CN101970593A - Adhesive composition, surface protective film, and mother glass surface protective film for flat panel display - Google Patents
Adhesive composition, surface protective film, and mother glass surface protective film for flat panel display Download PDFInfo
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- CN101970593A CN101970593A CN2009801087175A CN200980108717A CN101970593A CN 101970593 A CN101970593 A CN 101970593A CN 2009801087175 A CN2009801087175 A CN 2009801087175A CN 200980108717 A CN200980108717 A CN 200980108717A CN 101970593 A CN101970593 A CN 101970593A
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- surface protective
- protective film
- surface protection
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/005—Dendritic macromolecules
-
- 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
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
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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
- 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
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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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Liquid Crystal (AREA)
Abstract
Disclosed is an adhesive composition with which a surface protective film can be easily bonded to a glass surface. By using the adhesive composition, residues resulting from the surface protective film (specifically, from an adhesive layer thereof) can be easily cleaned/removed after removal of the surface protective film. An adhesive layer and a mother glass surface protective film for flat display panels, which uses the adhesive composition or the adhesive layer, are also disclosed. The adhesive composition is characterized by containing 0.01-2 parts by weight of an alkylene oxide group-containing compound per 100 parts by weight of a thermoplastic resin.
Description
Technical field
The present invention relates to a kind of binder composition, in more detail, relate to the binder layer that uses these binder compositions and use the flat-panel monitor basic pattern glass surface protective film of these binder compositions.
Background technology
In the manufacturing of flat-panel monitors such as liquid-crystal display, plasma display, OLED display, all use glass substrate.The sheet glass of factory's manufacturing circulates (carrying) with the form of basic pattern glass, and then is processed to glass substrate.When basic pattern glass is carried, is taken care of at client place etc. in conveyance or keeping even along with delivery; in case being scratched, glass surface will cause product percent of pass to reduce, give the quality aspect to bring detrimentally affect, therefore usually at glass surface wall-attached surface protective membrane.
The flat-panel monitor that has attached surface protection film meets at panel manufacturers with basic pattern glass; to carry out the operation of stripper surface protective membrane at the panel manufacturers place; under the situation of peeling off weight (being difficult to peel off), operability worsens, and produces to peel off not exclusively and peel off bad problem.
In addition, peel off back the grade and clean the residue of removing surface protection film, also can produce the very difficult problem that falls down from glass surface of residue thing with scavenging solution.
And, because the residue that brings of surface protection film can make problems such as occurring the quality reduction in the manufacturing process of TFT substrate, therefore to the cleaning of residue thing in the matting with remove higher requirement.
In this case, proposed the scheme of following surface protection film in the patent documentation 1: the surface of the substrate layer that forms at polyethylene, stacked to contain the above density of 50 weight % be 0.91～0.93g/cm
3New LDPE (film grade), center line average roughness Ra be the surface protection film of the following binder layer of 0.05 μ m.
But, after the surface protection film of patent documentation 1 record attaches to glass, can produce be difficult to peel off, the problem of operability difference, or adhere to the problem that (transfer printing) is difficult to wash at the residue thing of glass surface.
The duplicature that a kind of one side at the substrate layer that is formed by thermoplastic resin is formed with the binder layer that comprises ethylene vinyl acetate copolymer is disclosed in the patent documentation 2; And disclose in the patent documentation 3 one side at substrate layer by the acrylic acid series that comprises butyl acrylate and acrylic acid multipolymer bonding and utilize as the aromatic isocyanate of linking agent crosslinked the surface protection self adhesive tape that constitutes of binder layer.
But above-mentioned duplicature and adhesive tape also can produce same problem.
The prior art document
Patent documentation 1: No. 3103190 communique of Japanese Patent
Patent documentation 2: No. 2980434 communique of Japanese Patent
Patent documentation 3: Japanese kokai publication hei 7-143643 communique
Summary of the invention
The objective of the invention is to; in order to solve the problems referred to above that exist in the present surface protection film (thin slice); provide a kind of easily the subsides to pay protective membrane at glass surface; then after peeling off surface protection film, the flat-panel monitor basic pattern glass surface protective film that the residue that is caused by surface protection film (binder layer wherein) can easily clean binder composition, the binder layer of removing and use them.
The inventor etc. further investigate in order to achieve the above object, and binder composition, binder layer shown in below having found that and the flat-panel monitor basic pattern glass surface protective film that uses them have finally been finished the present invention.
That is, a kind of binder composition wherein, with respect to 100 parts by weight of thermoplastic resin, contains the compound that contains alkylene oxide group of 0.01～2 weight part.By when adding thermoplastic resin, adding the compound that contains alkylene oxide group; thereby when using it as the binder layer of surface protection film; though details is not clear; but the attaching to glass surface becomes easy as can be known; the residue that utilization is caused by surface protection film (binder layer wherein), for example the low molecular compound from binder layer carries out double replacement mutually with the compound that contains alkylene oxide group, can realize the minimizing of residue.And, also be useful in the matting after surface protection film is peeled off, can easily clean, remove residue.
In addition, binder composition of the present invention, the preferred above-mentioned compound that contains alkylene oxide group is a tensio-active agent.By adding tensio-active agent; when its binder layer as surface protection film is used; though details is not clear; but the attaching to glass surface becomes easy as can be known; and utilize the residue that causes by surface protection film (binder layer wherein), for example the low molecular compound from binder layer carries out double replacement mutually with tensio-active agent, can realize the minimizing of residue.And, also useful in the matting after surface protection film is peeled off, can easily clean, remove residue by adding tensio-active agent.
Surface protection film of the present invention preferably forms with above-mentioned binder composition.Used the surface protection film of binder composition to be processed into film like or laminar, band shape etc. easily, very useful.
Flat-panel monitor of the present invention basic pattern glass surface protective film, the single layer that preferably forms by using above-mentioned binder composition constitutes.The single layer that uses above-mentioned binder composition and form itself has as the function of flat-panel monitor with the basic pattern glass surface protective film, so manufacturing process is few, and operability is better.
Flat-panel monitor of the present invention forms with the one or both sides that the basic pattern glass surface protective film preferably is formed on above-mentioned binder composition base material.Utilize binder composition to be formed at flat-panel monitor basic pattern glass surface protective film on the base material by use, can protect that to be attached thing (glass) surface not contaminated, and prevent the generation of scratch etc., very useful.
Need to prove that so-called among the present invention " flat-panel monitor basic pattern glass " is a kind of sheet glass that can be processed in the preceding state that circulates of being in of various goods, typically refers to the basic pattern glass that uses in the manufacturing of flat-panel monitor.As flat-panel monitor, display unit such as liquid-crystal display, plasma display, OLED display are for example arranged.
Embodiment
Below embodiment of the present invention are described in detail
Binder composition of the present invention is characterised in that, with respect to 100 parts by weight of thermoplastic resin, contains the compound that contains alkylene oxide group of 0.01～2 weight part.
The matrix polymer of the binder composition that uses as the present invention uses thermoplastic resin.
As above-mentioned thermoplastic resin, all can suit to use so long as bring into play fusible thermoplastic resin, can enumerate well-known thermoplastic bonded resins such as the block base polymer of for example polythylene resin, polypropylene-based resin, propylene-ethylene, random base polymer, grafting base polymer, polystyrene resins, acrylic resin.These resins can use separately also and can two or more mixing use.
As above-mentioned polythylene resin, for example have: polyolefin resines such as new LDPE (film grade), straight chain shape new LDPE (film grade), polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, ethylene-propylene copolymer, ethene butene-1 copolymer, ethene 1-hexene copolymer, ethene 4 methyl 1 pentene copolymer, ethene 1-octene copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer etc.
Above-mentioned polystyrene resins for example has: styrene butadiene (SB), styrene isoprene (SI), styrene ethylene-butylene copolymer (SEB), styrene ethylene-propylene copolymer A-B type diblock polymers such as (SEP), styrene butadiene styrene (SBS), styrene isoprene vinylbenzene (SIS), styrene ethylene-butylene copolymer vinylbenzene (SEBS), the multi-block polymer that styrene ethylene-propylene copolymer vinylbenzene A-B-A type three blocks such as (SEPS) or A-B-A-B type four blocks are above, styrene butadiene ribber polystyrene random copolymerss such as (SBR), styrene ethylene-butylene copolymer alkene crystallization A-B-C such as (SEBC) type vinylbenzene alkene crystal system segmented copolymer etc.
As thermoplastic resin, to use under the situation of above-mentioned polyethylene-based resin, preferred density is 0.880～0.950g/cm
3New LDPE (film grade) be resin, more preferably 0.880～0.923g/cm
3, preferred especially 0.880～0.915g/cm
3Above-mentioned low density polyethylene vinyl resin has good flexibility, and practicality.Need to prove density (g/cm of the present invention
3) be value according to ISO 1183 standard tests.
In the binder composition of the present invention, with respect to the above-mentioned thermoplastic resin of 100 weight parts, the content that contains the compound of alkylene oxide group is 0.01～2 weight part, is preferably 0.05～1.5 weight part, more preferably 0.1～1 weight part.When it was lower than 0.01 weight part, the performance of removing residue in the matting reduced; When surpassing 2 weight parts, (situation of extrusion molding) can cause forming defect when making surface protection film.Owing to these reasons, mix in large quantities and exist the low viscous compound that contains alkylene oxide group will cause mobile inhomogeneous with thermoplastic resin, cause forming defect.In addition, even form film, when the scavenging solution that uses is removed residue, must use more scavenging solution in matting, the cost aspect is not preferred yet.
The compound that contains alkylene oxide group as above-mentioned can make spent glycol, propylene glycol, butyleneglycol, the Whitfield's ointment glycol, the propylene glycol mono fatty acid ester, polyoxyethylene polyoxypropylene glycol (polyethylene polyoxypropylene glycol), polyoxyalkylene decyl ethers (polyoxyalkylene decyl ether), polyoxyethylene styryl phenyl ether, Voranol EP 2001, polyoxyethylene lauryl ether, polyoxyethylene wool alcohol ether, polyoxyethylene alkyl amine ether, polyoxyethylene (2) lauric monoethanolamide, polyoxyethylene (5) coconut oil fatty acid monoethanolamide, the polyoxyethylene Sodium Lauryl Sulphate BP/USP, polyoxyethylene sorbitan carboxylic ester, sorbitan carboxylic esters, polyoxyethylenated castor oil, the high Viscotrol C that solidifies of polyoxyethylene, compounds such as Wool wax alcohols,ethoxylated fatty acid ester.Above-claimed cpd can be used as uses such as emulsifying agent, dispersion agent, lubricant, clouding agent, anti-thixotropic agent, tensio-active agent, static inhibitor, special preferred surfactant.
Above-mentioned tensio-active agent, can use so long as contain the compound of alkylene oxide group, be not particularly limited, specifically, as above-mentioned ether compound, preferred polyoxyethylene polyoxypropylene glycol, polyoxyalkylene decyl ethers, polyoxyethylene styryl phenyl ether, Voranol EP 2001, polyoxyethylene lauryl ether, polyoxyethylene wool alcohol ether, polyoxyethylene alkyl amine ether.In addition, as above-mentioned amides, preferred polyoxyethylene (2) lauric monoethanolamide, polyoxyethylene (5) coconut oil fatty acid monoethanolamide, polyoxyethylene Sodium Lauryl Sulphate BP/USP etc.In addition, as the compound of above-mentioned ester class, preferred polyoxyethylene sorbitan carboxylic ester, sorbitan carboxylic esters, polyoxyethylenated castor oil, high Viscotrol C, the Wool wax alcohols,ethoxylated fatty acid ester etc. of solidifying of polyoxyethylene.
In the binder layer that uses in the surface protection film of the present invention; in order to reach the purpose of control adhesion characteristic; can suitably add according to the purposes of using various additives: present known various tenderizers; tackifier; the ethylene series resin that can in substrate layer, use; silicone based polymkeric substance; the liquid methacrylate based copolymer; the phosphoric acid ester based compound; protective agent; hindered amine is a photostabilizer; UV light absorber; surface lubricant; flow agent; softening agent; low-molecular(weight)polymer; antioxidant; sanitas; stopper; silane coupling agent; inorganic and organic filler (for example, calcium oxide; magnesium oxide; silicon-dioxide; zinc oxide; titanium oxide etc.); metal-powder; tinting material; powders such as pigment; granular; foil material; heat-resisting stabilizing agents etc. are known various additives at present.
In addition, by with above-mentioned binder composition heating and melting, can make binder layer.That the binder layer that obtains by fusion heated adhesive composition is easy to be processed into is membranaceous, sheet, band shape etc., very useful.
The formation method of above-mentioned tackiness agent is not particularly limited, and can use known method, for example melted extrusion modeling, rolling process etc.
And, on the surface of binder layer, as required also can embodiment such as Corona discharge Treatment, uviolizing processing, flame treating, Cement Composite Treated by Plasma, sputter etching processing etc., with the control binding property or paste that to pay operability etc. be the surface treatment of purpose.
For binder layer, in during before using, dividing plate also can be installed as required temporarily wait and protect.
In the surface protection film of the present invention, the thickness of binder layer is generally about 1～50 μ m, preferred 2～40 μ m, more preferably 3～20 μ m.During thickness low LCL 1 μ m, be difficult to bring into play binding property; When surpassing 50 μ m, peel off the difficulty that becomes, and the usage quantity of adding the compound that contains alkylene oxide group in the binder layer to increases, unfavorable aspect cost, not preferred.
By using the single layer of above-mentioned binder layer, can make surface protection film, particularly can make dull and stereotyped with indicating meter basic pattern glass surface protective film.Because binder layer itself has the function of surface protection film, thereby manufacturing process is few, practicality.
In addition, above-mentioned binder layer is formed at the single or double of base material, can forms flat-panel monitor basic pattern glass surface protective film.By using the surface protection film that has formed binder layer on the base material, can protect effectively that to be attached thing (glass) surface not contaminated, and the generation that can prevent to scratch etc., very useful.
The base material that uses among the present invention (layer) can form laminar, film like, band shape etc., is not particularly limited, and for example polyolefin-based resins is owing to also have pliability when having thermotolerance and solvent resistance, thereby preferred the use.By making substrate layer have pliability, can be wound in the roller shape, carry out various suitable processing.
The said polyolefins resin for example can be enumerated polyethylene-based resin, propylene or comprise the propylene composition and propylene resin of ethene composition, ethylene vinyl acetate copolymer etc.
Concrete example is if any new LDPE (film grade), straight chain shape new LDPE (film grade), polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, ethylene propylene copolymer, the ethene butene-1 copolymer, ethene 1-hexene copolymer, the ethene 4 methyl 1 pentene copolymer, ethene 1-octene copolymer, ethylene-methyl acrylate copolymer, the ethylene methacrylic acid methyl terpolymer, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, polyolefin resines such as ethylene-vinyl alcohol copolymer etc.
For the present invention, can suitably contain the various additives that normally used crowd knows in the base materials such as this membranaceous or laminar, band shape in the above-mentioned substrate layer.For example, various weighting agents, pigment, uv-absorbing agent, oxidation inhibitor, heat-resisting stabilizing agent, lubricant etc.
The thickness of above-mentioned substrate layer, usually about preferred 20～300 μ m, more preferably about 20～250 μ m, about preferred especially 25～200 μ m, during substrate layer less than 20 μ m, base material can take place to destroy or break when peeling off, when surpassing 300 μ m, it is big that the elasticity of base material becomes, and decortication etc. also easily takes place after subsides are paid.
In addition,, have property of tearing (hand is cut れ) or anti-skid, can implement processing patterns and concavo-convex processing etc. in order to make it for the substrate layer side of surface protection film.
Manufacture method as surface protection film of the present invention; from can high-level efficiency, make surface protection film of the present invention aspect at an easy rate; the starting material fusion heating and coextruded profiled respectively of the binder layer that preferably will constitute the substrate layer that forms by polyolefin-based resins and form by thermoplastic resin; become one at the one or both sides that make binder layer and substrate layer, make the method for the film of bilayer structure (the perhaps multilayer more than 3 layers) with specific thicknesses.
As above-mentioned coextruded profiled, can adopt normally used method in the manufacturings such as film, thin slice, be not particularly limited.For example, can use methods such as blow moulding (inflation), coextrusion T-die head method.Use above-mentioned coextruded profiled, aspect cost and the productivity aspect more satisfactory.
In addition, there is no particular restriction for the stacked stacked number of difference in above-mentioned each layer, and above-mentioned substrate layer and above-mentioned binder layer can be respectively individual layers, also can make multilayered structure as required.
In addition, the integral thickness of surface protection film of the present invention is preferably 20～150 μ m, more preferably 30～100 μ m.If integral thickness less than 20 μ m, operability is relatively poor when then peeling off, and is easy to generate problem such as break; If thickness surpasses 150 μ m, can produce the problem of decortication after then can occurring attaching, also unfavorable aspect cost, preferably do not use.
Embodiment
Below formation of the present invention and effect waited by the illustration specific embodiment illustrate, but the present invention is not limited to these embodiment.In addition, the assessment item among embodiment etc. is measured as described below.
1) peeling force
(the NH technical glass is made with basic pattern glass at crystal liquid substrate; NA35) crimping (0.2Mpa, 1.0m/ minute) behind the last wall-attached surface protective membrane; 23 ℃ of down keepings one day, by the peeling force (N/20mm) of tensile testing machine (manufacturing of NMB company, TCM-5KNB-3, draw speed 0.3m/ minute, angle 180 °) when measuring the stripper surface protective membrane.Need to prove, below the preferred 0.02N/20mm of peeling force, more preferably below the 0.015N/20mm.In addition, as peeling force, from the determination limit value of adaptation on trier, more than the preferred 0.001N/20mm.Under the high situation of peeling force, the strip operation variation, the residue that surface protection film causes increases easily.
2) contact angle
Crimping (0.2Mpa, 1.0m/ minute) after glass (manufacturing of NH technical glass, NA35) is gone up the wall-attached surface protective membrane; under 40 ℃ through after 4 days; measure the contact angle before cleaning; then; with above-mentioned glass surface; the aqueous solution of the inorganic alkaline clean-out system of use 2.0% (manufacturing of Yokohama oil prodution industry, KG) carries out ultrasonic cleaning in 2 minutes, again with the drip washing of distilled water through 3 minutes, measures the contact angle after cleaning.
3) cleaning performance (cleaning rate)
Formula calculated below cleaning performance (cleaning rate) utilized.Need to prove that cleaning performance is preferred more than 65%, more preferably more than 70%.During cleaning performance less than 65%, residue can cause peel off bad, therefore not preferred.
Cleaning performance (cleaning rate) (%)=100 * [(contact angle after the contact angle-cleaning before cleaning)/(contact angle before cleaning)]
4) condition of molding
For each embodiment (except the embodiment 10), comparative example, by the blow moulding moulding.In addition, melt temperature and substrate layer and binder layer, mold temperature and coextrusion temperature all are set at 180 ℃.And, in embodiment 10, by the moulding of T-die head method.Melt temperature, extrusion machine temperature and mold temperature all are made as 190 ℃.
Embodiment 1
Use comprises the substrate layer (thickness is 26 μ m) of new LDPE (film grade) (LDPE) (eastern Cao's corporate system, ペ ト ロ セ Application 183) and with respect to straight chain shape new LDPE (film grade) (LLDPE) (the Sumitomo Chemical manufacturing of 100 weight parts; ア ミ カ セ Application EFV402) contains the binder layer of the polyoxyethylene polyoxypropylene glycol (the first industrial manufacturing company makes, エ パ Application 485) of 0.06 weight part; by having adopted the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μ m) of two-layer structure.
Embodiment 2
The addition of polyoxyethylene polyoxypropylene glycol is set at 0.36 weight part, in addition, utilizes the method identical to make surface protection film (thickness: 30 μ m) with embodiment 1.
Embodiment 3
The addition of polyoxyethylene polyoxypropylene glycol is set at 0.6 weight part, in addition, utilizes the method identical to make surface protection film (thickness: 30 μ m) with embodiment 1.
Embodiment 4
The addition of polyoxyethylene polyoxypropylene glycol is set at 0.9 weight part, in addition, utilizes the method identical to make surface protection film (thickness: 30 μ m) with embodiment 1.
Embodiment 5
Use comprises the substrate layer (thickness is 26 μ m) of new LDPE (film grade) (LDPE) (eastern Cao's corporate system, ペ ト ロ セ Application 183) and (pula nurse (プ ラ イ system) Polymer Company makes with respect to the straight chain shape new LDPE (film grade) of 100 weight parts; エ Port リ ユ-SP1540) contains the binder layer (thickness: 4 μ m) of polyoxyethylene (2) lauric monoethanolamide (river is ground fine chemistry and made ア ミ ゼ Star ト 2L-Y) of 0.06 weight part; by having utilized the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μ m) of two-layer structure.
Embodiment 6
Replace polyoxyethylene (2) lauric monoethanolamide among the embodiment 5; add polyoxyalkylene decyl ethers (the first industrial pharmacy manufacturing of 0.18 weight part; ノ イ ゲ Application XL-400), in addition, utilize the method identical to make surface protection film (thickness: 30 μ m) with embodiment 5.
Embodiment 7
Use comprises new LDPE (film grade) (LDPE) (eastern Cao's corporate system; ペ ト ロ セ Application 183) substrate layer (thickness is 26 μ m); and with respect to the straight chain shape new LDPE (film grade) of 100 weight parts (nurse Polymer Company in pula makes; エ Port リ ユ-SP1540) 50 weight parts and straight chain shape new LDPE (film grade) (LLDPE) (Sumitomo Chemical manufacturing; ス ミ カ セ Application EFV402) total of 50 weight parts and contain polyoxyethylene styryl phenyl ether (the first industrial pharmacy manufacturing of 0.06 weight part; ノ イ ゲ Application EA-177) binder layer (thickness: 4 μ m); by having adopted the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μ m) of two-layer structure.
Embodiment 8
Except that the addition that makes polyoxyethylene styryl phenyl ether is 0.18 weight part, utilize the method identical with embodiment 7, make surface protection film (thickness: 30 μ m).
Embodiment 9
Except that the addition that makes polyoxyethylene styryl phenyl ether is 0.36 weight part, utilize the method identical with embodiment 7, make surface protection film (thickness: 30 μ m).
Embodiment 10
Use is with respect to ethylene-vinyl alcohol copolymer (EVA) (the JPE manufacturing of 100 weight parts; ノ バ テ Star Network LV440) contains polyoxyethylene polyoxypropylene glycol (the first industrial pharmacy manufacturing of 1.2 weight parts; the simple layer of binder layer エ パ Application 485) makes the surface protection film (thickness: 35 μ m) of single structure by T-die head method.
Embodiment 11
Use comprises ethylene-vinyl alcohol copolymer (EVA), and (JPE makes; ノ バ テ Star Network LV440) substrate layer (thickness is 26 μ m) and with respect to the styrene-ethylene butylene-ethylene block copolymer (SEBC) of 100 weight parts (JSR makes; DYNARON4600P) contain polyoxyethylene polyoxypropylene glycol (the first industrial pharmacy manufacturing of 1.8 weight parts; エ パ Application 485) binder layer (thickness: 4 μ m); by having adopted the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μ m) of two-layer structure.
Comparative example 1
Use comprises the substrate layer (thickness: 26 μ m) of new LDPE (film grade) (LDPE) (eastern Cao's corporate system, ペ ト ロ セ Application 183); and comprise straight chain shape new LDPE (film grade) (LLDPE) (Sumitomo Chemical manufacturing; ス ミ カ セ Application EFV402) binder layer (thickness: 4 μ m); by having adopted the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μ m) of two-layer structure.
Comparative example 2
Use comprises the substrate layer (thickness: 26 μ m) of new LDPE (film grade) (LDPE) (eastern Cao's corporate system, ペ ト ロ セ Application 183); and (JPE makes to comprise ethylene-vinyl alcohol copolymer (EVA); ノ バ テ Star Network LV440) binder layer (thickness: 4 μ m); by having adopted the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μ m) of two-layer structure.
Comparative example 3
At the substrate layer (thickness: one side 26 μ m) that comprises new LDPE (film grade) (LDPE) (eastern Cao's corporate system, ペ ト ロ セ Application 183); the coating polymerization isocyanate-based linking agent of 94 parts by weight of acrylic butene esters, 6 parts by weight of acrylic and 30 weight parts (Japanese polyurethane manufacturing, コ ロ ネ one ト L) and the binder solution that forms; form binder layer (thickness: 4 μ m), obtain the surface protection film (thickness: 30 μ m) of two-layer structure thus.
Comparative example 4
Comprising new LDPE (film grade) (LDPE) (eastern Cao's corporate system; ペ ト ロ セ Application 183) substrate layer (thickness: one side 26 μ m); use is with respect to straight chain shape new LDPE (film grade) (LLDPE) (the pula nurse Polymer Company manufacturing of 50 weight parts; エ Port リ ユ-SP1540) and straight chain shape new LDPE (film grade) (LLDPE) (Sumitomo Chemical system; ア ミ カ セ Application EFV402) 50 weight parts and contain the polyoxyethylene styryl phenyl ether of 2.5 weight parts (the first industrial drugmaker makes; ノ イ ゲ Application EA-17 7) binder layer (thickness: 4 μ m); by having adopted the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μ m) of two-layer structure.But for this surface protection film, it is bad that the system film has taken place, and the uneven thickness degree is big, can not carry out evaluating characteristics.As the bad reason of system film, think that the content of above-mentioned polyoxyethylene styryl phenyl ether is too much, cause mobile heterogeneity with thermoplastic resin.
According to the method described above the surface protection film that makes is measured and estimated, the result who obtains is as shown in table 1.Table 1
Notes) A in the table 1: polyoxyethylene polyoxypropylene glycol, B: polyoxyethylene (2) lauric monoethanolamide, C: polyoxyalkylene decyl ethers, D: polyoxyethylene styryl phenyl ether.
According to the result of above-mentioned table 1, can confirm to use among the embodiment of the surface protection film that the present invention makes, the strip operation that all situations suppresses peeling force down is all good, and cleaning performance (cleaning rate) is also very good.
On the other hand, confirm in the comparative example that does not have to use the compound contain alkylene oxide group, peeling force height, strip operation are poor, and cleaning performance is also poor.
According to the above, can confirm surface protection film of the present invention, after it was attached at glass surface, surface protection film was peeled off easily, also can easily be cleaned, be removed by the caused residue of surface protection film afterwards.
Claims (5)
1. a binder composition is characterized in that, with respect to 100 parts by weight of thermoplastic resin, contains the compound that contains alkylene oxide group of 0.01～2 weight part.
2. composition as claimed in claim 1 is characterized in that, the above-mentioned compound that contains alkylene oxide group is a tensio-active agent.
3. a surface protection film is characterized in that, is to use claim 1 or 2 described binder compositions to form.
4. a flat-panel monitor basic pattern glass surface protective film is characterized in that, the single layer that forms by using claim 1 or 2 described binder compositions constitutes.
5. a flat-panel monitor basic pattern glass surface protective film is characterized in that, is by claim 1 or 2 described binder compositions being formed at the one side or two-sided formation of base material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008099596 | 2008-04-07 | ||
| JP2008-099596 | 2008-04-07 | ||
| PCT/JP2009/055956 WO2009125672A1 (en) | 2008-04-07 | 2009-03-25 | Adhesive composition, surface protective film, and mother glass surface protective film for flat panel display |
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| CN101970593A true CN101970593A (en) | 2011-02-09 |
| CN101970593B CN101970593B (en) | 2015-09-02 |
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| CN200980108717.5A Active CN101970593B (en) | 2008-04-07 | 2009-03-25 | Binder composition, surface protection film and flat-panel monitor mother glass surface protection film |
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| Country | Link |
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| JP (1) | JP5592615B2 (en) |
| KR (1) | KR101553090B1 (en) |
| CN (1) | CN101970593B (en) |
| TW (1) | TWI434909B (en) |
| WO (1) | WO2009125672A1 (en) |
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| JP5582726B2 (en) * | 2008-06-05 | 2014-09-03 | 日東電工株式会社 | Protective sheet and its use |
| JP2012054006A (en) * | 2010-08-31 | 2012-03-15 | Gunze Ltd | Transparent conductive gas barrier film and method for producing the same |
| JP5588361B2 (en) * | 2011-01-06 | 2014-09-10 | 日東電工株式会社 | Surface protection sheet |
| WO2012169479A1 (en) * | 2011-06-10 | 2012-12-13 | 住友化学株式会社 | Aqueous adhesive and laminate structure |
| WO2012169480A1 (en) * | 2011-06-10 | 2012-12-13 | 住友化学株式会社 | Aqueous adhesive and laminate structure |
| WO2012169482A1 (en) * | 2011-06-10 | 2012-12-13 | 住友化学株式会社 | Aqueous adhesive and laminate structure |
| WO2012169481A1 (en) * | 2011-06-10 | 2012-12-13 | 住友化学株式会社 | Aqueous adhesive and laminate structure |
| KR101123268B1 (en) * | 2012-01-06 | 2012-03-21 | 주식회사 아이.엠.텍 | Large-area film wrinkle removal device that is attached to a glass |
| WO2016083862A1 (en) | 2014-11-28 | 2016-06-02 | Corning Incorporated | Methods for producing shaped glass articles |
| KR102584782B1 (en) * | 2021-12-28 | 2023-10-10 | 한국성전(주) | printed circuit board for processing having protection cover |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000109777A (en) * | 1998-10-01 | 2000-04-18 | Konishi Co Ltd | One-component aqueous adhesive composition |
| CN1689934A (en) * | 2004-04-21 | 2005-11-02 | 日东电工株式会社 | Film for protecting mother glass for flat panel display and use thereof |
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| JP2001066430A (en) * | 1999-08-25 | 2001-03-16 | Nitto Denko Corp | Surface protective film, optical member and liquid crystal display device |
| JP4686960B2 (en) * | 2003-06-30 | 2011-05-25 | 綜研化学株式会社 | Adhesive for surface protective film and surface protective film |
| JP4453977B2 (en) * | 2004-07-16 | 2010-04-21 | 日東電工株式会社 | Adhesive composition, adhesive sheet and surface protective film |
| JP2007063298A (en) * | 2005-08-29 | 2007-03-15 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive solution composition and surface protective film |
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- 2009-03-06 JP JP2009053842A patent/JP5592615B2/en active Active
- 2009-03-25 WO PCT/JP2009/055956 patent/WO2009125672A1/en active Application Filing
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000109777A (en) * | 1998-10-01 | 2000-04-18 | Konishi Co Ltd | One-component aqueous adhesive composition |
| CN1689934A (en) * | 2004-04-21 | 2005-11-02 | 日东电工株式会社 | Film for protecting mother glass for flat panel display and use thereof |
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| Publication number | Publication date |
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| JP5592615B2 (en) | 2014-09-17 |
| KR20100134096A (en) | 2010-12-22 |
| WO2009125672A1 (en) | 2009-10-15 |
| JP2009270092A (en) | 2009-11-19 |
| KR101553090B1 (en) | 2015-09-14 |
| TW201005062A (en) | 2010-02-01 |
| TWI434909B (en) | 2014-04-21 |
| CN101970593B (en) | 2015-09-02 |
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