylate monomer and at least one polymerizable co-monomers.Exemplary polymerizable co-monomers comprise acrylonitrile, acrylamide, Methacrylamide, vinyl esters, vinyl ethers, vinylamide, vinyl ketone, styrene, halogen containing monomer, ionic comonomer, acidiferous monomer, containing alkali monomer, the monomer with reactive silicon-containing group and polymerizable unsaturated group, alkene, or their any combination.In another example, acrylic polymer main chain can by the macromonomer grafting with polyether backbone, described macromonomer such as PEG (PEG), poly-(propane diols) (PPG) with polyether backbone, with poly-(tetramethylene glycol) (PTMG), or their any combination.
In another example, pressure sensitive adhesive layer 104 comprises polyurethane.Such as, polyurethane contact adhesive can be formed by the reaction of isocyanates and polyalcohol.Isocyanate component can comprise '-diphenylmethane diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), hexamethylene diisocyanate (HDI), IPDI (IPDI), or their any combination.In an example, isocyanates can comprise '-diphenylmethane diisocyanate (MDI) or toluene di-isocyanate(TDI) (TDI).Especially, isocyanates comprises '-diphenylmethane diisocyanate (MDI) or derivatives thereof.
In an example, polyalcohol can be polyether polyol, polyester polyol, their derivative through modification or grafting, or their any combination.Suitable polyether polyol obtains by such as under type: double metal cyanide-catalyzed by inserting polymerization (polyinsertion), by as under the alkali metal hydroxide of catalyst or the existence of alkali alcoholate via epoxyalkane, and in interpolation containing 2 to 6, the anionic polymerisation of the epoxyalkane when at least one initiator molecule of the preferred hydrogen atoms of 2 to 4 bonding schemes, or by the cationic polymerization of the epoxyalkane under the existence of lewis acid (as Antimony pentachloride or boron fluoride etherate).Suitable epoxyalkane can contain 2 to 4 carbon atoms in alkylidene residue.Example comprises oxolane, 1,2-expoxy propane, 1,2-or 2,3-epoxy butane, oxirane, 1,2-expoxy propane, or their any combination.Epoxyalkane can use individually, continuously or as mixture.The example of initiator molecule comprises water or dihydroxylic alcohols or trihydroxylic alcohol, as ethylene glycol, 1,2-PD and 1,3-PD, diethylene glycol, DPG, ethane-Isosorbide-5-Nitrae-glycol, glycerine, trimethylolpropane, or their any combination.
Curable pressure-sensitive adhesive composition can comprise crosslinking agent, catalyst, tackifying resin, or their any combination.
An exemplary crosslinking agent comprises multifunctional ethylenically unsaturated monomers.This monomer comprises such as divinyl aromatic compound, divinyl ether, multifunctional maleimide, polyfunctional acrylic ester and methacrylate etc., or their any combination.An exemplary divinyl aromatic compound comprises divinylbenzene.Exemplary multifunctional (methyl) acrylate can comprise three (methyl) acrylate or two (methyl) acrylate, and they are for comprising the compound of three or two (methyl) acrylate groups.Exemplary three (methyl) acrylate comprises trimethylolpropane tris (methyl) acrylate, propenoxylated trimethylolpropane triacrylate, the trimethylolpropane triacrylate of ethoxylation, three (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, or their any combination.Exemplary two (methyl) acrylate comprises ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, 1, 4-butanediol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, oxyalkylated 1, 6-hexanediyl ester, tripropylene glycol diacrylate, propylene glycol diacrylate, cyclohexanedimethanol two (methyl) acrylate, oxyalkylated cyclohexane dimethanol diacrylate, bisphenol-A two (methyl) acrylate of ethoxylation, neopentylglycol diacrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, carbamate two (methyl) acrylate, or their any combination.
Another Exemplary cross linking agents comprises alkyl methacrylate (as methyl methacrylate) and the copolymer of monomer providing reactive amino, epoxy radicals, hydroxyl and/or carboxyl and terminal ethylenyl groups end blocks, (it is at least partially epoxidized with the gradual change of styrene and butadiene or isoprene or random copolymer, and containing terminal ethylenyl groups), or their any combination.
Another exemplary crosslinking agent comprises isocyanates based cross-linker, as aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic polyisocyanate, aromatic aliphatic PIC, and their dimer and tripolymer and their product or polymer.The example of isocyanates based cross-linker comprises product, polyethers PIC, the polyester PIC of the product of toluene di-isocyanate(TDI), hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, methyl diphenylene diisocyanate, the dimer of methyl diphenylene diisocyanate, trimethylolpropane and toluene di-isocyanate(TDI), trimethylolpropane and hexamethylene diisocyanate, or their any combination.Another crosslinking agent comprises Si-H end-cap molecule.
Crosslinking agent to be enough to cause the crosslinked to provide enough cohesive strengths of contact adhesive, thus for interested base material produce needed for the effective dose use of final adhesion properties.Crosslinking agent can with 0.01 part to 20 parts, as the amount of 0.1 to 10 part uses, with total monomer weight.Such as, the amount of isocyanate-based compound to be used is about 0.01 to 20 weight portion, as 0.05 to 15 weight portion, in 100 parts by weight polymer.
Catalyst can include organic metal catalyst, amine catalyst, or their combination.Organo-metallic catalyst such as can comprise dibutyl tin laurate, carboxylic acid lithium, butyl titanate, bismuth carboxylate, or their any combination.In another example, catalyst can comprise platinum-vinyl siloxane, platinum-alkene complex, as Pt-divinyl tetramethyl disiloxane, or their any combination.
An exemplary titanium catalyst comprises organic functional titanate esters, siloxy titanate esters, or their any combination.Exemplary organic functional titanate esters comprises 1, 3-third dioxy base titanium two (acetoacetate ethyl ester), 1, 3-third dioxy base titanium two (acetylacetone,2,4-pentanedione), diisopropoxy titanium two (acetylacetone,2,4-pentanedione), 2, 3-diisopropoxy-bis-(ethyl acetate) titanium, aphthenic acids titanium, metatitanic acid orthocarbonate, butyl titanate, tetraethyl hexyl titanate esters, metatitanic acid tetraphenyl ester, metatitanic acid four (octadecyl) ester, four titanium butoxide, tetraisopropoxy titanium, ethyl triethanol amine titanate, β Dicarbonyl Titanium compound (as two (acetylacetone based) diisopropyl titanate esters), or their any combination.Siloxy titanate esters comprises four (trimethylsiloxy) titanium, two (trimethylsiloxy) two (isopropoxy) titanium, or their any combination.
Exemplary tin compound comprises dibutyl tin laurate, dibutyltin diacetate, dimethanol dibutyl tin, three suberic acid methoxycarbonyl phenyltins, tin octoate, three ceriums acid isobutyl tin (isobutyl tintriceroate), two butyric acid stannous methides, two neodecanoic acid stannous methides, tartaric acid tin triethyl, dibenzoic acid dibutyl tin, oleic acid tin, aphthenic acids tin, three-2 ethyl hexanoic acid butyl tin, butyric acid tin, or their any combination.In another example, catalyst can comprise zirconium compounds, as zirconium caprylate.
Amine catalyst can comprise tertiary amine (as tri-butylamine), N-methylmorpholine, N-ethylmorpholine, N, N, N ', N '-tetramethylethylenediamine, pentamethyl dimethylene triamine and Geng Gao homologue, 1, 4-diazabicylo-[2, 2, 2]-octane, N-methyl-N '-dimethylaminoethyl piperazine, two (dimethylamino) piperazine, N, N-dimethyl benzylamine, N, N-dimethyl cyclohexyl amine, N, N-diethyl benzylamine, two (N, N-diethylamino ethyl) adipate ester, N, N, N ', N '-tetramethyl-1, 3-butanediamine, N, N-dimethyl-β-phenyl-ethylamine, two (dimethylaminopropyl) urea, two (dimethylaminopropyl) amine, 1, 2-methylimidazole, glyoxal ethyline, monocycle and bicyclic amidine, two (dialkyl amido) alkyl ether (such as two (dimethyl aminoethyl) ether), there is the tertiary amine of amide groups (as carbonylamino group), or their any combination.Another example of catalytic component comprises Mannich alkali, comprise secondary amine (as dimethylamine), or aldehyde (as formaldehyde), or ketone (as acetone, MEK or cyclohexanone), or phenols (as phenol, nonyl phenol or bis-phenol).The catalyst that to have for isocyanate groups be the form of the tertiary amine of active hydrogen atom can comprise triethanolamine, triisopropanolamine, N methyldiethanol amine, N-ethyldiethanolamine, N, the product of N-dimethylethanolamine, they and epoxyalkane (as expoxy propane or oxirane), or the second month in a season-tertiary amine, or their any combination.The silicon amine (silamine) with carbon-silicon key also can be used as catalyst, such as 2,2,4-trimethyl-2-silicon morpholines, 1,3-diethylamino methyl tetramethyl disiloxane, or their any combination.
In another example, amine catalyst is selected from five methyl diethylentriamine, dimethylaminopropyl amine, N, N ' lupetazin and dimorpholine base ether, N, N ' dimethyl aminoethyl N methyl piperazine, the DM-70 mixture of lupetazin and dimorpholine base ether (N, the N '), imidazoles (imadozole), triazine, or their any combination.
Catalyst for radical polymerization can comprise radical initiator, as azo-type initiator, and such as 2,2 '-azo two (isobutyronitrile).Other initators comprise peroxide initiator, comprise dialkyl peroxide (as di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy)-3-hexin, dicumyl peroxide, tert-butyl cumyl peroxide and α, 60 '-bis(t-butylperoxy) cumene), diacyl peroxide is (as benzoyl peroxide, chloro benzoyl peroxide, chlorobenzoyl between peroxidating, peroxidating 2, 4-dichloro-benzoyl, lauroyl peroxide), peroxy ester (as t-butyl perbenzoate), peroxydicarbonate (as diisopropyl peroxydicarbonate and peroxide two carbonic acid two-2-Octyl Nitrite), peroxy ketal is (as 1, 1-bis-(t-butylperoxy) cyclohexane and 1, 1-bis-(t-butylperoxy)-3, 3, 5-trimethyl-cyclohexane), or their any combination.Peroxy ester comprises peroxy-2 ethyl hexanoic acid tert-pentyl ester, peroxy-2 ethyl hexanoic acid tert-butyl ester, or their any combination.Can be used as the second initator especially to reduce the peroxy ester of residual monomer for peroxy neopentanoic acid tert-pentyl ester.
Tackifier can combine with adhesive composition.Tackifier can be substantially compatible with base polymer." substantially compatible " means when combining tackifier and polymer, contrary with opaque, and it is substantial transparent that gained to be combined under desciccator diaphragm form for normal vision.Exemplary tackifier comprise rosin and rosin derivative, be included in naturally occurring rosin material in the oleoresin of pine tree, and their derivative, comprise rosin ester, through the rosin (rosin as through fractionation, hydrogenation, dehydrogenation and polymerization) of modification, the rosin ester through modification, or their any combination.
Another exemplary tackifier comprise terpene resin, and (it is the formula C existed in the oleoresin of most of essential oil and plant 10h 16hydro carbons), and the terpene resin of phenol modification (as α firpene, beta pinene, cinene, citrene, laurene, bornylene, amphene), or their any combination.Exemplary tackifier also can comprise aliphatic hydrocarbon resins, aromatic hydrocarbon resins (such as based on the styrene and styrene derivative etc. of C9, C5, bicyclopentadiene, benzofuran, indenes, styrene, replacement), or their any combination.Another exemplary tackifier comprise atoleine, as alkyl naphthene.
The amount of tackifier can in 0% to 60% scope, as in 5% to 60% scope, with the total weight of one or more tackifier.
Contact adhesive composition also can comprise diluent, softening agent, plasticizer, excipient, antioxidant, UV stabilizing agent, counter-stimulus, opacifier, filler (as clay and silica, pigment and their mixture), anticorrisive agent, and other components or additive.
Be back to Fig. 1, pressure sensitive adhesive layer 104 can have in the scope of 0.1 mil to 10 mil, in the scope as 0.25 mil to 5.0 mil, in the scope of 0.25 mil to 2 mil, or the thickness in the scope of even 0.25 mil to 1 mil.
Peel ply or coating 108 can comprise the non-miscible composition with contact adhesive composition.Peel ply or coating 108 directly can contact with pressure sensitive adhesive layer 104.Especially, can being easily separated with pressure sensitive adhesive layer 104 at least partially of peel ply or coating 108.Such as, peel ply or coating 108 can comprise release liner, as silicone based material, fluorine-based material, chain alkyl sill, fatty acid acyl amine based material, silicon dioxide powder powder material, or their any combination.An exemplary release liner is organic silica-based release liner, as the organosilicon of addition-curable and condensation curable.In this type of release liner, platinum (Pt) or rhodium (Rh) catalyst are typically used as the curing catalysts for remover.
Or release liner can be formed by keeping the grease of certain viscosity or oil.Such as, release liner can comprise silicone grease, fluorosilicon oil, phenyl silicone oil, paraffin, or their any combination.
In a particular instance, release coating 108 comprises the reagent of the solidification actively promoting curable pressure-sensitive adhesive composition, as catalyst.Such as, reagent can promote the crosslinked of at least one component of contact adhesive composition.Especially, release coating 108 can be included in the scope of 0.01wt% to 5.0wt%, as in the scope of 0.1wt% to 2.5wt%, in the scope of 0.5wt% to 2.0wt%, or the reagent of amount even in the scope of 0.5wt% to 1.5wt%, as above-mentioned catalyst.
Release coating 108 can have in the scope of 0.025 mil to 10 mil, in the scope as 0.025 mil to 5.0 mil, in the scope of 0.25 mil to 2 mil, or the thickness in the scope of even 0.25 mil to 1 mil.
In the specific embodiment of shown in Fig. 2, multilayer film 200 comprises base material film 202, and described base material film 202 comprises and exceedes one deck.Such as, polymeric substrate 202 can comprise polymer film 204 and antistatic layer 206.Pressure sensitive adhesive layer 208 can be coated on polymer film 204, and release coating 210 can be coated on pressure sensitive adhesive layer 208.Optionally, lining form 212 can be applied on release coating 210.Or release coating 210 can be coated on lining form 212, combination layer (210,212) is at release coating surface (210) place contact pressure sensitive adhesive layer 208.
Polymeric layer 204 can be formed by the polymer as above being relevant to base material film 102.Antistatic coating 206 can comprise dissipative polymer, as polyether block amide, ionomer, polyimides, polyamide, or their any combination.
In another example, antistatic coating 206 can comprise the polymer through filling.Polymer can comprise acrylate, polyolefin, polyurethane, polyester, polyethers, polyamide, polyimides, PAEK, or their any combination.An exemplary filler can comprise conductive filler, as metallic, conductivity ceramics particle, carbon black, conductive fiber, CNT, Graphene, or their any combination.In another example, antistatic coating can comprise the metal level of deposition, as the layer that sputtering or steam deposit.
Especially, antistatic coating 206 can have 10 5to 10 12surface resistivity within the scope of ohm/sq.Such as, the surface resistivity of antistatic coating can 10 8to 10 12ohm/sq, as 10 9to 10 12in the scope of ohm/sq.
Pressure sensitive adhesive layer 208 and release coating 210 can be formed by above-mentioned material.Especially, release coating 210 comprises the reagent of at least one component of activated pressure sensitive adhesive phase 208, as catalyst.
Optionally, lining form 212 can be applied on release coating 210.In an example, lining form 212 comprises the film or paper that are attached to release coating.An exemplary polymer film can comprise polyolefin, acetic acid esters, acrylic compounds, PAEK, polyester, polyethers, polyamide, polyimides, thermoplastic elastomer (TPE), styrenic polymer, liquid crystal polymer, fluoropolymer, or their any combination.In an example, release liner 212 comprises cellulose acetate membrane.In another example, lining form 212 comprises polyolefin film.In another example, lining form 212 comprises polyester film.In an example, the process lining forms 212 such as corona discharge, plasma discharge, ion processing can such as be used, to improve the adhesion to release coating.Lining form 212 can have in the scope of 0.5 mil to 5 mil, as in the scope of 0.5 mil to 3 mil, or the thickness even in the scope of 1 mil to 3 mil.
In another exemplary embodiment shown in Fig. 3, multilayer film 300 can comprise base material film 302.In an example, base material film 302 comprises polymer film 304 and antistatic layer 306.In exemplary multiple layer film 300, contact adhesive 308 can be arranged on the first first type surface 312 of base material film 302, and release coating 310 can be arranged on the relative first type surface 314 of base material film 302.When being rolled into multilayer film for subsequent allocations, release coating 310 contacts with pressure sensitive adhesive layer 308 and arranges, and promotes the solidification of pressure sensitive adhesive layer 308 or crosslinked.
Although multiple layer polymer base material is shown as the antistatic layer 306 on the first type surface of base material film 302 having and contact with release coating 310, antistatic coating and other layers can be rearranged.Such as, the multilayer film shown in Fig. 4 comprises polymeric substrate 402, and wherein polymeric layer 404 contacts with release coating 410, and antistatic layer 406 contacts with pressure sensitive adhesive layer 408.When scrolling film 400, the release coating 410 comprised at least one component of the contact adhesive composition in pressure sensitive adhesive layer 408 is the reagent of activity contacts with pressure sensitive adhesive layer, thus causes the solidification of the contact adhesive composition of layer 408 and be cross-linked.
Fig. 5 comprises the diagram of an example process for the formation of multilayer film.Such as, process 500 comprises the volume of base material film 502, and base material film distributes from described volume.Base material film 502 can comprise one or more layers of polymer film.Optionally, base material film comprises antistatic layer.Or antistatic layer at coating station 504 place as painting Layer assignment, and can solidify.Antistatic coating (not shown) can be designed at room temperature to solidify, respond heat and solidify, respond the actinic radiation with some other curing mechanisms and solidify.Such as, antistatic coating can process in baking oven 514.
In addition, contact adhesive composition can be on base material film 502 at coating station 506 and be coated with.Contact adhesive composition is optional from as above disclosed composition.Optionally, contact adhesive composition can such as baking or dry in baking oven 516.Or contact adhesive composition can use actinic radiation process.
In addition, release coating can be applied on contact adhesive composition at coating station 508 place.It is active reagent that release coating comprises at least one component of the contact adhesive composition distributed at 506 places.In an example, not heat treatment release coating after deposition.Or release coating is cured by actinic radiation or heat treatment.
Or release coating can be applied to the relative first type surface of base material film 502 relative to the contact adhesive composition used at 506 places.When by multilayer film scrolling rolling 510, the release coating contact of using at 508 places has the apparent surface of the multilayer film of coatings of pressure sensitive adhesive.
Distribute on base material film 502 although coating station (504,506 or 508) is shown as, other coating techniques can be used to use coating layer.Such as, the coating of roller coat, intaglio plate, blade coating, dip-coating, spraying, slit extrusion coated, or their distortion.
Optionally, system 500 comprises the roller 512 distributing lining form on the release coating in the distribution of 508 places.By multilayer film scrolling rolling 510 to be stored for use afterwards.The distortion of described process is possible.Such as, as disclosed above, release coating can be dispensed to lining form from roller 512 by release coating station 508, and this minor structure can be bonded to the minor structure of base material film/release-coated by laminated station.
Once be formed, then multilayer film can have the peel strength being not more than 1000g/in, as in 2g/in to 500g/in scope, and the peel strength in 3g/in to 200g/in or 4g/in to 100g/in scope.Measure under the detachment rate of the angle of 180 ° and 12in/min relative to the peel strength of corrosion resistant plate.
In addition, curing performance can be used as cure index and records, and described cure index is defined as in the ratio of 18 little peel strengths constantly divided by peel strength during at 7 days.Especially, multilayer film can have and is not more than 2, as be not more than 1.5 or be not even greater than 1.2 cure index.
Example
Preparation comprises the binder combination of acrylic adhesives, isocyanate crosslinking and dibutyltin dilaurate catalyst.Mixture is watered cast from 2 mil thick PETG (PET) sheet material on, and in baking oven at 135 DEG C dry 1.5 minutes.The final thickness of contact adhesive is between 0.55 mil to 0.6 mil.The one pack material liner of stanniferous organosilicon release-coated covers, and another pack material uses the liner of the not organosilicon release-coated of tin-containing catalyst to cover.Sample at room temperature aging 18 hours, 3 days or 7 days.After the aging fixed time, remove the liner of release-coated, use 4.5lb laboratory roller that psa layer is bonded to PET base material.After stopping 20 minutes, test and record the peel adhesion of PSA.Peeling off test parameter is 180 ° and 12in/min.
As shown in the following Table 1, after 18 hours, the peel strength with the sample of the liner of stanniferous organosilicon release-coated has reached solidifies completely, but the peel strength with the sample of the liner of not stanniferous organosilicon release-coated is still high.After 3 days aging, there is the PSA of the liner of not stanniferous organosilicon release-coated close to solidifying completely.
The peel adhesion of table 1. sample
Especially, find by catalyst is added into peel ply and reduce hardening time.Although hardening time accelerates by being added in contact adhesive composition by catalyst, the catalytic amount increased in contact adhesive composition causes low storage life and the high viscosity in coating process.When without this discovery, the solidification that the low catalyst in contact adhesive composition causes long hardening time and may differ from.There is catalyst in release coating, the amount of the catalyst in contact adhesive composition can be reduced or eliminated, thus long storage life is provided in the fabrication process, and the short hardening time after simultaneously providing coating.
It should be noted that and do not need as above to describe or all activities described in example in generality, a concrete movable part may not be needed, and one or more other activities can be carried out except described those.In addition, the order that activity is listed also need not carry out movable order.
In the foregoing specification, concept is described with reference to specific embodiment.But, it will be understood by those skilled in the art that and can carry out various amendment and change when not departing from the scope of the present invention described in following claims.Therefore, description and accompanying drawing should be regarded as illustrative and nonrestrictive, and all such modifications are intended to be included in scope of the present invention.
As used herein, term " comprises ", " comprising ", " having " or their any other variant are intended to contain comprising of nonexcludability.Such as, comprise the process of series of features, method, goods or device and need not be only limitted to those features, but other features that clearly do not list or that these processes, method, goods or device are intrinsic can be comprised.In addition, point out on the contrary unless clear and definite, "or" refer to comprising property or, and nonexcludability or.Such as, condition A or B is by any one meets as follows: A is true (or existence) and B is false (or not existing), A is false (or not existing) and B is true (or existence), and A and B is very (or existence).
And the use of " one " is for describing element described herein and parts.This only conveniently, and provides the general sense of scope of the present invention.This description is understood to include one or at least one, and odd number also comprises plural number, unless it obviously has contrary.
Benefit, other advantages and way to solve the problem are as above described about specific embodiment.But, benefit, advantage, way to solve the problem and any benefit, advantage or solution may be made to occur or become more obvious any feature and should not be interpreted as the key of any claim or all authority requirement, required or essential feature.
After reading description, it will be apparent to those skilled in the art that in order to clear, also can provide in conjunction with single embodiment in some feature described herein in the embodiment of separating.On the contrary, in order to easy, the various features described in single embodiment also can provide dividually or in any sub-combination.In addition, quote to the value described in scope each value comprised within the scope of this.

Claims (31)

1. a multilayer film, it comprises:
There is the base material film of the first and second first type surfaces;
Be arranged at the pressure sensitive adhesive layer on the first first type surface of described base material film, described pressure sensitive adhesive layer comprises curable compositions; With
Be relatively arranged on the peel ply on described pressure sensitive adhesive layer with described base material film, described peel ply comprises release liner and the catalyst in order to solidify described curable compositions.
2. multilayer film according to claim 1, wherein said release liner is silica-base material, fluorine-based material, chain alkyl sill, fatty acid acyl amine based material, silicon dioxide powder powder material, or their any combination.
3. multilayer film according to claim 1, wherein said curable compositions comprises polymer, described polymer comprises natural rubber, styrene block copolymer, acrylate, polyurethane, organosilicon, polydiorganosiloxanepolyurea polyurea copolymer, or their any combination.
4. multilayer film according to claim 1, wherein said curable compositions comprises crosslinking agent.
5. multilayer film according to claim 1, wherein said catalyst is organo-metallic catalyst, amine catalyst, or their combination.
6. multilayer film according to claim 1, wherein said base material film comprises polymer film.
7. multilayer film according to claim 6, wherein said polymer film is polyolefin, acetate polymer, acrylic polymer, PAEK, polyester, polyethers, Merlon, polyvinyl chloride, polyamide, polyimides, thermoplastic elastomer (TPE), liquid crystal polymer, fluoropolymer, or their any combination.
8. multilayer film according to claim 1, wherein said base material film comprises antistatic layer.
9. multilayer film according to claim 8, wherein said antistatic layer comprises dissipative polymer.
10. multilayer film according to claim 8, wherein said antistatic layer comprises conductive filler.
11. multilayer films according to claim 8, wherein said antistatic layer has 10 5to 10 12surface resistivity within the scope of ohm/sq.
12. multilayer films according to claim 1, it also comprises and that be arranged at described peel ply on lining form relative with described pressure sensitive adhesive layer.
13. multilayer films according to claim 12, wherein said lining form is polyolefin, acetate polymer, acrylic compounds, PAEK, polyester, polyethers, Merlon, polyvinyl chloride, polyamide, polyimides, thermoplastic elastomer (TPE), styrenic polymer, liquid crystal polymer, fluoropolymer, or their any combination.
14. multilayer films according to claim 12, wherein said lining form comprises paper.
15. multilayer films according to claim 1, wherein said curable compositions has the peel strength being not more than 1000g/in.
16. multilayer films according to claim 15, wherein peel strength is in the scope of 2g/in to 500g/in.
17. multilayer films according to claim 16, wherein peel strength is in the scope of 3g/in to 200g/in.
18. multilayer films according to claim 17, wherein peel strength is in the scope of 4g/in to 100g/in.
19. multilayer films according to claim 1, wherein said multilayer film has the cure index being not more than 2.
20. multilayer films according to claim 1, wherein said cure index is not more than 1.5.
21. multilayer films according to claim 1, wherein said cure index is not more than 1.2.
22. 1 kinds of multilayer films, it comprises:
There is the base material film of the first and second first type surfaces;
Be arranged at the pressure sensitive adhesive layer on the first first type surface of described base material film, described pressure sensitive adhesive layer comprises curable compositions, and described curable compositions comprises polymer and crosslinking agent;
Be relatively arranged on the peel ply on described pressure sensitive adhesive layer with described base material, described peel ply comprises release liner and the catalyst in order to solidify described curable compositions; With
Lining form on described release coating.
23. multilayer films according to claim 22, wherein said release liner is silica-base material, fluorine-based material, chain alkyl sill, fatty acid acyl amine based material, silicon dioxide powder powder material, or their any combination.
24. multilayer films according to claim 22, wherein said polymer comprises natural rubber, SBC, acrylate, polyurethane, organosilicon, polydiorganosiloxanepolyurea polyurea copolymer, or their any combination.
25. multilayer films according to claim 22, wherein said catalyst is organo-metallic catalyst, amine catalyst, or their combination.
26. multilayer films according to claim 22, wherein said lining form is polyolefin, acetic acid esters, acrylic compounds, PAEK, polyester, Merlon, polyvinyl chloride, polyethers, polyamide, polyimides, thermoplastic elastomer (TPE), styrenic polymer, liquid crystal polymer, fluoropolymer, or their any combination.
27. multilayer films according to claim 22, wherein said curable compositions has the peel strength being not more than 1000g/in.
28. multilayer films according to claim 22, wherein said multilayer film has the cure index being not more than 2.
29. 1 kinds of methods forming multilayer film, described method comprises:
Distribute the base material with the first and second first type surfaces;
Curable pressure-sensitive adhesive composition is used to be coated with the first first type surface of described base material; With
Use release coating is coated with, and to contact described curable pressure-sensitive adhesive composition, described release coating comprises release liner and the catalyst in order to solidify described curable compositions.
30. methods according to claim 29, it is also included on described release coating and distributes lining form.
31. methods according to claim 29, wherein use release coating coating comprise relative with described curable pressure-sensitive adhesive composition and on the second first type surface of described base material, be coated with described release coating, and multilayer film described in rolling contact with described curable pressure-sensitive adhesive composition to make described release coating.
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CN104936776B (en) 2017-10-27
WO2014092700A1 (en) 2014-06-19

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