CN104936776B - Multilayer film with pressure sensitive adhesive layer - Google Patents

Multilayer film with pressure sensitive adhesive layer Download PDF

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Publication number
CN104936776B
CN104936776B CN201280078163.0A CN201280078163A CN104936776B CN 104936776 B CN104936776 B CN 104936776B CN 201280078163 A CN201280078163 A CN 201280078163A CN 104936776 B CN104936776 B CN 104936776B
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Prior art keywords
multilayer film
film according
sensitive adhesive
base material
polymer
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CN201280078163.0A
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CN104936776A (en
Inventor
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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a kind of multilayer film, it includes the base material film with the first and second main surfaces and the pressure sensitive adhesive layer being arranged on the first main surface of the base material film.The pressure sensitive adhesive layer includes curable compositions.The multilayer film also includes relative with the base material film and is arranged at the peel ply on the pressure sensitive adhesive layer.The peel ply includes release liner and the catalyst to solidify the curable compositions.

Description

Multilayer film with pressure sensitive adhesive layer
Technical field
The disclosure is usually directed to the multilayer stripping film with pressure sensitive adhesive layer, and the method for preparing this film.
Background technology
Multilayer film has increasingly increased purposes in the industry.For example, film can be used as protection shaft coupling, mask, label, face When safety device, or their any combination.Hyaline membrane be used as display equipment (such as mobile telephone display, handheld game device or Even TV) on protection coating.Film also serves as the protection coating on part, to reduce scraping and protect color.
Many this films adhere to surface using adhesive.Especially, film may include contact adhesive.However, obtaining The required adherence for the contact adhesive being coated on multilayer film is time-consuming process, and high temperature is needed in some cases.
Unsuitable solidification can cause the poor adhesion of multilayer film, or can cause undesirable excessive adhesion power, special It is not in it can remove film.In many cases, catalyst is added in pressure-sensitive adhesion agent prescription to control solidification.However, Excessive catalyst, which is added in pressure-sensitive adhesion agent prescription, can cause significantly reduced storage life and unacceptably high Viscosity.
So, the improved multilayer film with contact adhesive is required.
Brief description of the drawings
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 include the diagram of exemplary multiple layer film.
Fig. 5 includes being used to be formed the diagram of an illustrative methods of multilayer film.
Embodiment
In a particular embodiment, multilayer film includes the pressure sensitive adhesive layer of base material film described in base material film, overlying, and The peel ply or coating contacted with the pressure sensitive adhesive layer.Peel ply or coating include release liner and to pressure sensitive adhesive layer The active reagent of component.Base material may include polymer film, and may include to be arranged at polymer film and pressure sensitive adhesive layer Between or the antistatic layer that is arranged on the surface relative with pressure sensitive adhesive layer of polymer film.In another example, can be by Lining form is applied on release coating, to be conducive to removing release coating from pressure sensitive adhesive layer in final use.At one In particular instance, multilayer film can be distributed from roller.
In a further exemplary embodiment, forming the method for multilayer film includes distribution base material film, and contact adhesive is combined Thing is coated on the base material film, and release coating is coated on the pressure-sensitive adhesive composition.Release coating includes Release liner and the active reagent of the component to pressure-sensitive adhesive composition.Optionally, lining form can be applied to stripping to apply On layer.Or, release coating can be applied on the apparent surface of base material film relative to pressure sensitive adhesive layer, so as to work as multilayer film When being rolled into volume, release coating contact pressure-sensitive adhesive composition.In another example, base material film may include antistatic layer.Or, Antistatic layer can be coated on the main surface of polymer film and solidify.
Fig. 1 includes the diagram of an exemplary multiple layer film 100.For example, multilayer film 100 includes base material film 102, pressure-sensitive adhesion Oxidant layer 104 and release coating 108.Release coating 108 is to contact pressure sensitive adhesive layer 104.Pressure sensitive adhesive layer 104 can be with base The main surface 110 of material film 102 is directly contacted, or can have intermediate layer between base material film 102 and pressure sensitive adhesive layer 104. As indicated, the second main surface 112 of base material film 102 can form the outer layer of multilayer film 100.
In an example, base material film 102 includes one or more layers of polymeric material.For example, polymeric material can For thermoplastic, polymeric materials.In another example, polymeric layer can be thermosets.In a particular instance, polymerization Nitride layer is extruding layer.Extruding layer may include other coating.In an example, polymeric material includes polyolefin, acetic acid esters Polymer, acrylic polymer, PAEK, polyester, makrolon, polyvinyl chloride, polyethers, polyamide, polyimides, heat Thermoplastic elastic, liquid crystal polymer, fluoropolymer, or their any combination.
A kind of exemplary polyolefins include polyolefin homopolymer (such as polyethylene, polypropylene, polybutene, polypenthylene or poly- first Base amylene), polyolefin copolymer (such as ethylene-propylene copolymer, ethylene-butene copolymer, or ethylene-octene copolymer), or Their any blend or combination.One exemplary polyethylene includes high density polyethylene (HDPE) (HDPE), the poly- second of intermediate density Alkene (MDPE), low density polyethylene (LDPE) (LDPE), ultra-low density polyethylene, or their any combination.One exemplary polyamides Amine includes nylon 6, nylon 6,6, nylon 11, nylon 12, or their any combination.One specific vinyl acetate includes second Alkene vinyl acetate (EVA).One exemplary PAEK may include polyether-ketone, polyether-ether-ketone, polyether ether ketone ketone, or they Any combination.In a particular instance, PAEK may include polyether-ether-ketone (PEEK).
One exemplary fluoropolymer includes PEP (FEP), polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride Alkene (PVDF), perfluoro alkoxy (PFA), the terpolymer (THV) of tetrafluoroethene, hexafluoropropene and vinylidene, polychlorostyrene three PVF (PCTFE), ethylene tetrafluoroethylene copolymer (ETFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), ethene, hexafluoro The terpolymer of propylene and tetrafluoroethene, or their any combination.
Acrylic polymer may include polyacrylate, polymethyl methacrylate, polymethacrylates or any Combination, and can be for such as lashing stage or through impact modified acrylic compounds.Generally wrapped through impact modified acrylic polymer The monomer of acrylic monomer and the suitable comonomer of effective dose or the copolymer of graft are included, to produce required bullet Property modulus and impact resistance.Can be used acrylic elastomer, its be sometimes referred to as ACM, lactoprene, Polyacrylic elastomer or " ACM ", it is the mixture based on polyacrylate and polymethacrylates, polyacrylate With the mixture of ethylene methyl acrylate copolymer (" EMAC ") (such as Chevron Chemicals EMAC 2260), it is or poly- The composition of the mixture of acrylate and ethylene butyl acrylate (" EBAC ").Or, it is thermoplastic through impact modified third Alkene acids polymers can for transparent glassy acrylic polymer (plastic copolymer of such as ethene and carboxylic acid compound, it is described Carboxylic acid compound is selected from acrylic acid, methacrylic acid and their mixture) with the blend of elastomeric component.
One exemplary thermoplastic elastomer (TPE) may include the blend of polyolefin and elastomer vulcanizate.For example, hot Thermoplastic elastic may include polyolefin and the elastomer being scattered in polyolefin.A kind of exemplary elastomer may include diene bullet Property body.Diene elastomer is the cross-linkable copolymers comprising diene monomers, the diene monomers such as ethylene propylene diene monomer (EPDM), ABS, or their any combination.Other exemplary elastomers may include the elastomer blend of alkene (commonly referred to as For thermoplastic olefin (TPO)).
In another example, polymer is polyester, such as polyethylene terephthalate.In another example, polyester is Liquid crystal polymer.One exemplary liquid crystal polymer includes aromatic polyester polymer, such as can be with trade name (Amoco (Amoco)),(Hirst Celanese Corp. (Hoechst Celanese)), SUMIKOSUPERTM (sumitomo chemical company (Sumitomo Chemical)), EKONOLTM(company of Saint-Gobain (Saint- Gobain))、DuPont HXTMOr DuPont ZENITETM(E.I.Du Pont Company (E.I.DuPont de Nemours)), RODRUNTM (You Niji can company (Unitika)), GRANLARTMThose of (Ge Langmeng companies (Grandmont)) acquisition, or their times Meaning combination.Liquid crystal polymer includes thermic (melt processible) liquid crystal polymer, wherein limited microbedding crystallinity can be spy It is not favourable.
Fig. 1 is back to, base material film 102 can have in the range of 0.5 mil to 10 mils, such as 0.5 mil to 5.0 mils In the range of, in the range of 1 mil to 5.0 mils, or the thickness in the range of even 1 mil to 3 mils.
Pressure sensitive adhesive layer 104 can be formed by curable pressure-sensitive adhesive composition.Contact adhesive is a kind of adhesive, Its combination degree is influenceed by the amount of the pressure for adhesive to be applied to surface.For example, pressure-sensitive adhesive composition can Include natural rubber, styrene block copolymer, acrylate, polyurethane, organosilicon, polydiorganosiloxanepolyurea polyurea copolymerization Thing, or their any combination.One exemplary styrene block copolymer include styrene-butadiene-copolymer (SBR), Styrene/isoprene/styrene block copolymer (SIS), acrylonitrile/styrene block copolymer, or their any group Close.
Acrylic polymer can be derived from monomer, such as (methyl) alkyl acrylate, alkyl acrylate, or methyl-prop Olefin(e) acid Arrcostab.The example of (methyl) alkyl acrylate includes (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) third The secondary butyl ester of olefin(e) acid, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) propylene Sour peopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) propylene Misery ester, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid last of the ten Heavenly stems Ester, (methyl) isodecyl acrylate, the ester of (methyl) acrylic acid 11, (methyl) dodecyl acrylate, or their any combination. Especially, acrylic polymer can be poly- (methyl) methyl acrylate.
In another example, acrylic polymer can be for can derived from least one acrylate monomer and at least one The copolymer of polymerized comonomer.One exemplary polymerizable co-monomers includes acrylonitrile, acrylamide, methacryl Amine, vinyl esters, vinyl ethers, vinylamide, vinyl ketone, styrene, halogen containing monomer, ionic comonomer, list containing acid Body, monomer containing alkali, the monomer with both reactive silicon-containing group and polymerizable unsaturated group, alkene, or theirs are any Combination.In another example, acrylic polymer main chain can be grafted by the macromonomer with polyether backbone, described to have The macromonomer of polyether backbone such as PEG (PEG), poly- (propane diols) (PPG), and poly- (tetramethylene glycol) , or their any combination (PTMG).
In another example, pressure sensitive adhesive layer 104 includes polyurethane.For example, polyurethane contact adhesive can be by isocyanide The reaction of acid esters and polyalcohol is formed.Isocyanate component may include '-diphenylmethane diisocyanate (MDI), toluene diisocynate Ester (TDI), hexamethylene diisocyanate (HDI), IPDI (IPDI), or their any combination. In one example, isocyanates may include '-diphenylmethane diisocyanate (MDI) or toluene di-isocyanate(TDI) (TDI).Especially, Isocyanates includes '-diphenylmethane diisocyanate (MDI) or derivatives thereof.
In an example, polyalcohol can be polyether polyol, polyester polyol, their modified or grafting Derivative, or their any combination.Suitable polyether polyol can be made in the following way：Via the double of epoxyalkane Metal cyanide catalyst by inserting polymerization (polyinsertion), by the alkali metal hydroxide as catalyst or In the presence of alkali alcoholate, and contain 2 to 6 in addition, the hydrogen atoms of preferably 2 to 4 bonding schemes are extremely The anionic polymerisation of epoxyalkane in the case of a kind of few initiator molecule, or by lewis acid (such as Antimony pentachloride or Boron fluoride etherate) in the presence of epoxyalkane cationic polymerization.Suitable epoxyalkane can contain in alkylidene residue There are 2 to 4 carbon atoms.Example includes tetrahydrofuran, 1,2- expoxy propane, 1,2- or 2,3- epoxy butane, oxirane, 1,2- Expoxy propane, or their any combination.Epoxyalkane can individually, continuously or as mixture be used.Initiator molecule Example include water or dihydric alcohol or trihydroxylic alcohol, such as ethylene glycol, 1,2-PD and 1,3-PD, diethylene glycol, dipropyl two Alcohol, ethane-Isosorbide-5-Nitrae-glycol, glycerine, trimethylolpropane, or their any combination.
Curable pressure-sensitive adhesive composition can include crosslinking agent, catalyst, tackifying resin, or their any combination.
One exemplary crosslinking agent includes multifunctional ethylenically unsaturated monomers.This monomer includes such as divinyl Aromatic compounds, divinyl ether, multifunctional maleimide, polyfunctional acrylic ester and methacrylate etc., or they Any combination.One exemplary divinyl aromatic compound includes divinylbenzene.One exemplary multifunctional (first Base) acrylate may include three (methyl) acrylate or two (methyl) acrylate, they is include three or two (first Base) acrylate group compound.One three exemplary (methyl) acrylate includes trimethylolpropane tris (methyl) Acrylate, propenoxylated trimethylolpropane trimethacrylate, the trimethylolpropane trimethacrylate of ethoxylation, three (2- hydroxyethyls) isocyanurate triacrylate, pentaerythritol triacrylate, or their any combination.One example Property two (methyl) acrylate include ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, three second Glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6- Hexylene glycol two (methyl) acrylate, 1,6- hexanediyl esters, tripropylene glycol diacrylate, the dipropyl of alkoxylate Omega-diol diacrylate, cyclohexanedimethanol two (methyl) acrylate, the cyclohexane dimethanol diacrylate of alkoxylate, 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 crosslinking agent includes alkyl methacrylate (such as methyl methacrylate) with providing reactive ammonia The copolymer of base, epoxy radicals, hydroxyl and/or carboxyl and the monomer of terminal ethylenyl groups end blocks, and styrene and butadiene Or the gradual change of isoprene or random copolymer (it has been at least partially epoxidized, and contains terminal ethylenyl groups), or their any combination.
The crosslinking agent of another exemplary includes isocyanates based cross-linker, such as aliphatic polymeric isocyanate, alicyclic ring adoption isocyanide Acid esters, aromatic polyisocyanate, aromatic aliphatic PIC, and their dimer and tripolymer and their reaction are produced Thing or polymer.The example of isocyanates based cross-linker includes toluene di-isocyanate(TDI), hexamethylene diisocyanate, poly- methylene Base polphenyl isocyanate, methyl diphenylene diisocyanate, the dimer of methyl diphenylene diisocyanate, trihydroxy methyl third The reaction product of alkane and toluene di-isocyanate(TDI), the reaction product of trimethylolpropane and hexamethylene diisocyanate, polyethers PIC, polyester PIC, or their any combination.Another crosslinking agent includes Si-H end-cap molecules.
Crosslinking agent is to be enough to cause the crosslinking of contact adhesive to provide enough cohesive strengths, so as to be base interested The effective dose that material produces required final adhesion properties is used.Crosslinking agent can be with 0.01 part to 20 parts, such as 0.1 to 10 part Amount is used, with total monomer weight.For example, the amount of isocyanate-based compound to be used is about 0.01 to 20 parts by weight, such as 0.05 to 15 parts by weight, in terms of 100 parts by weight polymer.
Catalyst may include organo-metallic catalyst, amine catalyst, or combinations thereof.Organo-metallic catalyst for example may be used Including dibutyl tin laurate, carboxylic acid lithium, butyl titanate, bismuth carboxylate, or their any combination.In another example, Catalyst may include platinum-vinyl siloxane, platinum-alkene complex, such as Pt- divinyl tetramethyl disiloxanes, or they Any combination.
One exemplary titanium catalyst includes organic functional titanate esters, siloxy titanate esters, or theirs is any Combination.Exemplary organic functional titanate esters include the epoxide of the epoxide titaniums double (acetoacetate ethyl esters) of 1,3- the third two, 1,3- the third two Titanium double (acetylacetone,2,4-pentanediones), diisopropoxy titanium double (acetylacetone,2,4-pentanedione), 2,3- diisopropoxies-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 fourths Epoxide titanium, tetraisopropoxy titanium, ethyl triethanol amine titanate, β Dicarbonyl Titaniums compound are (such as double (levulinic ketone group) diisopropyls Base titanate esters)；Or their any combination.Siloxy titanate esters include four (trimethylsiloxy) titaniums, double (front threes Base siloxy) double (isopropoxy) titaniums, or their any combination.
Exemplary tin compound includes dibutyl tin laurate, dibutyltin diacetate, dimethanol dibutyl tin, three The sour isobutyl tin (isobutyl tin triceroate) of suberic acid methoxycarbonyl phenyltin, tin octoate, three ceriums, two butyric acid diformazans Ji Xi, two neodecanoic acid stannous methides, tartaric acid tin triethyl, dibenzoic acid dibutyl tin, oleic acid tin, aphthenic acids tin, three -2- second Base caproic acid butyl tin, butyric acid tin, or their any combination.In another example, catalyst may include zirconium compounds, such as octanoic acid Zirconium.
Amine catalyst may include tertiary amine (such as tri-butylamine), N-methylmorpholine, N-ethylmorpholine, N, N, N ', N '-tetramethyl Ethylenediamine, pentamethyl dimethylene triamine and Geng Gao homologues, Isosorbide-5-Nitrae-diazabicylo-[2,2,2]-octane, N- methyl-N '- Dimethylaminoethyl piperazine, double (dimethylamino) piperazines, N, N- dimethyl benzylamines, N, N- dimethyl cyclohexyl amines, N, N- diethyl benzylamines, double (N, N- diethylamino ethyl) adipate esters, N, N, N ', N '-tetramethyl -1,3- butanediamine, N, N- Dimethyl-β-phenyl-ethylamine, double (dimethylaminopropyl) ureas, double (dimethylaminopropyl) amine, 1,2- methylimidazoles, 2- Methylimidazole, monocyclic and bicyclic amidine, double (dialkyl amido) alkyl ethers (such as double (dimethyl aminoethyl) ethers), with acid amides The tertiary amine of base (such as carbonylamino group), or their any combination.Another example of catalytic component includes Mannich base, bag Include secondary amine (such as dimethylamine), or aldehyde (such as formaldehyde), or ketone (such as acetone, MEK or cyclohexanone), or phenols (such as phenol, nonyl Phenol or bis-phenol).It may include three second with the catalyst for isocyanate groups for the form of the tertiary amine of the hydrogen atom of activity Hydramine, triisopropanolamine, N methyldiethanol amine, N- ethyldiethanolamines, N, N- dimethylethanolamines, they and epoxyalkane The reaction product of (such as expoxy propane or oxirane), or sec- tertiary amine, or their any combination.Silicon amine with carbon-silicon key (silamine) catalyst, such as 2,2,4- trimethyl -2- silicon morpholines, 1,3- diethylamino methyl tetramethyl two also are used as Siloxanes, or their any combination.
In another example, amine catalyst is selected from five methyl diethylentriamine, dimethylaminopropyl amine, N, N ' diformazans Base piperazine and dimorpholine base ether, N, N ' dimethyl aminoethyls N methyl piperazine,DM-70 (N, N ' diformazan The mixture of base piperazine and dimorpholine base ether), imidazoles (imadozole), triazine, or their any combination.
Catalyst for radical polymerization may include radical initiator, such as azo-type initiator, such as 2,2 '-azo Double (isobutyronitriles).Other initiators include peroxide initiator, including dialkyl peroxide (such as di-tert-butyl peroxide Thing, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hexane, 2,5- dimethyl -2,5- bis- (t-butylperoxy) -3- oneself Alkynes, dicumyl peroxide, tert-butyl cumyl peroxide and α, 60 '-bis(t-butylperoxy) cumene), diacyl Peroxide (chlorobenzoyl, peroxidating 2 such as between benzoyl peroxide, chloro benzoyl peroxide, peroxidating, 4- dichloro-benzenes first Acyl, lauroyl peroxide), peroxide base ester (such as t-butyl perbenzoate), peroxydicarbonate (such as diisopropyl peroxydicarbonate With -2- the ethylhexyls of two carbonic acid of peroxide two), peroxy ketal ((t-butylperoxy) hexamethylenes of such as 1,1- bis- and (the tertiary fourth of 1,1- bis- Base peroxy) -3,3,5- trimethyl-cyclohexanes), or their any combination.Peroxide base ester includes peroxy -2 ethyl hexanoic acid Tert-pentyl ester, peroxy -2 ethyl hexanoic acid tert-butyl ester, or their any combination.Particularly useful as the second initiator to reduce The peroxide base ester of residual monomer is peroxy neopentanoic acid tert-pentyl ester.
Tackifier can be combined with adhesive composition.Tackifier can be substantially compatible with base polymer." substantially may be used It is compatible " mean when combining tackifier and polymer, with opaque on the contrary, gained is combined in the case where drying form membrane for normally regarding Feel for substantial transparent.Exemplary tackifier include rosin and rosin derivative, are included in day in the oleoresin of pine tree The rosin material so existed, and their derivative, including rosin ester, modified rosin (be such as fractionated into, hydrogenate, dehydrogenation With the rosin of polymerization), modified rosin ester, or their any combination.
The tackifier of another exemplary include terpene resin, and (it is to exist in most of essential oils and the oleoresin of plant Formula C10H16Hydro carbons), and phenol be modified terpene resin (such as α firpenes, beta pinene, cinene, limonene, laurene, borneol Alkene, amphene), or their any combination.Exemplary tackifier may also comprise aliphatic hydrocarbon resins, aromatic hydrocarbon resins (example Such as based on C9, C5, bicyclopentadiene, benzofuran, indenes, styrene, the styrene and styrene derivative replaced), or it Any combination.The tackifier of another exemplary include atoleine, such as alkyl naphthene.
The amount of tackifier can be in the range of 0% to 60%, such as in the range of 5% to 60%, with one or more tackifier Gross weight meter.
Pressure-sensitive adhesive composition also can be stable comprising diluent, softening agent, plasticizer, excipient, antioxidant, UV Agent, counter-stimulus, opacifier, filler (such as clay and silica, pigment and their mixture), preservative, and other Component or additive.
Fig. 1 is back to, pressure sensitive adhesive layer 104 can have in the range of 0.1 mil to 10 mils, and such as 0.25 mil is extremely In the range of 5.0 mils, in the range of 0.25 mil to 2 mils, or the thickness in the range of even 0.25 mil to 1 mil.
Peel ply or coating 108 can be included and the non-miscible composition of pressure-sensitive adhesive composition.Peel ply or coating 108 can directly contact with pressure sensitive adhesive layer 104.Especially, at least a portion of peel ply or coating 108 can easily with pressure Sensitive adhesive layer 104 is separated.For example, peel ply or coating 108 can include release liner, such 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.One exemplary Release liner be organic silicon substrate release liner, the organosilicon of such as addition-curable and condensation curable.In such release liner In, platinum (Pt) or rhodium (Rh) catalyst are typically used as the curing catalysts for remover.
Or, release liner can be formed by the grease or oil of holding certain viscosity.For example, release liner may include silicone grease, Fluorosilicon oil, phenyl silicone oil, paraffin, or their any combination.
In a particular instance, release coating 108 includes the solidification for actively promoting curable pressure-sensitive adhesive composition Reagent, such as catalyst.For example, reagent can promote the crosslinking of at least one component of pressure-sensitive adhesive composition.Especially, shell It is can be included in from coating 108 in the range of 0.01wt% to 5.0wt%, such as in the range of 0.1wt% to 2.5wt%, In the range of 0.5wt% to 2.0wt%, or the amount even in the range of 0.5wt% to 1.5wt% reagent, urge as described above Agent.
Release coating 108 can have in the range of 0.025 mil to 10 mils, such as the model of 0.025 mil to 5.0 mils In enclosing, in the range of 0.25 mil to 2 mils, or the thickness in the range of even 0.25 mil to 1 mil.
In a specific embodiment shown in Fig. 2, multilayer film 200 includes base material film 202, and the base material film 202 includes More than one layer.For example, polymeric substrate 202 may include polymer film 204 and antistatic layer 206.Pressure sensitive adhesive layer 208 can be applied It is distributed on polymer film 204, release coating 210 can be coated on pressure sensitive adhesive layer 208.Optionally, lining form 212 can be applied To release coating 210.Or, release coating 210 can be coated on lining form 212, and combination layer (210,212) is in release coating table Face (210) place contacts pressure sensitive adhesive layer 208.
Polymeric layer 204 can be formed by the polymer as described above for being relevant to base material film 102.Antistatic coating 206 can Comprising dissipative polymer, such as polyether block amide, ionomer, polyimides, polyamide, or their any group Close.
In another example, antistatic coating 206 can include the polymer being filled through.Polymer may include acrylate, Polyolefin, polyurethane, polyester, polyethers, polyamide, polyimides, PAEK, or their any combination.One exemplary Filler may include conductive filler, such as metallic, conductivity ceramics particle, carbon black, conductive fiber, CNT, graphene, or Their any combination.In another example, antistatic coating can include the metal level of deposition, such as sputtering or vapor deposition Layer.
Especially, antistatic coating 206 can have 105To 1012Surface resistivity in the range of ohm/sq.For example, anti- The surface resistivity of electrostatic coating can be 108To 1012Ohm/sq, such as 109To 1012In the range of ohm/sq.
Pressure sensitive adhesive layer 208 and release coating 210 can be formed by above-mentioned material.Especially, release coating 210 includes work Change the reagent of at least one component of pressure sensitive adhesive layer 208, such as catalyst.
Optionally, lining form 212 can be applied on release coating 210.In an example, lining form 212 includes being attached to The film or paper of release coating.One exemplary polymer film can be comprising polyolefin, acetic acid esters, acrylic compounds, PAEK, poly- Ester, polyethers, polyamide, polyimides, thermoplastic elastomer (TPE), styrenic polymer, liquid crystal polymer, fluoropolymer, or Their any combination.In an example, release liner 212 includes cellulose acetate membrane.In another example, lining form 212 Including polyolefin film.In another example, lining form 212 includes polyester film.In an example, can for example using corona discharge, Plasma discharge, ion processing etc. handle lining form 212, to improve the adhesion to release coating.Lining form 212 can have In the range of 0.5 mil to 5 mils, such as in the range of 0.5 mil to 3 mils, or even in the scope of 1 mil to 3 mils Interior thickness.
In the another exemplary embodiment shown in Fig. 3, multilayer film 300 may include base material film 302.In an example, Base material film 302 includes polymer film 304 and antistatic layer 306.In exemplary multiple layer film 300, contact adhesive 308 can be set In on the first main surface 312 of base material film 302, and release coating 310 may be disposed at the relative main surface 314 of base material film 302 On.When by multilayer film rolled for subsequent allocations, release coating 310 contacts setting with pressure sensitive adhesive layer 308, and promotees Enter the solidification or crosslinking of pressure sensitive adhesive layer 308.
Although multiple layer polymer base material is shown as with being contacted with release coating 310 on the main surface of base material film 302 Antistatic layer 306, but antistatic coating and other layers can be rearranged.For example, the multilayer film shown in Fig. 4 includes polymer matrix Material 402, its middle polymeric layer 404 is contacted with release coating 410, and antistatic layer 406 is contacted with pressure sensitive adhesive layer 408.Work as volume During dynamic film 400, reagent of at least one component to the pressure-sensitive adhesive composition in pressure sensitive adhesive layer 408 for activity is included Release coating 410 contacted with pressure sensitive adhesive layer, so as to cause the solidification and crosslinking of the pressure-sensitive adhesive composition of layer 408.
Fig. 5 includes being used to be formed the diagram of an example process of multilayer film.For example, process 500 includes base material film 502 Volume, base material film distributes from the volume.Base material film 502 may include one or more layers of polymer film.Optionally, base material film bag Include antistatic layer.Or, antistatic layer can be at coating station 504 as painting Layer assignment, and solidifies.Antistatic coating (not shown) It may be designed as solidifying at room temperature, respond heat and solidify, respond the actinic radiation with some other curing mechanisms and solidify.Example Such as, antistatic coating can be handled in baking oven 514.
In addition, pressure-sensitive adhesive composition can be coated with coating station 506 on base material film 502.Contact adhesive is combined Thing may be selected from composition disclosed above.Optionally, pressure-sensitive adhesive composition can be toasted or dried for example in baking oven 516. Or, actinic radiation processing can be used in pressure-sensitive adhesive composition.
In addition, release coating can be applied on pressure-sensitive adhesive composition at coating station 508.Release coating include to At least one component of the pressure-sensitive adhesive composition distributed at 506 is active reagent.In an example, not in deposition After be heat-treated release coating.Or, release coating can be solidified by actinic radiation or heat treatment.
Or, release coating can be applied to the phase of base material film 502 relative to the pressure-sensitive adhesive composition applied at 506 To main surface.When multilayer film scrolling is coiled 510, there is contact adhesive to apply for the release coating contact applied at 508 The apparent surface of the multilayer film of layer.
Although coating station (504,506 or 508) is shown as distributing on base material film 502, other coating techniques can be used To apply coating layer.For example, roller coat, intaglio plate coating, blade coating, dip-coating, spraying, slit extrusion coated, or their deformation.
Optionally, system 500 includes being used for the roller 512 for distributing lining form on the release coating of distribution at 508.By multilayer film Scrolling coiled 510 is to be stored the use for after.The deformation of the process is possible.For example, as disclosed above, peeling off Coating station 508 can distribute release coating to lining form from roller 512, and the minor structure can be bound to base material film/stripping by laminated station The minor structure of coating.
Once being formed, then multilayer film can have no more than 1000g/in peel strength, such as in 2g/in to 500g/in models In enclosing, the peel strength in the range of 3g/in to 200g/in or 4g/in to 100g/in.Relative to the peel strength of stainless steel plate Measured under 180 ° of angle and 12in/min detachment rate.
In addition, curing performance can be measured as cure index, the stripping that the cure index was defined as at 18 hours is strong The ratio of degree divided by the peel strength at 7 days.Especially, multilayer film can have no more than 2, such as no more than 1.5 or not even Cure index more than 1.2.
Example
Prepare the adhesive for including acrylic adhesives, isocyanate crosslinking and dibutyltin dilaurate catalyst Mixture.Mixture is poured and cast from polyethylene terephthalate (PET) sheet material of 2 mil thicks, and the baking at 135 DEG C Dried 1.5 minutes in case.The final thickness of contact adhesive is 0.55 mil between 0.6 mil.One pack timber-used is stanniferous to be had Machine silicon release-coated pad covering, another pack timber-used not the organosilicon release-coated of tin-containing catalyst pad covering.Sample Product aging 18 hours, 3 days or 7 days at room temperature.After the time is specified in aging, the pad of release-coated is removed, 4.5lb is used Psa layer is bonded to PET base material by laboratory roller.After stopping 20 minutes, PSA peel adhesion is tested and recorded.Peel off and survey It is 180 ° and 12in/min to try parameter.
As shown in the following Table 1, after 18 hours, the stripping of the sample of the pad with stanniferous organosilicon release-coated is strong Degree, which has reached, to be fully cured, but the peel strength of the sample of the pad with not stanniferous organosilicon release-coated is still high. After aging in 3 days, the PSA of the pad with not stanniferous organosilicon release-coated is close to be fully cured.
The peel adhesion of the sample of table 1.
Especially, discovery can reduce hardening time by by catalyst added to peel ply.Although hardening time can lead to Cross and catalyst is added in pressure-sensitive adhesive composition and accelerated, but the catalytic amount in increase pressure-sensitive adhesive composition is led Cause low storage life and the high viscosity in coating process.In the case of without this discovery, in pressure-sensitive adhesive composition Low catalyst causes the solidification of long hardening time and possible difference.In the case of there is catalyst in release coating, it can subtract The amount of catalyst less or in elimination pressure-sensitive adhesive composition, so that long storage life is provided in the fabrication process, and together When provide coating after short hardening time.
It should be noted that all activities that need not as above described in general description or example, it may not be necessary to specific living A dynamic part, and one or more other activities can be carried out in addition to those described.In addition, activity list it is suitable Sequence is not necessarily the order of carry out activity.
In the foregoing specification, concept has been described with reference to particular embodiments.However, it will be understood by those skilled in the art that Various modifications and changes can be carried out in the case of without departing from the scope of the present invention described in claims below.Therefore, say Bright book and accompanying drawing should be regarded as illustrative and not restrictive, and all such modifications are intended to be included in the scope of the present invention It is interior.
As used herein, term "comprising", " comprising ", " having " or their any other variant are intended to non-exclusive Property includes.E.g., including the process of series of features, method, product or device are not necessarily limited to those features, but can wrap Include not expressly listed or these processes, method, product or device other intrinsic features.In addition, unless clearly conversely referring to Go out, "or" refer to it is inclusive or, rather than it is exclusive or.For example, condition A or B is by any one following satisfaction：A is true (or deposits ) and B is false (or in the absence of), A is false (or in the absence of) and B is true (or presence), and A and B are true (or presence).
Moreover, the use of " one kind " is used to describe element described herein and part.Facility has been only for, and this hair is provided The general sense of bright scope.The description is understood to include a kind of or at least one, and odd number also includes plural number, unless its is bright It is aobvious that there is contrary.
Benefit, other advantages and way to solve the problem are on specific embodiment description executed as described above.However, benefit, Advantage, way to solve the problem and any feature that any benefit, advantage or solution may be made to occur or become more apparent upon It is not necessarily to be construed as any claim or crucial, the required or essential feature of all authority requirement.
After specification is read, it will be apparent to those skilled in the art that for clarity, herein in separated embodiment Some features of description can also combine single embodiment and provide.On the contrary, for simplicity, the various spies described in single embodiment Levying can also provide dividually or in any sub-combination.In addition, including to the reference of the value described in scope every in the range of this One value.

Claims (29)

1. a kind of multilayer film, it includes：
Base material film with the first and second main surfaces；
The pressure sensitive adhesive layer on the first main surface of the base material film is arranged at, the pressure sensitive adhesive layer includes curable group Compound；With
Be relatively arranged on the peel ply on the pressure sensitive adhesive layer with the base material film, the peel ply comprising release liner and Catalyst, the catalyst is adapted to the solidification curable compositions, wherein the catalyst is organo-metallic catalyst, amine Catalyst, or combinations thereof.
2. multilayer film according to claim 1, wherein the 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 the curable compositions include polymer, the polymer includes Natural rubber, styrene block copolymer, acrylate, polyurethane, organosilicon, polydiorganosiloxanepolyurea polyurea copolymer, or Their any combination.
4. multilayer film according to claim 1, wherein the curable compositions include crosslinking agent.
5. multilayer film according to claim 1, wherein the base material film includes polymer film.
6. multilayer film according to claim 5, wherein the polymer film is polyolefin, acetate polymer, acrylic acid Birds of the same feather flock together compound, PAEK, polyester, polyethers, makrolon, polyvinyl chloride, polyamide, polyimides, thermoplastic elastomer (TPE), liquid Crystalline polymer, fluoropolymer, or their any combination.
7. multilayer film according to claim 1, wherein the base material film includes antistatic layer.
8. multilayer film according to claim 7, wherein the antistatic layer includes dissipative polymer.
9. multilayer film according to claim 7, wherein the antistatic layer includes conductive filler.
10. multilayer film according to claim 7, wherein the antistatic layer has 105To 1012In the range of ohm/sq Surface resistivity.
11. multilayer film according to claim 1, it also includes relative with the pressure sensitive adhesive layer and is arranged at the stripping Lining form on absciss layer.
12. multilayer film according to claim 11, wherein the lining form be polyolefin, acetate polymer, acrylic compounds, PAEK, polyester, polyethers, makrolon, polyvinyl chloride, polyamide, polyimides, thermoplastic elastomer (TPE), styrene polymer Compound, liquid crystal polymer, fluoropolymer, or their any combination.
13. multilayer film according to claim 11, wherein the lining form includes paper.
14. multilayer film according to claim 1, wherein the curable compositions have no more than 1000g/in stripping Intensity.
15. multilayer film according to claim 14, wherein peel strength are in the range of 2g/in to 500g/in.
16. multilayer film according to claim 15, wherein peel strength are in the range of 3g/in to 200g/in.
17. multilayer film according to claim 16, wherein peel strength are in the range of 4g/in to 100g/in.
18. multilayer film according to claim 1, wherein the multilayer film has no more than 2 cure index.
19. multilayer film according to claim 1, wherein the cure index is not more than 1.5.
20. multilayer film according to claim 1, wherein the cure index is not more than 1.2.
21. a kind of multilayer film, it includes：
Base material film with the first and second main surfaces；
The pressure sensitive adhesive layer on the first main surface of the base material film is arranged at, the pressure sensitive adhesive layer includes curable group Compound, the curable compositions include polymer and crosslinking agent；
The peel ply on the pressure sensitive adhesive layer is relatively arranged on the base material, the peel ply is comprising release liner and urges Agent, the catalyst is adapted to the solidification curable compositions, wherein the catalyst is organo-metallic catalyst, amine is urged Agent, or combinations thereof；With
Lining form on the release coating.
22. multilayer film according to claim 21, wherein the release liner is silica-base material, fluorine-based material, long alkane Base sill, fatty acid acyl amine based material, silicon dioxide powder powder material, or their any combination.
23. multilayer film according to claim 21, wherein the polymer includes natural rubber, styrenic block copolymer Thing, acrylate, polyurethane, organosilicon, polydiorganosiloxanepolyurea polyurea copolymer, or their any combination.
24. multilayer film according to claim 21, wherein the lining form is polyolefin, acetic acid esters, acrylic compounds, polyarylether Ketone, polyester, makrolon, polyvinyl chloride, polyethers, polyamide, polyimides, thermoplastic elastomer (TPE), styrenic polymer, liquid Crystalline polymer, fluoropolymer, or their any combination.
25. multilayer film according to claim 21, wherein the curable compositions have no more than 1000g/in stripping From intensity.
26. multilayer film according to claim 21, wherein the multilayer film has no more than 2 cure index.
27. a kind of method for forming multilayer film, methods described includes：
Base material of the distribution with the first and second main surfaces；
The first main surface of the base material is coated with using curable pressure-sensitive adhesive composition；With
It is coated with using release coating, to contact the curable pressure-sensitive adhesive composition, the release coating includes stripping material Material and catalyst, the catalyst are adapted to the solidification curable compositions, wherein the catalyst is metal organic catalysis Agent, amine catalyst, or combinations thereof.
28. method according to claim 27, it is additionally included on the release coating and distributes lining form.
29. method according to claim 27, wherein including bonding with the curable pressure sensitive using release coating coating Agent composition is relative and the release coating is coated with the second main surface of the base material, and multilayer film described in rolling is so that institute Release coating is stated to contact with the curable pressure-sensitive adhesive composition.
CN201280078163.0A 2012-12-12 2012-12-12 Multilayer film with pressure sensitive adhesive layer Expired - Fee Related CN104936776B (en)

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CN104936776A (en) 2015-09-23
WO2014092700A1 (en) 2014-06-19
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KR101892432B1 (en) 2018-10-04
JP2016501945A (en) 2016-01-21

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