WO2009002110A2 - Pressure sensitive adhesive composition with improved peeling characteristics and protection films using the same - Google Patents
Pressure sensitive adhesive composition with improved peeling characteristics and protection films using the same Download PDFInfo
- Publication number
- WO2009002110A2 WO2009002110A2 PCT/KR2008/003693 KR2008003693W WO2009002110A2 WO 2009002110 A2 WO2009002110 A2 WO 2009002110A2 KR 2008003693 W KR2008003693 W KR 2008003693W WO 2009002110 A2 WO2009002110 A2 WO 2009002110A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- protective film
- pressure
- sensitive adhesive
- adhesive composition
- meth
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 58
- 230000001681 protective effect Effects 0.000 claims abstract description 104
- 239000000853 adhesive Substances 0.000 claims abstract description 64
- 230000001070 adhesive effect Effects 0.000 claims abstract description 64
- 239000012948 isocyanate Substances 0.000 claims abstract description 35
- -1 isocyanate compound Chemical class 0.000 claims abstract description 33
- 239000012790 adhesive layer Substances 0.000 claims abstract description 28
- 238000006748 scratching Methods 0.000 claims abstract description 16
- 230000002393 scratching effect Effects 0.000 claims abstract description 16
- 238000003825 pressing Methods 0.000 claims abstract description 15
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000002216 antistatic agent Substances 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- DKJBREHOVWISMR-UHFFFAOYSA-N 1-chloro-2,3-diisocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1N=C=O DKJBREHOVWISMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims 2
- 239000004417 polycarbonate Substances 0.000 claims 2
- 229920000515 polycarbonate Polymers 0.000 claims 2
- 229920000098 polyolefin Polymers 0.000 claims 2
- 229920002223 polystyrene Polymers 0.000 claims 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 1
- 239000004695 Polyether sulfone Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- 229920002492 poly(sulfone) Polymers 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 239000004926 polymethyl methacrylate Substances 0.000 claims 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 41
- 238000000576 coating method Methods 0.000 description 25
- 229920006267 polyester film Polymers 0.000 description 25
- 150000002513 isocyanates Chemical class 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 14
- 230000003247 decreasing effect Effects 0.000 description 14
- 238000012546 transfer Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000012258 stirred mixture Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 210000002307 prostate Anatomy 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
Definitions
- the present invention relates to a pressure-sensitive adhesive composition for pressure-sensitive adhesive tapes or protective films (hereinafter, referred to as "a protective film”), which has improved peeling performance, and, more particularly, to a pressure-sensitive adhesive for protective films, which can improve a phenomenon (hereinafter, referred to as "an adhesive transfer phenomenon from local pressing or scratching") in which a part of an adhesive layer of a protective film remains on the surface of an adherend or is transferred to the surface of the adherend when a strong force is locally applied to the surface of the protective film attached to the surface of an electronic part or an electronic product, for example, the protective film is scratched by the corners or edges of a workbench.
- a protective film which has improved peeling performance
- a pressure-sensitive adhesive for protective films which can improve a phenomenon (hereinafter, referred to as "an adhesive transfer phenomenon from local pressing or scratching") in which a part of an adhesive layer of a protective film remains on the surface of an adherend or is transferred to the surface of the adherend when
- FPDs flat panel displays
- polarizing films such as polarizing films, mobile phone screens, and the like
- workbench in a state in which a protective film is attached to them in order to protect their surfaces.
- a pressure-sensitive film or a protective film is a film having an adhesive layer, which is formed by applying a mixture in which an acrylic or methacrylic copolymer adhesive having curable functional groups is mixed with an initiator or a curing agent at a predetermined mixing ratio on one side or both sides of a base film made of polyester, such as polyethyleneterephthalate (PET), polyethylene (PE), polypropylene (PP), ethylenevinyl acetate (EVA), or the like, and then heating the base film coated with the mixture or irradiating the base film coated with the mixture with ultraviolet rays.
- PET polyethyleneterephthalate
- PE polyethylene
- PP polypropylene
- EVA ethylenevinyl acetate
- various functions can be imparted to the respective surfaces of the protective film.
- a typical example of the protective film includes an antistatic film imparted with an antistatic property.
- a layer facing an adherend is an adhesive layer.
- This adhesive layer is a very important factor for determining the peeling force between the adhesive layer and the adherend or determining the adhesive transfer phenomenon from local pressing or scratching.
- This phenomenon usually occurs during a process of handling a polarizing film for liquid crystal displays (LCDs). Further, the polarizing film, the surface of which is composed of triacetyl cellulose or is functionally coated with triacetyl cellulose, may be locally scratched. In this process of handling a polarizing film for liquid crystal displays (LCDs), it is most important to completely remove the adhesive adhered to the surface of the polarizing film before conducting subsequent procedures. Therefore, this work incurs the result that working time is increased and the surface of the polarizing film is damaged. Recently, in a process of removing a protective film from LCDs, a sash frame is applied, and then the protective film is removed. In this case, the protective film is pressed by the edges of the sash made of Steel Use Stainless (SUS), so that adhesive residues are left between the protective film and the sash, with the result that it is difficult to suitably conduct subsequent procedures.
- SUS Steel Use Stainless
- an object of the present invention is to provide a pressure-sensitive adhesive composition for a protective film, by which, in a protective film to be used for protecting the surface of optical products, the protective film being used for flat panel displays (FPDs), an adhesive layer of the protective film does not remain on the surface of an adherend at the time of removing the protective film even when the protective film has been locally pressed or scratched by an external force during treatment or transportation, that is, an adhesive transfer phenomenon from local pressing or scratching is remarkably improved, thereby improving the peeling performance of the protective film.
- FPDs flat panel displays
- Another object of the present invention is to provide a protective film manufactured using the pressure-sensitive adhesive composition, in which an adhesive transfer phenomenon from local pressing or scratching is remarkably improved.
- the present invention provides a pressure- sensitive adhesive composition for a protective film, which prevents a phenomenon in which an adhesive is transferred to an adherend from local pressing or scratching, thus improving the peeling performance of the protective film, including a curing agent having a monofunctional group or a difunctional group.
- the pressure-sensitive adhesive composition according to the present invention may include an acrylic copolymer or a methacrylic copolymer as an adhesive and an isocyanate compound as a curing agent.
- a protective film having improved peeling performance can be manufactured using the pressure-sensitive adhesive composition according to the present invention.
- an adhesive layer is formed on the surface of a base film to have a predetermined thickness.
- the desired peeling force of an adhesive layer can be attained by suitably controlling the kind of an adhesive, the content ratio of the adhesive to a reaction initiator, and reaction conditions, such as temperature, pressure, reaction time, etc.
- a functional protective film can also be manufactured by imparting additional functions, such as antistatic properties, etc., thereto.
- the present inventors discovered a very important fact concerning adhesive transfer phenomenon from local pressing or scratching while researching into methods of improving the adhesive transfer phenomenon from local pressing or scratching.
- the adhesive layer for a protective film is formed by mixing an acrylic copolymer or methacrylic copolymer having a hydroxyl group, an amino group or a carboxyl group, this copolymer being a major component of an adhesive, with a reaction initiator or curing agent, such as a metal chelate compound, an isocyanate compound, a melamine compound or an epoxy compound, in a predetermined mixing ratio, applying the resulting mixture onto the surface of a base film, and then drying the base film coated with the mixture by passing it through a drying furnace of a coating machine, which also induces a reaction. After the coating and drying, the coated and dried base film may be additionally cured at a temperature ranging from room temperature to 6O 0 C for 1 day ⁇ 1 week.
- a reaction initiator or curing agent such as a metal chelate compound, an isocyanate compound, a melamine compound or an epoxy compound
- the adhesivity of an adhesive is determined depending on the content ratio of an acrylic/methacrylic copolymer to a reaction initiator.
- the adhesivity of the adhesive is decreased as the amount of the reaction initiator is increased.
- the amount of the reaction initiator may be suitably adjusted in order to obtain an adhesive having desired adhesivity.
- the trifunctional cross-linking agent enables the adhesive to have a gel fraction of 92% through a sufficiently complete cross-linking reaction and enables the adhesive to exhibit a peeling force of 40 gf/inch at a rate of 2000 mm/min, as the adhesivity of the adhesive is sufficiently decreased compared to the initial adhesivity thereof.
- the adhesive becomes hard due to the rapid reaction of the trifunctional curing agent, but becomes poor in toughness.
- the adhesive prepared using a monofunctional or difunctional curing agent can prevent an adhesive transfer phenomenon caused by scratching.
- the reason for this is determined to be because the multifunctional curing agent causes a rapid curing reaction, and thus the hardness of an adhesive layer is increased, but the toughness of the adhesive layer is decreased. Now, when the monofunctional or difunctional curing agent is used as a curing agent, the rapid curing reaction is prevented, with the result that the toughness of the adhesive layer is increased, thereby preventing extraneous matter from being locally deposited on the adhesive layer.
- the amount of a monofunctional isocyanate curing agent used is three times the amount of trifunctional isocyanate curing agent used, and other curing conditions are maintained constant. That is, as described above, when a multifunctional curing agent is used in the preparation of an adhesive composition, the gel fraction of the prepared adhesive is increased, and the contamination of an adherend is prevented, but the adhesive has a compact net structure, rather than a compact linear structure.
- (meth)acrylic monomers having an alkyl group of 1 to 14 carbon atoms are used as major components of the pressure-sensitive adhesive composition.
- the alkyl group of 1 to 14 carbon atoms may include methyl, ethyl, n-butyl, s-butyl, t- butyl, iso-butyl, hexyl, 2-ethylhexyl, n-octyl, iso-octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, and the like.
- the (meth) acrylic monomers having an alkyl group of 1 to 14 carbon atoms may be each independently used or may be used by mixing two or more monomers.
- (meth)acrylic monomers having a hydroxy group which are copolymerized with the (meth)acrylic monomers having an alkyl group of 1 to 14 carbon atoms, are also used as major components of the pressure-sensitive adhesive composition.
- the hydroxy group is a functional group acting as an origin of cross-linking, and a (meth)acrylic monomer having the hydroxy group serves to impart cohesion to the pressure-sensitive adhesive by reacting with an isocyanate-based cross-linking agent.
- Examples of the (meth)acrylic monomers having the hydroxy group may include 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate, and the like.
- the (meth)acrylic monomers having the hydroxy group may be independently used or may be used by mixing two or more monomers.
- a pressure-sensitive adhesive composition of the present invention includes a
- the (meth)acrylic copolymer serving as an adhesive; and a monofunctional or difunctional isocyanate compound, serving as a cross-linking agent.
- the (meth)acrylic copolymer may be prepared by copolymerizing 80 ⁇ 99 wt% of (meth)acrylic monomer having an alkyl group of 1 to 14 carbon atoms with 1 - 20 wt% of (meth) acrylic monomer having a hydroxy group.
- the amount of the (meth)acrylic monomer having a hydroxy group is below 1 wt%, there is a problem in that the pressure-sensitive adhesive is not sufficiently cross-linked, so that the cohesion of the pressure-sensitive adhesive is decreased, thereby the pressure-sensitive adhesive may remain on an adherend, and when the amount thereof is above 20 wt%, there is a problem in that the cohesion of the pressure-sensitive adhesive is excessively decreased, so that the pressure-sensitive adhesive becomes hard, thereby deteriorating workability.
- polymerizable monomers in order to control the adhesion, peeling performance, cohesion, heat resistance and other physical properties of the pressure- sensitive adhesive, other polymerizable monomers may be used.
- examples of such polymerizable monomers may include carboxyl group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, aromatic vinyl monomers, alkylene oxide-containing monomers, and the like.
- the amounts of the polymerizable monomers are not limited as long as the effects of the present invention do not become deteriorated.
- (meth)acrylic monomer having an alkyl group of 1 to 14 carbon atoms with the (meth)acrylic monomer having a hydroxy group have a weight-average molecular weight of 300,000 ⁇ 3,000, 000.
- the weight- average molecular weight of the (meth)acrylic copolymer is below 300,000, there is a problem in that the cohesion of the pressure-sensitive adhesive is overly decreased, and thus pressure-sensitive adhesive remains on an adherend even when a weak force is applied thereto.
- the weight- average molecular weight thereof is above 3,000, 000, there is a problem in that the fluidity of the pressure-sensitive adhesive is decreased, thus deteriorating workability.
- a cross- linking reaction is performed using a monofunctional or difunctional isocyanate-based cross-linking agent.
- the monofunctional or difunctional isocyanate-based cross-linking agent is referred to as a compound having two or less isocyanate groups in a single molecule, and its structure is not particularly limited.
- Examples of the monofunctional or difunctional isocyanate-based cross-linking agent may include tolylene di- isocyanate, xylene diisocyanate, chlorophenylene diisocyanate, hexamethylene di- isocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrated diphenylmethane diisocyanate, and commonly-known isocyanate compounds.
- tri or more functional isocyanate-based curing agents be used. These curing agents may be each independently used or may be used by mixing two or more kinds of curing agents.
- the amount of the isocyanate- based curing agent may be 0.1 ⁇ 20 parts by weight based on 100 parts by weight of the (meth)acrylic copolymer. When the amount of the isocyanate-based curing agent is below 0.1 parts by weight, a curing reaction has a low completion rate, so that the adhesion of the pressure-sensitive adhesive is decreased, and an adherend may be contaminated.
- the amount of the isocyanate-based curing agent be 0.1 ⁇ 20 parts by weight based on the total amount of the (me th) acrylic copolymer.
- the pressure-sensitive adhesive composition prepared as above is dried, and is then additionally cured at from room temperature to 6O 0 C for 1 day ⁇ 1 week to exhibit a gel fraction of 85 ⁇ 99%.
- the gel fraction is below 85%, the cohesion and toughness of the pressure-sensitive adhesive is decreased.
- the gel fraction is above 99%, even though a pressure-sensitive adhesive having a high cohesion can be prepared using a monofunctional or difunctional curing agent, the cohesion of the pressure-sensitive adhesive is excessively increased, so that the hardness thereof is also excessively increased, with the result that the pressure- sensitive adhesive may be cracked when a force is locally applied thereto.
- the pressure-sensitive adhesive composition of the present invention can be applied to a base film of optical or general protective films.
- the base film may be made of polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), heat-treated polyethyleneterephthalate (PET), polyethylene (PE), polypropylene (PP), ethylene vinyl acetate copolymer (EVA), polyimide, or the like.
- PET polyethyleneterephthalate
- PEN polyethylenenaphthalate
- PET heat-treated polyethyleneterephthalate
- PET polyethylene
- PE polypropylene
- EVA ethylene vinyl acetate copolymer
- polyimide polyimide
- the pressure-sensitive adhesive composition of the present invention may be used for functional protective films in which layers other than an adhesive layer are imparted with functionality.
- the pressure-sensitive adhesive composition may be used for an antistatic protective film, which has been imparted with an antistatic property, before the pressure-sensitive adhesive composition is applied on its surface on which an adhesive layer to be formed, or may be used for protective films, which have been imparted with other properties, such as water repellency, contamination resistance, and the like, on the opposite surface to the surface on which an adhesive layer is to be formed. Since the present invention is a technology for controlling the physical properties of an adhesive layer, it may be used regardless of the functionality imparted to layers other than the adhesive layer.
- an antistatic agent containing a conductive polymer as an active component may be included in an intermediate layer located between the base film and the adhesive layer, and poly(3,4-ethylenedioxythiophene) may be used as the conductive polymer.
- the adhesive layer formed from the pressure-sensitive adhesive composition of the present invention can be imparted with various functions.
- ionic liquids including lithium ionic liquid, and/or alkaline metal salts including a quaternary ammonium metal salt may be mixed with the pressure-sensitive adhesive composition as an antistatic agent.
- the antistatic agent must be used in a suitable amount because the curing ability and cohesion of the pressure-sensitive adhesive are subject to being decreased, so that the pressure-sensitive adhesive is pressed or scratched by a local impact and is thus detached from an adherend. Further, it is preferred that the antistatic agent be used after its characteristics are evaluated.
- the protective film manufactured using the pressure-sensitive adhesive composition of the present invention is advantageous in that an adhesive layer of the protective film does not remain on the surface of an adherend at the time of removing the protective film from the adherend even when the protective film is locally pressed or scratched by an external force, and in that an adhesive transfer phenomenon from local pressing or scratching is remarkably improved at the time of removing the protective film, thus greatly decreasing the process loss. Further, the pressure-sensitive adhesive composition of the present invention can be applied to protective films having various functions, such as antistatic properties, and the like. Mode for the Invention
- the present invention provides a novel peeling performance test method.
- a protective film having a predetermined width and length is attached to the surface of an adherend using a rubber roller, and then this protective film is detached from the adherend, and simultaneously the force necessary for peeling the protective film from the surface of the adherend is measured.
- a protective film having a width of 25 mm or 1 inch is chiefly used, and as a result, the unit of adhesion is represented by g /25mm or g /inch.
- a tool for locally applying a force to the test piece was fabricated.
- the tool is a metal pin having a shape similar to that of the tip of a ball point pen which is a kind of pencil and has a curvature radius of 300 ⁇ m.
- an apparatus for applying a constant force to the test piece using the tool was fabricated. When this apparatus is used, the time taken to apply the force to the test piece and the intensity of the force can be controlled.
- a method of simulating situations in which a force is locally applied to the test piece using this apparatus is performed as follows. First, a test piece (a protective film) is unif oraily attached to the surface of an adherend by applying a uniform force to the entire test piece using a rubber roller. Subsequently, the adherend to which the test piece is attached is placed in the above apparatus, and then desired load is applied to the adherend for a predetermined time (in the present invention, 10 seconds), thereby locally applying a force to the surface of the adherend. This procedure simulates a circumstance in which a force is locally applied to a product to which the protective film has been attached. Subsequently, the test piece is taken out of the apparatus and is then peeled from the adherend. Finally, whether or not the adhesive materials of the protective film remain on the surface of the adherend is determined.
- a test piece a protective film
- a metal pin with a sharp point such as the tip of the ball point pen, is used in order to simulate a circumstance in which the test piece is sharply pressed.
- various types of pressed marks such as longitudinal pressed marks, circular pressed marks, and the like, can be simulated by changing the shape of the tool or varying the curvature radius of the portion of the tool contacting the test piece.
- the time taken to press the test piece and the force used to test the test piece may alter depending on various factors, such as experimental conditions, kinds of materials used, and the like.
- a tool made of polymer or ceramic may be used.
- a voltage of 1000 V was applied to a protective film using a CPM 288, manufactured by Monroe Electronics Corp., and then the time taken to be attenuated to a voltage of 100 V was measured through an FTMS 101C method.
- the above adhesive and curing agent were mixed with each other in a predetermined mixing ratio to form a mixture, stirred, and then applied on a base film. Subsequently, the base film coated with the mixture was dried at 8O 0 C for 2 minutes to a coating thickness of 10 ⁇ 20 ⁇ m, and then the dried base film coated with the above mixture was aged at a temperature of 25 0 C and a relative humidity of 50% for 7 days.
- Example 7 was conducted using the same method as in Example 3, except that the mixture has a coating thickness of 20 ⁇ m.
- the physical properties of the polyester film coated with the mixture are shown in Table 1. [102] [103] Table 1
- An antistatic agent was prepared by mixing 4 g of LiN(CF SO ) with 6 g of polyethyleneglycol dilaurate at a temperature of 7O 0 C for 6 hours.
- 0.1 g of the prepared antistatic agent was mixed with 20 g of SK1499M, manufactured by Soken Corp., as an acrylate adhesive, and 0.16 g of monofunctional isocyanate, as a curing agent, to form a mixture, the mixture was stirred, and then the stirred mixture was applied on a polyester film having a thickness of 38 ⁇ m to a coating thickness of 10 ⁇ m using the above coating method.
- the physical properties of the polyester film coated with the mixture are shown in Table 2.
- Example 9 was conducted using the same method as in Example 8, except that 0.5 g of the prepared antistatic agent was added.
- the physical properties of the polyester film coated with the mixture are shown in Table 2.
- Example 10> Before the coating composition of Example 1 was applied on the polyester film, an antistatic composition including a conductive polymer as a main component (refer to Korean Patent Registration No.
- Example 11 was conducted using the same method as in Example 10, except that the coating composition of Example 9 was applied on the polyester film instead of the coating composition of Example 1.
- the physical properties of the polyester film coated with the mixture are shown in Table 2.
- the pressure-sensitive adhesive composition of the present invention is used to manufacture protective films for various displays, such as polarizing films, mobile phone screens, etc., or surface protection products.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Priority Applications (1)
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KR1020107000374A KR101198929B1 (ko) | 2007-06-27 | 2008-06-26 | 박리 성능이 개선된 점착제 조성물 및 이를 이용한 보호 필름 |
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KR20070063995 | 2007-06-27 | ||
KR10-2007-0063995 | 2007-06-27 |
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WO2009002110A2 true WO2009002110A2 (en) | 2008-12-31 |
WO2009002110A3 WO2009002110A3 (en) | 2009-03-19 |
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PCT/KR2008/003693 WO2009002110A2 (en) | 2007-06-27 | 2008-06-26 | Pressure sensitive adhesive composition with improved peeling characteristics and protection films using the same |
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KR (1) | KR101198929B1 (ko) |
TW (1) | TW200920806A (ko) |
WO (1) | WO2009002110A2 (ko) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103937429A (zh) * | 2014-04-04 | 2014-07-23 | 广东达美新材料有限公司 | 一种耐高温不黄变高剥离力压敏胶及其制备方法 |
KR20140095922A (ko) * | 2013-01-25 | 2014-08-04 | 도레이첨단소재 주식회사 | 유전 점착필름 및 전자종이용 디스플레이 소자 |
JP2018104514A (ja) * | 2016-12-26 | 2018-07-05 | 日本合成化学工業株式会社 | 粘着剤組成物、およびそれを用いてなる粘着剤、粘着シート、並びに粘着剤層付偏光板 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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KR102494761B1 (ko) * | 2017-12-20 | 2023-02-02 | 주식회사 케이씨씨글라스 | 다층 시트 및 이의 제조방법 |
JP6497476B1 (ja) * | 2018-09-20 | 2019-04-10 | 東洋インキScホールディングス株式会社 | 粘着剤および粘着シート |
KR102214896B1 (ko) * | 2019-10-08 | 2021-02-15 | 주식회사 라온티알엠 | 재박리형 건축용 윈도우 필름용 점착제 조성물 및 이를 포함하는 재박리형 건축용 윈도우 필름 |
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KR101989869B1 (ko) | 2013-01-25 | 2019-06-17 | 도레이첨단소재 주식회사 | 유전 점착필름 및 전자종이용 디스플레이 소자 |
CN103937429A (zh) * | 2014-04-04 | 2014-07-23 | 广东达美新材料有限公司 | 一种耐高温不黄变高剥离力压敏胶及其制备方法 |
JP2018104514A (ja) * | 2016-12-26 | 2018-07-05 | 日本合成化学工業株式会社 | 粘着剤組成物、およびそれを用いてなる粘着剤、粘着シート、並びに粘着剤層付偏光板 |
Also Published As
Publication number | Publication date |
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KR101198929B1 (ko) | 2012-11-07 |
TW200920806A (en) | 2009-05-16 |
WO2009002110A3 (en) | 2009-03-19 |
KR20100032885A (ko) | 2010-03-26 |
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