KR20150091505A - Multilayer film having pressure sensitive adhesive layer - Google Patents

Multilayer film having pressure sensitive adhesive layer Download PDF

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Publication number
KR20150091505A
KR20150091505A KR1020157017777A KR20157017777A KR20150091505A KR 20150091505 A KR20150091505 A KR 20150091505A KR 1020157017777 A KR1020157017777 A KR 1020157017777A KR 20157017777 A KR20157017777 A KR 20157017777A KR 20150091505 A KR20150091505 A KR 20150091505A
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South Korea
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film
multilayer film
sensitive adhesive
layer
combination
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KR1020157017777A
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Korean (ko)
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KR101892432B1 (en
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시펭 리우
제임스 켐프스키
마이클 제이. 지바니스
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생-고뱅 퍼포먼스 플라스틱스 코포레이션
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C09J7/02—
    • C09J7/0207—
    • C09J7/0228—
    • 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

The multilayered film includes a base film having first and second major surfaces and a pressure-sensitive adhesive layer disposed on a first main surface of the base film. The pressure-sensitive adhesive layer includes a curable composition. The multilayered film further comprises a release layer in the pressure-sensitive adhesive layer on the opposite side of the base film. The release layer comprises a release material and a curing composition curing catalyst.

Description

[0001] MULTILAYER FILM HAVING PRESSURE SENSITIVE ADHESIVE LAYER [0002]

The present invention broadly relates to a multilayer release film having a pressure-sensitive adhesive layer and a method for producing such a film.

Multilayer films have been increasing in industrial applications. For example, the film may be used with protective coupling, mask, label, temporary security device or any combination thereof. The transparent film is used as a protective cover in display devices such as mobile phones, portable game devices, or even displays on televisions. The film is also used as a protective cover for parts to reduce scratches and protect the color.

Many such films are attached to surfaces using adhesives. In particular, the film may comprise a tackifier. However, achieving the desired tack in the tack applied to the multilayer film is a time consuming process and in some cases requires a temperature rise.

Due to inadequate curing, the multilayered film may be poorly adhered or undesirably over-adhered, especially in the removable film. In many cases, catalysts are added to the tackifier formulation to control cure. However, if too much catalyst is added to the tackifier formulation, the time available will be significantly reduced and unacceptably high viscosity can be achieved.

Thus, an improved multilayer film with a tackifier would be desirable.

Figures 1, 2, 3, and 4 illustrate exemplary multilayer films.
Figure 5 illustrates a method of making an exemplary multilayer film.

In certain embodiments, the multilayer film comprises a substrate film, a pressure sensitive adhesive layer overlying the substrate film, and a release layer or coating in contact with the pressure sensitive adhesive layer. The release layer or coating comprises a release agent and a formulation having activity on the pressure-sensitive adhesive layer component. The substrate may comprise a polymer film and an antistatic layer interposed between the polymer film and the pressure sensitive adhesive layer or disposed on the surface of the polymer film opposite to the pressure sensitive adhesive layer. In another embodiment, a liner film is applied to the top of the release coating to facilitate removal of the release coating from the adhesive at the time of final use. In certain embodiments, the multilayer film is fed from a roll.

In another exemplary embodiment, the method for making a multilayered film comprises providing a substrate film, applying the adhesive composition to a substrate film, and applying the release coating to the adhesive composition. The release coating comprises the release agent and the active agent to the components of the adhesive composition. Optionally, a liner film can be applied to the top of the release coating. Alternatively, the release coating may be applied to the opposite surface of the substrate film to the pressure sensitive adhesive layer so that when the multilayered film is dried with a roll, the release coating is contacted with the pressure sensitive adhesive composition. In a further embodiment, the substrate film comprises an antistatic layer. Alternatively, the antistatic layer may be applied to the polymer film major surface and cured.

FIG. 1 illustrates an exemplary multilayer film 100. For example, the multilayer film 100 includes a base film 102, a pressure-sensitive adhesive layer 104, and a release coating 108. The release coating 108 is in contact with the pressure-sensitive adhesive layer 104. The pressure sensitive adhesive layer 104 may be in direct contact with the main surface 110 of the base film 102 or may have an interposed layer between the base film 102 and the pressure sensitive adhesive layer 104. As shown, the second major surface 112 of the base film 102 forms the outer layer of the multilayer film 100.

In an embodiment, the substrate film 102 comprises one or more layers of polymeric material. For example, the polymeric material may be a thermoplastic polymeric material. In yet another embodiment, the polymer layer may be a thermoset material. In certain embodiments, the polymer layer is an extruded layer. The extruded layer may comprise additional coatings. In an embodiment, the polymeric material is selected from the group consisting of polyolefins, acetate polymers, acrylic polymers, polyaryl ether ketones, polyesters, polycarbonates, polyvinyl chloride, polyethers, polyamides, polyimides, thermoplastic elastomers, Or any combination thereof.

Exemplary polyolefins include polyolefin homopolymers such as polyethylene, polypropylene, polybutene, polypentene, or polymethylpentene; Polyolefin copolymers such as ethylene-propylene copolymers, ethylene-butene copolymers, or ethylene-octene copolymers; Or any blend or combination thereof. Exemplary polyethylenes include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), ultra low density polyethylene, or any combination thereof. Exemplary polyamides include nylon 6, nylon 6,6, nylon 11, nylon 12, or any combination thereof. Certain vinyl acetates include ethylene vinyl acetate (EVA). Exemplary polyaryl ether ketones include polyether ketone, polyetheretherketone, polyetheretherketoneketone, or any combination thereof. In certain embodiments, the polyaryl ether ketone comprises polyetheretherketone (PEEK).

Exemplary fluoropolymers include fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluoroalkoxy (PFA), tetrafluoroethylene, hexafluoropropylene, (THF), polychlorotrifluoroethylene (PCTFE), ethylene tetrafluoroethylene copolymer (ETFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), ethylene, hexafluoropropylene, And trimers of tetrafluoroethylene, or any combination thereof.

The acrylic polymers include polyacrylates, polymethyl methacrylates, polymethacrylates, or any combination thereof, such as impact grade or impact-reinforced acrylic. Impact-reinforced acrylic polymers generally include copolymers of an effective comonomer or grafting moiety with an acrylic monomer to have the desired elastic modulus and impact resistance. Polyacrylates and polymethacrylates, polyacrylates and ethylene methacrylate copolymers ("EMAC"), such as those sold under the trade names Chevron Chemicals EMAC 2260 ), Or a mixture based on polyacrylate and ethylene butyl acrylate ("EBAC") may be used. Alternatively, the thermoplastic impact-reinforced acrylic polymer may be a blend of a transparent glassy acrylic polymer, such as a plastic copolymer of a carboxylic acid compound selected from ethylene and acrylic acid, methacrylic acid, and mixtures thereof, and elastomeric components .

Exemplary thermoplastic elastomers include blends of polyolefins and elastomer vulcanizates. For example, the thermoplastic elastomer comprises an elastomer dispersed in a polyolefin and a polyolefin. Exemplary elastomers include diene elastomers. The diene elastomer is a crosslinkable copolymer comprising diene monomers such as ethylene propylene diene monomer (EPDM), ABS, or any combination thereof. Additional exemplary elastomers include elastomer blends of olefins, commonly known as thermoplastic olefins (TPO).

In a further embodiment, the polymer is a polyester, such as polyethylene terephthalate. In another embodiment, the polyester is a liquid crystal polymer. Exemplary liquid crystal polymers include aromatic polyester polymers such as the trademarks XYDAR® (Amoco), VECTRA® (Hoechst Celanese), SUMIKOSUPER ™ (Sumitomo Chemical), EKONOL ™ (Saint-Gobain), DuPont HX ™ or DuPont ZENITE ™ DuPont de Nemours, RODRUN (TM) (Unitika), GRANLAR (Grandmont), or any combination thereof. Liquid crystal polymers include thermotropic (melt-processible) liquid crystal polymers in which constrained microlayer crystallinity may be particularly advantageous.

Referring to FIG. 1, the thickness of the base film 102 is 0.5 to 10 mils, for example, 0.5 to 5.0 mils, 1 to 5.0 mils, or 1 to 3 mils.

The pressure-sensitive adhesive layer 104 is formed from a curable pressure-sensitive adhesive composition. The adhesive is an adhesive to which the degree of bonding is affected by the degree of pressure applied to apply the adhesive to the surface. For example, the pressure sensitive adhesive composition may comprise a natural rubber, a styrene block copolymer, an acrylate, a polyurethane, a silicone, a polydiorganosiloxane polyurea copolymer, or any combination thereof. Exemplary styrene block copolymers include styrene butadiene copolymers (SBR), styrene / isoprene / styrene block copolymers (SIS), acrylonitrile / styrene block copolymers, or any combination thereof.

Acrylic polymers may be derived from monomers such as alkyl (meth) acrylates, alkyl acrylates, or alkyl methacrylates. Exemplary alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) (Meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, isoamyl (meth) acrylate, (Meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, isohexyl (meth) acrylate, (Meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, or any combination thereof. In particular, the acrylic polymer may be polymethyl (meth) acrylate.

In another embodiment, the acrylic polymer may be a copolymer derived from at least one acrylate monomer and at least one polymerizable comonomer. Exemplary polymerizable comonomers include but are not limited to acrylonitrile, acrylamide, methacrylamide, vinyl esters, vinyl ethers, vinyl amides, vinyl ketones, styrenes, halogen containing monomers, ionic monomers, acid containing monomers, Containing monomer and a polymerizable deblocking group, a monomer having both olefins, or any combination thereof. In a further embodiment, the acrylic polymer backbone comprises a macromonomer having a polyether backbone such as poly (ethylene glycol) (PEG), poly (propylene glycol) (PPG), and poly (tetramethylene glycol) These combinations can be grafted.

In yet another embodiment, the pressure-sensitive adhesive layer 104 comprises polyurethane. For example, a polyurethane adhesive is formed by the reaction of an isocyanate and a polyol. The isocyanate component includes methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or any combination thereof. In an embodiment, the isocyanate comprises methylene diphenyl diisocyanate (MDI) or toluene diisocyanate (TDI). In particular, the isocyanates include methylene diphenyl diisocyanate (MDI) or derivatives thereof.

In an embodiment, the polyol can be a polyether polyol, a polyester polyol, a modified or grafted derivative thereof, or any combination thereof. Suitable polyether polyols may be prepared by polyinsertion of an alkylene oxide by a double metal cyanide catalyst or by 2 to 6, preferably 2 to 4, at least one initiator molecule containing reactive hydrogen atoms Is produced by anionic polymerization of an alkylene oxide in the presence of an alkali hydroxide or alkali alcoholate as a catalyst or by cationic polymerization of an alkylene oxide in the presence of a Lewis acid such as antimony pentachloride or boron fluoride etherate. Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical. Examples include tetrahydrofuran, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide; Ethylene oxide, 1,2-propylene oxide, or any combination thereof. The alkylene oxides may be subsequently used individually or as a mixture. One example of an initiator molecule is water or a mixture of ethylene glycol, 1,2-propanediol and 1,3-propanediol, diethylene glycol, dipropylene glycol, ethane-1,4-diol, glycerol, trimethylol propane, Include di- or tri-alcohols such as any combination.

The curable pressure sensitive adhesive composition includes a crosslinking agent, a catalyst, a tackifying resin, or any combination thereof.

Exemplary crosslinking agents include polyfunctional ethylenically unsaturated monomers. Such monomers include, for example, divinyl aromatic, divinyl ether, multifunctional maleimide, multifunctional acrylates and methacrylates, and the like, or any combination thereof. Exemplary divinyl aromatics include divinylbenzene. Exemplary multi-functional (meth) acrylates include tri (meth) acrylates or di (meth) acrylates, which are compounds containing three or two (meth) acrylate groups. Exemplary tri (meth) acrylates include trimethylolpropane tri (meth) acrylate, propoxylated trimethylol propane, ethoxylated trimethylol propane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate , Pentaerythritol triacrylate, or any combination thereof. Exemplary di (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, alkoxylated 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclo (Meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, neopentyl glycol diacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, urethane di (meth) acrylate, or any combination thereof.

Another exemplary crosslinking agent is a copolymer of an alkyl methacrylate such as methyl methacrylate and a monomer providing reactive amino, epoxy, hydroxyl and / or carboxyl groups and terminal vinyl groups, butadiene or isoprene containing epoxidized and terminal vinyl groups A tapered block, a tapered or random copolymer, or any combination thereof.

Additional exemplary crosslinking agents include isocyanate-based crosslinking agents such as aliphatic polyisocyanates, aliphatic ring polyisocyanates, aromatic polyisocyanates, aromatic aliphatic polyisocyanates, and dimers and trimers thereof and reaction products or polymers thereof. Exemplary isocyanate-based crosslinkers include the reaction products of tolylene diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, diphenylmethane diisocyanate, dimer of diphenylmethane diisocyanate, trimethylol propane and tolylene diisocyanate, Trimethylol propane and hexamethylene diisocyanate, polyether polyisocyanate, polyester polyisocyanate, or any combination thereof. Another cross-linking agent comprises a Si-H terminal molecule.

The crosslinking agent is used in an effective amount sufficient to provide a suitable tack strength that can impart desired final adhesion properties to the substrate of interest with tackifier crosslinking. The crosslinking agent is used in an amount of 0.01 to 20 parts, for example, 0.1 to 10 parts based on the total weight of the monomers. For example, the amount of the isocyanate-based compound used is about 0.01 to 20 parts by weight, for example 0.05 to 15 parts by weight, based on 100 parts by weight of the polymer.

The catalyst comprises an organometallic catalyst, an amine catalyst, or a combination thereof. The organometallic catalyst includes, for example, dibutyltin dilaurate, lithium carboxylate, tetrabutyl titanate, bismuth carboxylate, or any combination thereof. In another embodiment, the catalyst comprises platinum-vinylsiloxane, platinum-olefin complexes such as Pt-divinyltetramethyldisiloxane, or any combination thereof.

Exemplary titanium catalysts include oleophilic titanates, siloxytitanates, or any combination thereof. Exemplary oily organoleptic titanates include 1,3-propanedioxytitanium bis (ethylacetoacetate); 1,3-propanedioxy titanium bis (acetylacetonate); Diisopropoxy titanium bis (acetylacetonate); 2,3-di-isopropoxy-bis (ethyl acetate) titanium; Titanium naphthenate; Tetrapropyl titanate; Tetrabutyl titanate; Tetraethylhexyl titanate; Tetraphenyl titanate; Tetraoctadecyl titanate; Tetrabutoxy titanium; Tetraisopropoxy titanium; Ethyl triethanol amine titanate; Beta-dicarbonyl titanium compounds such as bis (acetylacetonyl) diisopropyl titanate; Or any combination thereof. The siloxytitanate includes tetrakis (trimethylsiloxy) titanium, bis (trimethylsiloxy) bis (isopropoxy) titanium, or any combination thereof.

Exemplary tin compounds include dibutyltin dilaurate; Dibutyltin diacetate; Dibutyltin dimethoxide; Carbomethoxyphenyl tin tris-uberate; Tin octoate; Isobutyl tin tricalite; Dimethyl tin dibutyrate; Dimethyltin dineodecanoate; Triethyl tin tartrate; Dibutyltin dibenzoate; Tin oleate; Tin naphthenate; Butyl tin tri-2-ethylhexoate; Tin butyrate; Or any combination thereof. In another embodiment, the catalyst comprises a zirconium compound, such as zirconium octoate.

The amine catalysts are selected from the group consisting of tertiary amines such as tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N'- tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologues, N, N-dimethylbenzylamine, N, N-dimethylaminoethylpiperazine, bis (dimethylaminoalkyl) piperazine, (N, N-diethylaminoethyl) adipate, N, N, N ', N'-tetramethyl-1,3-butanediamine, N (Dimethylaminopropyl) urea, bis (dimethylaminopropyl) amine, 1,2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amidine, bis Alkylamino) alkyl ethers such as bis (dimethylaminoethyl) ether, tertiary amines having an amide group (e.g., amide group formation), or any combination thereof. Another catalyst component embodiment is a mixture of a Mannich base such as a secondary amine such as dimethylamine or an aldehyde such as formaldehyde or a ketone such as acetone, methyl ethyl ketone or cyclohexanone or a phenol such as phenol, nonylphenol or bisphenol . Catalysts in the form of tertiary amines having active hydrogen atoms on isocyanate groups include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, Propylene oxide or their reaction products with ethylene oxide, or secondary-class amines, or any combination thereof. Silanes having carbon-silicon bonds such as 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyltetramethyldisiloxane, or any combination thereof may also be used as catalysts .

In a further embodiment, the amine catalyst is selected from the group consisting of pentamethyldiethylenetriamine, dimethylaminopropylamine, N, N'dimethylpiperazine and dimorpholinoethyl ether, N, N'dimethylaminoethyl N-methylpiperazine, JEFFCAT® DM-70 (of a mixture of N, N 'dimethylpiperazine and dimorpholinoethyl ether), imidazole, triazine, or any combination thereof.

Catalysts for free-radical polymerization include free-radical initiators such as azo-type initiators such as 2,2'-azobis (isobutyronitrile). Other initiators include peroxide initiators and include dialkyl peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5- , T-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide and?, 60 '-bis (t- butylperoxy) isopropylbenzene, diacyl peroxide Benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, peroxy ester such as t-butyl perbenzoate, peroxydicarbonate, Di (t-butylperoxy) cyclohexane and 1,1-di (t-butylperoxy) cyclohexane, diisopropylperoxy dicarbonate and di-2-ethylhexylperoxydicarbonate, peroxyketals such as 1,1- Hydroxy-3,3,5-trimethylcyclohexane, or any combination thereof. Peroxy esters include t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, or any combination thereof. A particularly useful peroxy ester as a secondary initiator for reducing residual monomers is t-amyl peroxypivalate.

The tackifier may be combined with the adhesive composition. The tackifier is substantially compatible with the base polymer. By " substantially compatible " is meant that when the tackifier and polymer are combined, the resulting combination is substantially opaque and substantially transparent at normal vision in the dry film form. Exemplary tackifiers include rosin and rosin derivatives, natural rosin materials of pine tree oleoresin and derivatives thereof such as rosin esters, modified rosins such as fractionation, hydrogenation, dehydrogenation, and polymerized rosins, modified rosin esters , Or any combination thereof.

Another exemplary tackifier is terpene resin, a hydrocarbon of formula C 10 H 16 in the majority of the plant essential oils and oleoresin, and phenol modified terpene resins such as alpha pinene, betapinene, dipentene, limonene, Nylon, camphene, or any combination thereof. Exemplary tackifiers may also include aliphatic hydrocarbon resins, aromatic hydrocarbon resins such as C9, C5 based, dicyclopentadiene, coumarone, indene, styrene, substituted styrene and styrene derivatives and the like, These combinations are included. Other exemplary tackifiers include liquid paraffins, such as alkyl naphthenes.

The tackifier content is 0% to 60%, such as 5% to 60%, by total weight of the at least one tackifier.

The pressure-sensitive adhesive composition also includes a diluent, a softener, a plasticizer, an excipient, an antioxidant, a UV stabilizer, an anti-irritant, an opacifying agent, a filler such as clay and silica, a pigment and mixtures thereof, a preservative, do.

1, the thickness of the pressure-sensitive adhesive layer 104 is 0.1 to 10 mils, for example, 0.25 to 5.0 mils, 0.25 to 2 mils, or 0.25 to 1 mmils.

The release layer or coating 108 comprises a composition that is incompatible with the pressure-sensitive adhesive composition. The release layer or coating 108 may be in direct contact with the pressure sensitive adhesive layer 104. In particular, at least a part of the release layer or coating 108 can be easily separated from the pressure-sensitive adhesive layer 104. For example, the release layer or coating 108 includes release materials such as silicone-based, fluorine-based, long chain alkyl-based, fatty acid amide-based, silica powder materials, or any combination thereof. Exemplary release materials are silicone-based release materials, such as addition-curable and condensation-curable silicone. In this type of release material, platinum (Pt) or rhodium (Rh) catalysts are generally used as curing catalysts for the release agent.

Alternatively, the release material may be formed of grease or oil that maintains a certain viscosity. For example, the release material may comprise silicone grease, fluorosilicone oil, phenyl silicone oil, paraffin wax, or any combination thereof.

In certain embodiments, the release coating 108 comprises a curing agent, such as a catalyst, that activates curing of the curable pressure sensitive adhesive composition. For example, the assistant enables crosslinking of at least one component of the adhesive composition. In particular, the release coating 108 may comprise a formulation, such as 0.01 wt% to 5.0 wt%, such as 0.1 wt% to 2.5 wt%, 0.5 wt% to 2.0 wt%, or 0.5 wt% to 1.5 wt% have.

The thickness of the release coating 108 is 0.025 millimeters to 10 millimeters, such as 0.025 millimeters to 5.0 millimeters, 0.25 millimeters to 2 millimeters, or 0.25 millimeters to 1 millimeter.

In the particular embodiment shown in Figure 2, the multilayer film 200 comprises a substrate film 202 having one or more layers. For example, the polymer substrate 202 includes a polymer film 204 and an antistatic layer 206. The pressure-sensitive adhesive layer 208 is applied to the polymer film 204 and the release coating 210 is applied to the pressure-sensitive adhesive layer 208. Optionally, a liner film 212 may be applied on the release coating 210. Alternatively, the release coating 210 can be applied to the liner film 212 and the combined layers 210 and 212 are in contact with the adhesive layer 208 at the release coating surface 210.

The polymer layer 204 is formed of the polymer described above with reference to the base film 102. The antistatic coating 206 comprises a dissipative polymer, such as a polyether block amide, an ionomer, a polyimide, a polyamide, or any combination thereof.

In yet another embodiment, the antistatic coating 206 comprises a filler polymer. The polymer includes acrylates, polyolefins, polyurethanes, polyesters, polyethers, polyamides, polyimides, polyaryl ether ketones, or any combination thereof. Exemplary fillers include conductive fillers such as metal particles, conductive ceramic particles, carbon black, conductive fibers, carbon nanotubes, graphene, or any combination thereof. In a further embodiment, the antistatic coating comprises a laminated metal layer, such as a sputtering or vapor deposition layer.

In particular, the surface resistivity of the antistatic coating 206 is 10 5 to 10 12 ohm / sq. For example, the surface resistivity of the antistatic coating is 10 8 to 10 12 ohm / sq, such as 10 9 to 10 12 ohm / sq.

The pressure-sensitive adhesive layer 208 and the release coating 210 are formed of the above materials. In particular, the release coating 210 comprises a builder, such as a catalyst, that activates at least one component of the pressure-sensitive adhesive layer 208.

Optionally, a liner film 212 is applied over the release coating 210. In an embodiment, the liner film 212 comprises a film or paper that adheres to the release coating. Exemplary polymeric films include polyolefins, acetates, acrylics, polyaryl ether ketones, polyesters, polyethers, polyamides, polyimides, thermoplastic elastomers, styrene polymers, liquid crystal polymers, fluoropolymers, or any combination thereof. In an embodiment, the release liner 212 comprises a cellulose acetate film. In yet another embodiment, the liner film 212 comprises a polyolefin film. In a further embodiment, the liner film 212 comprises a polyester film. In an embodiment, the liner film 212 is treated, for example, by corona discharge, plasma discharge, ion treatment or the like so as to improve the adhesion to the release coating. The thickness of the liner film 212 is 0.5 to 5 mils, such as 0.5 to 3 mils, or 1 to 3 mils.

In another exemplary embodiment shown in FIG. 3, the multilayer film 300 comprises a substrate film 302. In an embodiment, the substrate film 302 comprises a polymer film 304 and an antistatic layer 306. In the exemplary multilayer film 300, the adhesive 308 is disposed on the first major surface 312 of the base film 302 and the release coating 310 is disposed on the major surface 314 opposite the base film 302. When the multilayer film is dried in roll form for subsequent supply, the release coating 310 contacts the pressure-sensitive adhesive layer 308 to enable curing or crosslinking of the pressure-sensitive adhesive layer 308.

Although the antistatic layer 306 on the main surface of the base film 302 in the multilayer polymer substrate is shown in contact with the release coating 310, the antistatic coating and other layers may be rearranged. For example, the multilayer film shown in FIG. 4 includes a polymeric substrate 402 wherein a polymeric layer 404 is in contact with the release coating 410 and an antistatic layer 406 is in contact with the adhesive layer 408. When the film 400 is dried, the release coating 410 comprising the active agent for at least one component of the adhesive composition in the adhesive layer 408 is contacted with the adhesive layer 408, Curing and crosslinking of the composition occurs.

Figure 5 illustrates an exemplary multilayer film manufacturing process. For example, the process 500 includes a roll of the base film 502 to which the base film is fed. The base film 502 comprises at least one polymer film layer. Optionally, the substrate film comprises an antistatic layer. Alternatively, the antistatic layer is fed into the coating at the coating station 504 and cured. An antistatic coating (not shown) is designed to cure at room temperature for actinic radiation having some other curing mechanism with respect to heat. For example, the antistatic coating may be processed in the oven 514.

Further, the adhesive composition is applied to the base film 502 in the coating station 506. A pressure sensitive adhesive composition is selected from the above compositions. Optionally, the adhesive composition may be baked or dried, for example, in an oven 516. Alternatively, the adhesive composition may be treated with actinic radiation.

Also, a release coating is applied to the top of the pressure sensitive adhesive composition at the coating station 508. The release coating comprises an active agent that is active on at least one component of the pressure-sensitive adhesive composition being fed at (506). In an embodiment, the release coating is not thermally treated after lamination. Alternatively, the release coating can be cured by actinic radiation or heat treatment.

Alternatively, the release coating may be applied to the opposite surface of the backing film 502 with respect to the pressure-sensitive adhesive composition applied in (506). When the multilayer film is dried with the roll 510, the release coating applied at 508 is contacted with the opposite side of the multilayer film having the adhesive coating.

Coating stations 504, 506, 508 are shown disposed on top of substrate film 502, but other coating techniques may be applied to apply the coating layer. For example, roll coating, gravure coating, knife coating, dip coating, spray coating, slot die coating, or variations thereof.

Optionally, the system 500 includes a roll 512 for disposing the liner film on top of the release coating supplied at 508. [ The multilayer film is wound with a roll 510 and stored for later use. Variations of these processes are possible. For example, as noted above, the release coating station 508 feeds the release coating to the liner film leaving the roll 512 and the lamination station bonds the support to the substrate film / release coated sub-structure.

After forming, the peel strength of the multilayered film is 1000 g / in or less, for example, the peel strength is 2 g / in to 500 g / in, 3 g / in to 200 g / in, or 4 g / in to 100 g / in . The peel strength is measured on a stainless steel plate at an angle of 180 ° and a peel rate of 12 in / min.

Further, the curing performance is measured by a cure index defined as a ratio obtained by dividing the peel strength of 18 hours by the peel strength of 7 days. Particularly, the curing index of the multilayered film is 2 or less, for example, 1.5 or less or 1.2 or less.

Example

Acrylic adhesive, an isocyanate crosslinking agent, and a dibutyltin dilaurate catalyst. The mix was poured into 2 mil thick polyethylene terephthalate (PET) sheets and dried in an oven at 135 DEG C for 1.5 minutes. The final thickness of the adhesive is 0.55 to 0.6 mils. Covering a sheet of sheets with a tin-containing silicone-modified application liner; Another set was covered with a silicone-modified release liner of tin catalyst material. Samples were aged at room temperature for 18 hours, 3 days, or 7 days. After a certain time aging, the release-applied liner was removed and the PSA was laminated to the PET substrate with a 4.5 lb wrap roller. After a 20 minute delay, the PSA peel force was tested and recorded. The peel test parameters are 180 o and 12 in / min.

As shown in Table 1 below, after 18 hours, the sample peel strength of the tin-containing silicone-modified application liners reached full cure, but the sample peel strength of the tin-free silicone-modified application liners was still high. After 3 days of aging, the PSA of the tin-free silicone-modified application liners was close to full cure.

Table 1. Peeling force of samples

Dispersion Liner Aging Peel strength (g / in) Presence of tin catalyst

18 hours 23.6 3 days 22.1 7 days 18.4 Tin catalyst member

18 hours 106.5 3 days 33.2 7 days 30.6

In particular, it has been found that curing time is reduced by adding a catalyst to the release layer. The catalyst can be added to the pressure sensitive adhesive composition to accelerate the cure time, but with increasing catalyst content in the pressure sensitive adhesive composition, the time available is shortened and high viscosity is generated during the application process. Without the contribution of the present invention, a low catalyst in the pressure-sensitive adhesive composition would result in long cure times and potentially poor cure. Since the catalyst is present in the release coating, the catalyst content of the pressure sensitive adhesive composition can be reduced or eliminated, providing a longer service time in the manufacturing process and providing a shorter curing time after application.

It is to be understood that not all of the acts described above in the broad description or embodiments are required, that some of the specific acts may not be required, and that one or more other acts may be practiced in addition to those described. In addition, the order in which the actions are listed does not have to be the order in which they are executed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, those of ordinary skill in the art will recognize that various modifications and variations are possible without departing from the scope of the present invention as set forth in the following claims. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having" Any other variation of these is intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of features need not necessarily be limited to such features, It should be understood that the phrase "or" is used in an inclusive sense to refer to a "or" in an inclusive sense, For example, condition A or B is satisfied by any of the following: A is true (or exists), B is false (or does not exist), and A False (or nonexistent) B is True (or present), and both A and B are true (or present).

Also, "a" or "an" is used to describe the elements and components described herein. This is done merely for convenience and to give the general meaning of the scope of the present invention. This description should be read to include one or at least one, and the singular also includes the plural unless it is expressly meant to mean differently.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, it is to be understood that advantages (s), advantages, solutions to problems, and any feature (s) that may cause or may cause any benefit, advantage, , Nor should it be interpreted as a required or essential feature.

After reading the specification, skilled artisans will appreciate that any feature described herein in connection with each of the embodiments for clarity may also be provided in combination in a single embodiment. Conversely, various features described in connection with a single embodiment for brevity may also be provided separately or in any subcombination. Also, reference to values described in ranges includes each value and all values within this range.

Claims (31)

A multilayer film comprising:
A base film having first and second major surfaces;
A pressure-sensitive adhesive layer disposed on the first main surface of the base film and comprising a curable composition; And
And a releasing layer disposed on the pressure-sensitive adhesive layer on the opposite side of the base film and including a releasing material and a catalyst for curing the curing composition. The multilayer film of claim 1, wherein the releasing material is a silicone-based, fluorine-based, long chain alkyl-based, fatty acid amide-based, silica powder material, or any combination thereof. The multilayer film of claim 1, wherein the curable composition comprises a polymer comprising a natural rubber, a styrene block copolymer, an acrylate, a polyurethane, a silicone, a polydiorganosiloxane polyurea copolymer, or any combination thereof. The multilayer film of claim 1, wherein the curable composition comprises a crosslinking agent. The multilayer film of claim 1, wherein the catalyst is an organometallic catalyst, an amine catalyst, or a combination thereof. The multilayer film of claim 1, wherein the substrate film comprises a polymer film. The method of claim 6, wherein the polymeric film is selected from the group consisting of polyolefins, acetate polymers, acrylic polymers, polyaryl ether ketones, polyesters, polyethers, polycarbonates, polyvinyl chloride, polyamides, polyimides, thermoplastic elastomers, Polymer, or any combination thereof. The multilayer film according to claim 1, wherein the base film comprises an antistatic layer. 9. The multilayer film of claim 8, wherein the antistatic layer comprises a dissipative polymer. 9. The multilayer film of claim 8, wherein the antistatic layer comprises a conductive filler. The multilayer film according to claim 8, wherein the antistatic layer has a surface resistivity of 10 5 to 10 12 ohm / sq. The multi-layer film of claim 1, further comprising a liner film disposed on the release layer opposite the pressure-sensitive adhesive layer. The method of claim 12, wherein the liner film is selected from the group consisting of polyolefins, acetates, acrylics, polyaryl ether ketones, polyesters, polyethers, polycarbonates, polyvinyl chloride, polyamides, polyimides, thermoplastic elastomers, styrene polymers, Fluoropolymer, or any combination thereof. 13. The multilayer film of claim 12, wherein the liner film comprises paper. The multilayer film according to claim 1, wherein the peel strength of the curable composition is 1000 g / in or less. 16. The multilayer film of claim 15, wherein the peel strength is from 2 g / in to 500 g / in. 17. The multilayer film of claim 16, wherein the peel strength is from 3 g / in to 200 g / in. 18. The multilayer film of claim 17, wherein the peel strength is from 4 g / in to 100 g / in. The multi-layer film according to claim 1, wherein the curing index of the multi-layer film is 2 or less. The multi-layer film of claim 1, wherein the curing index is 1.5 or less. The multilayer film according to claim 1, wherein the curing index is 1.2 or less. A multilayer film comprising:
A base film having first and second major surfaces;
A pressure-sensitive adhesive layer disposed on a first main surface of the base film, the pressure-sensitive adhesive layer comprising a curable composition having a polymer and a crosslinking agent;
A release layer disposed on the substrate opposite pressure sensitive adhesive layer, the release layer comprising a catalyst for curing the release material and the curable composition; And
And a liner film on the release film. 23. The multilayer film of claim 22, wherein the release material is a silicone-based, fluorine-based, long chain alkyl-based, fatty acid amide-based, silica powder material, or any combination thereof. 23. The multilayer film of claim 22, wherein the polymer comprises a natural rubber, a styrene block copolymer, an acrylate, a polyurethane, a silicone, a polydiorganosiloxane polyurea copolymer, or any combination thereof. 23. The multilayer film of claim 22, wherein the catalyst is an organometallic catalyst, an amine catalyst, or a combination thereof. The composition of claim 22, wherein the liner film is selected from the group consisting of polyolefins, acetates, acrylics, polyaryl ether ketones, polyesters, polycarbonates, polyvinyl chloride, polyethers, polyamides, polyimides, thermoplastic elastomers, Fluoropolymer, or any combination thereof. 23. The multilayer film of claim 22, wherein the peel strength of the curable composition is 1000 g / in or less. 23. The multi-layer film of claim 22, wherein the curing index of the multi-layer film is no greater than 2. A method of making a multilayer film, the method comprising:
A substrate supplying step having first and second main surfaces;
Applying a curable pressure-sensitive adhesive composition to a first main surface of the substrate; And
And applying a release coating comprising a release material and a curable composition curing catalyst to contact the curable pressure sensitive adhesive composition. 30. The method of claim 29, further comprising supplying a liner film to the release coating. The method of claim 29, wherein applying the release coating comprises applying the release coating to a second major side of the substrate opposite the curable pressure-sensitive adhesive composition, and rolling the multi-layer film to contact the release coating with the curable pressure sensitive adhesive composition / RTI >
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CN104936776A (en) 2015-09-23
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