CN101970593B - Binder composition, surface protection film and flat-panel monitor mother glass surface protection film - Google Patents
Binder composition, surface protection film and flat-panel monitor mother glass surface protection film Download PDFInfo
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- CN101970593B CN101970593B CN200980108717.5A CN200980108717A CN101970593B CN 101970593 B CN101970593 B CN 101970593B CN 200980108717 A CN200980108717 A CN 200980108717A CN 101970593 B CN101970593 B CN 101970593B
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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
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/005—Dendritic macromolecules
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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
- C09J7/20—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]
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- 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
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
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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
- C09J2301/10—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Liquid Crystal (AREA)
Abstract
The invention provides that a kind of to attach protective membrane at glass surface easy; then, after peeling off surface protection film, the residue caused by surface protection film (binder layer wherein) can easily be cleaned, the binder composition that removes, binder layer and employ their flat-panel monitor mother glass surface protection film.The feature of binder composition is, relative to the thermoplastic resin of 100 weight parts, and the compound containing alkylene oxide group containing 0.01 ~ 2 weight.
Description
Technical field
The present invention relates to a kind of binder composition, in more detail, relate to the binder layer using these binder compositions and the flat-panel monitor mother glass surface protection film using these binder compositions.
Background technology
All glass substrate is used in the manufacture of the flat-panel monitors such as liquid-crystal display, plasma display, OLED display.Sheet glass manufactured by factory carries out circulate (carrying) with the form of mother glass, and then is processed to glass substrate.Mother glass transport or keeping, even along with delivery carry out carrying, carry out keeping etc. at client place time; conforming product rate will be caused to reduce, bring detrimentally affect to quality aspect once glass surface is scratched, therefore usual at glass surface wall-attached surface protective membrane.
The flat-panel monitor mother glass having attached surface protection film meets at panel manufacturers; the operation of stripper surface protective membrane will be carried out at panel manufacturers place; when peeling off heavy (being difficult to peel off), operability worsens, and is peeling not exclusively and peels off bad problem.
In addition, clean the residue of removing surface protection film after stripping with scavenging solution etc., also can produce the problem that residue thing is difficult to fall down from glass surface.
And the residue brought due to surface protection film can make to occur the problems such as quality reduction in the manufacturing process of TFT substrate, therefore there is higher requirement to the cleaning of residue thing in matting and removing.
In this case, propose the scheme of following surface protection film in patent documentation 1: the surface of substrate layer formed at polyethylene, the stacked density containing more than 50 % by weight is 0.91 ~ 0.93g/cm
3low Density Polyethylene, center line average roughness Ra be the surface protection film of the binder layer of less than 0.05 μm.
But, after the surface protection film that patent documentation 1 is recorded attaches to glass, can produce be difficult to peel off, the problem of operability difference, or attachment (transfer printing) is difficult to the problem that washes at the residue thing of glass surface.
The one side that Patent Document 2 discloses a kind of substrate layer being formed by thermoplastic resin is formed with the duplicature of the binder layer comprising ethylene vinyl acetate copolymer; And Patent Document 3 discloses and bond and utilize by the acrylic acid series comprising butyl acrylate and acrylic acid multipolymer the protection adhesive tape that the binder layer be cross-linked as the aromatic isocyanate of linking agent forms in the one side of substrate layer.
But above-mentioned duplicature and adhesive tape also can produce same problem.
Prior art document
Patent documentation 1: Japanese Patent No. 3103190 publication
Patent documentation 2: Japanese Patent No. 2980434 publication
Patent documentation 3: Japanese Unexamined Patent Publication 7-143643 publication
Summary of the invention
The object of the invention is to; in order to solve the problems referred to above existed in current surface protection film (thin slice); there is provided a kind of and easily attach protective membrane at glass surface; then, after peeling off surface protection film, the residue caused by surface protection film (binder layer wherein) easily can clean the binder composition of removing, binder layer and employ their flat-panel monitor mother glass surface protection film.
The present inventor etc. in order to achieve the above object, conduct in-depth research, and found that shown binder composition, binder layer below and have used their flat-panel monitor mother glass surface protection film, finally completed the present invention.
That is, a binder composition, wherein, relative to the thermoplastic resin of 100 weight parts, the compound containing alkylene oxide group containing 0.01 ~ 2 weight part.By adding the compound containing alkylene oxide group while adding thermoplastic resin; thus when the binder layer using it as surface protection film; although details is not clear; but the known attaching to glass surface becomes easy; utilize caused by surface protection film (binder layer wherein) residue, such as from binder layer low molecular compound with contain the compound of alkylene oxide group and carry out phase double replacement, the minimizing of residue can be realized.And, be also useful in the matting after surface protection film is peeled off, easily can clean, remove residue.
In addition, binder composition of the present invention, preferably the above-mentioned compound containing alkylene oxide group is tensio-active agent.By adding tensio-active agent; when it can be used as the binder layer of surface protection film to use; although details is not clear; but the known attaching to glass surface becomes easy; and utilize caused by surface protection film (binder layer wherein) residue, such as carry out phase double replacement from the low molecular compound of binder layer with tensio-active agent, the minimizing of residue can be realized.And, also useful in the matting after surface protection film is peeled off, easily can clean by adding tensio-active agent, remove residue.
Surface protection film of the present invention is preferably formed with above-mentioned binder composition.The surface protection film employing binder composition is easily processed into film like or flake, band shape etc., very useful.
Flat-panel monitor mother glass surface protection film of the present invention, the single layer preferably formed by using above-mentioned binder composition is formed.Use above-mentioned binder composition and the single layer itself formed has function as flat-panel monitor mother glass surface protection film, therefore manufacturing process is few, and operability is better.
The one or both sides that above-mentioned binder composition is preferably formed in base material by flat-panel monitor mother glass surface protection film of the present invention are formed.Utilize binder composition by use and be formed at the flat-panel monitor mother glass surface protection film on base material, can protect by attaching thing (glass) surface not contaminated, and prevent the generation of scratch etc., very useful.
It should be noted that, so-called in the present invention " flat-panel monitor mother glass " is a kind of sheet glass be in the state of front circulation that can be processed into various goods, typically refers to the mother glass used in the manufacture of flat-panel monitor.As flat-panel monitor, such as, there are the display unit such as liquid-crystal display, plasma display, OLED display.
Embodiment
Below embodiment of the present invention are described in detail
The feature of binder composition of the present invention is, relative to the thermoplastic resin of 100 weight parts, and the compound containing alkylene oxide group containing 0.01 ~ 2 weight part.
As the matrix polymer of the binder composition that the present invention uses, use thermoplastic resin.
As above-mentioned thermoplastic resin, as long as play fusible thermoplastic resin all can be suitable for using, the well-known thermoplastic bonded resins such as the block base polymer of such as polythylene resin, polypropylene-based resin, propylene-ethylene, Random Copolymer polymkeric substance, grafting base polymer, polystyrene resins, acrylic resin can be enumerated.These resins can be used alone that two or more may be used in combination.
As above-mentioned polythylene resin, such as, have: the polyolefin resines etc. such as Low Density Polyethylene, straight-chain Low Density Polyethylene, 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 multipolymer, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer.
Above-mentioned polystyrene resins such as has: styrene butadiene (SB), styrene isoprene (SI), styrene ethylene-butylene copolymer (SEB), the A-B type diblock polymers such as styrene ethylene-propylene copolymer (SEP), styrene butadiene styrene (SBS), styrene-isoprene-styrene (SIS), styrene ethylene-butylene copolymer vinylbenzene (SEBS), multi-block polymer more than A-B-A type three blocks such as styrene ethylene-propylene copolymer vinylbenzene (SEPS) or A-B-A-B type four block, the polystyrene random copolymerss such as styrene butadiene ribber (SBR), the A-B-C type vinylbenzene alkene crystal system segmented copolymers etc. such as styrene ethylene-butylene copolymer alkene crystallization (SEBC).
As thermoplastic resin, when using above-mentioned polyethylene-based resin, preferred density is 0.880 ~ 0.950g/cm
3low Density Polyethylene system resin, more preferably 0.880 ~ 0.923g/cm
3, particularly preferably 0.880 ~ 0.915g/cm
3.Above-mentioned low density polyethylene vinyl resin has excellent flexibility, and practicality.It should be noted that, density (g/cm of the present invention
3) be value according to ISO 1183 standard test.
In binder composition of the present invention, relative to the above-mentioned thermoplastic resin of 100 weight parts, the content containing the compound of alkylene oxide group is 0.01 ~ 2 weight part, is preferably 0.05 ~ 1.5 weight part, is more preferably 0.1 ~ 1 weight part.When it is lower than 0.01 weight part, the performance removing residue in matting reduces; During more than 2 weight part, during manufacture surface protection film, (situation of extrusion molding) can cause forming defect.Due to these reasons, there is the low viscous compound containing alkylene oxide group and will cause with the mobility of thermoplastic resin uneven in mixing in large quantities, causes forming defect.In addition, even if form film, when with the scavenging solution removing residue used in matting, must use more scavenging solution, cost aspect is not preferred yet.
As the above-mentioned compound containing alkylene oxide group, spent glycol can be made, propylene glycol, butyleneglycol, Whitfield's ointment glycol, propylene glycol mono, 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, polyoxyethylene laural base sodium sulfate, polyoxyethylene sorbitan carboxylic ester, sorbitan carboxylic esters, polyoxyethylenated castor oil, polyoxyethylene height solidification Viscotrol C, the compounds such as Wool wax alcohols,ethoxylated fatty acid ester.Above-claimed cpd can as uses such as emulsifying agent, dispersion agent, lubricant, clouding agent, anti-thixotropic agent, tensio-active agent, static inhibitor, particularly preferably tensio-active agent.
Above-mentioned tensio-active agent, as long as can use containing 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 laural base sodium sulfate etc.In addition, as the compound of above-mentioned ester class, preferred polyoxyethylene sorbitan carboxylic ester, sorbitan carboxylic esters, polyoxyethylenated castor oil, polyoxyethylene height solidification Viscotrol C, Wool wax alcohols,ethoxylated fatty acid ester etc.
In the binder layer used in surface protection film of the present invention, in order to reach the object controlling adhesion characteristic, suitably can add according to using the purposes of various additive: current known various tenderizer, tackifier, the ethylene series resin that can use in substrate layer, silicone-based polymers, liquid methacrylate based copolymer, phosphoric acid ester based compound, protective agent, hindered amine system photostabilizer, UV light absorber, surface lubricant, flow agent, softening agent, low-molecular(weight)polymer, antioxidant, sanitas, stopper, silane coupling agent, inorganic and organic filler (such as, calcium oxide, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide etc.), metal-powder, tinting material, the powders such as pigment, granular, foil material, the current known various additive such as heat-resisting stabilizing agent.
In addition, by by above-mentioned binder composition heating and melting, binder layer can be obtained.The binder layer obtained by melting heated adhesive composition is easy to be processed into membranaceous, sheet, band shape etc., very useful.
The formation method of above-mentioned tackiness agent is not particularly limited, and can use known method, such as melted extrusion modeling, rolling process etc.
And, on the surface of binder layer, as required also can embodiment as Corona discharge Treatment, uviolizing process, flame treating, Cement Composite Treated by Plasma, sputter etching process etc., to control binding property or to attach the surface treatment for the purpose of operability etc.
For binder layer, in before during in, also dividing plate etc. can be installed as required temporarily and protect.
In surface protection film of the present invention, the thickness of binder layer is generally about 1 ~ 50 μm, preferably 2 ~ 40 μm, is more preferably 3 ~ 20 μm.During thickness low LCL 1 μm, be difficult to play binding property; During more than 50 μm, peel off and become difficulty, and the usage quantity of adding the compound containing alkylene oxide group in binder layer to increases, unfavorable in cost, not preferably.
By using the single layer of above-mentioned binder layer, can surface protection film be manufactured, particularly can manufacture flat board indicating meter mother glass surface protection film.Because binder layer itself has the function of surface protection film, thus manufacturing process is few, practical.
In addition, above-mentioned binder layer is formed at the single or double of base material, flat-panel monitor mother glass surface protection film can be formed.By using surface protection film base material defining binder layer, can available protecting to be attached thing (glass) surface not contaminated, and the generation that can prevent from scratching etc., very useful.
The base material (layer) used in the present invention, can be formed as flake, film like, band shape etc., be not particularly limited, such as polyolefin-based resins, owing to also having pliability while having thermotolerance and solvent resistance, thus preferably uses.By making substrate layer have pliability, can roll be wound in, carry out various processing suitably.
Said polyolefins resin such as can be enumerated polyethylene-based resin, propylene or comprise the propylene resin, ethylene vinyl acetate copolymer etc. of propylene composition and ethene composition.
Concrete example is if any Low Density Polyethylene, straight-chain Low Density Polyethylene, 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, ethylenemethylmethacrylate multipolymer, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, the polyolefin resines etc. such as ethylene-vinyl alcohol copolymer.
For the present invention, can suitably containing the various additives that normally used crowd in this base material such as membranaceous or laminar, banded knows in above-mentioned substrate layer.Such as, various weighting agent, pigment, uv-absorbing agent, oxidation inhibitor, heat-resisting stabilizing agent, lubricant etc.
The thickness of above-mentioned substrate layer, usually preferably about 20 ~ 300 μm, more preferably about 20 ~ 250 μm, particularly preferably about 25 ~ 200 μm, when substrate layer is less than 20 μm, during stripping, base material can occur to destroy or break, during more than 300 μm, the elasticity of base material becomes large, also easily decortication etc. occurs after attaching.
In addition, for the substrate layer side of surface protection film, in order to make it have lancinating (hand cuts れ) or anti-skid, processing patterns and concavo-convex processing etc. can be implemented.
As the manufacture method of surface protection film of the present invention; from can high-level efficiency, manufacture surface protection film aspect of the present invention at an easy rate; preferably will form the melting heating coextruded profiled respectively of the substrate layer that formed by polyolefin-based resins and the starting material of binder layer that formed by thermoplastic resin; make binder layer become to be integrated with the one or both sides of substrate layer, manufacture the method with the film of the bilayer structure (or multilayer of more than 3 layers) of specific thicknesses.
As above-mentioned coextruded profiled, normally used method during film, thin slice etc. can be adopted to manufacture, is not particularly limited.Such as, the method such as blow moulding (inflation), coextrusion T-die head method can be used.Use above-mentioned coextruded profiled, more satisfactory in cost and in productivity.
In addition, for the stacked stacked number of difference in above-mentioned each layer, there is no particular restriction, and above-mentioned substrate layer and above-mentioned binder layer can be individual layers respectively, also can be made multilayered structure as required.
In addition, the integral thickness of surface protection film of the present invention, is preferably 20 ~ 150 μm, more preferably 30 ~ 100 μm.If integral thickness is less than 20 μm, then when peeling off, operability is poor, easily produces problems such as breaking; If thickness is more than 150 μm, then can produce the problem of decortication after there will be attaching, also unfavorable in cost, preferably do not use.
Embodiment
Below formation of the present invention and effect are illustrated by illustrative embodiment etc., but the present invention is not limited to these embodiments.In addition, the assessment item in embodiment etc. measures as described below.
1) peeling force
At crystal liquid substrate, with mother glass, (NH technical glass manufactures; NA35) crimping (0.2Mpa, 1.0m/ minute) after upper wall-attached surface protective membrane; keeping one day at 23 DEG C, by the peeling force (N/20mm) during tensile testing machine (manufactures of NMB company, TCM-5KNB-3, draw speed 0.3m/ minute, angle 180 °) mensuration stripper surface protective membrane.It should be noted that, preferred below the 0.02N/20mm of peeling force, more preferably below 0.015N/20mm.In addition, as peeling force, from the determination limit value of adaptation on trier, preferred more than 0.001N/20mm.When peeling force is high, strip operation is deteriorated, and the residue that surface protection film causes easily increases.
2) contact angle
Crimping (0.2Mpa, 1.0m/ minute) after glass (manufacture of NH technical glass, NA35) upper wall-attached surface protective membrane; at 40 DEG C after 4 days; measure the contact angle before cleaning; then; by above-mentioned glass surface; use the aqueous solution of the inorganic alkaline clean-out system of 2.0% (manufacture of Yokohama oil prodution industry, KG) to carry out ultrasonic cleaning in 2 minutes, then with the drip washing of distilled water through 3 minutes, measure the contact angle after cleaning.
3) cleaning performance (cleaning rate)
Cleaning performance (cleaning rate) utilizes formula below to calculate.It should be noted that, cleaning performance preferably more than 65%, more preferably more than 70%.When cleaning performance is less than 65%, residue can cause stripping 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 embodiment 10), comparative example, shaping by blow moulding.In addition, melt temperature and substrate layer and binder layer, die temperatures and coextrusion temperature are all set as 180 DEG C.And, in embodiment 10, shaping by T-die head method.Melt temperature, extrusion machine temperature and die temperatures are all set to 190 DEG C.
Embodiment 1
Use comprises substrate layer (thickness is 26 μm) and straight-chain Low Density Polyethylene (LLDPE) (the Sumitomo Chemical manufacture relative to 100 weight parts of Low Density Polyethylene (LDPE) (Dong Cao Inc., ペ ト ロ セ Application 183); ア ミ カ セ Application EFV402) and the binder layer of polyoxyethylene polyoxypropylene glycol containing 0.06 weight part (the first industrial manufacturing company manufactures, エ パ Application 485); by have employed the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μm) of two-layer structure.
Embodiment 2
The addition of polyoxyethylene polyoxypropylene glycol is set as 0.36 weight part, in addition, utilizes the method identical with embodiment 1 to obtain surface protection film (thickness: 30 μm).
Embodiment 3
The addition of polyoxyethylene polyoxypropylene glycol is set as 0.6 weight part, in addition, utilizes the method identical with embodiment 1 to obtain surface protection film (thickness: 30 μm).
Embodiment 4
The addition of polyoxyethylene polyoxypropylene glycol is set as 0.9 weight part, in addition, utilizes the method identical with embodiment 1 to obtain surface protection film (thickness: 30 μm).
Embodiment 5
Use comprises Low Density Polyethylene (LDPE) (Dong Cao Inc., ペ ト ロ セ Application 183) substrate layer (thickness is 26 μm), and relative to 100 weight parts straight-chain Low Density Polyethylene (pula nurse (プ ラ イ system) Polymer Company manufacture, エ Port リ ユ-SP1540) and the binder layer (thickness: 4 μm) of polyoxyethylene (2) lauric monoethanolamide (river is ground fine chemistry and manufactured ア ミ ゼ Star ト 2L-Y) containing 0.06 weight part, by make use of the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μm) of two-layer structure.
Embodiment 6
Replace polyoxyethylene (2) lauric monoethanolamide in embodiment 5; add polyoxyalkylene decyl ethers (the first industrial pharmaceutical manufacture of 0.18 weight part; ノ イ ゲ Application XL-400); in addition, the method identical with embodiment 5 is utilized to obtain surface protection film (thickness: 30 μm).
Embodiment 7
Use comprises Low Density Polyethylene (LDPE) (Dong Cao Inc., ペ ト ロ セ Application 183) substrate layer (thickness is 26 μm), and relative to 100 weight parts straight-chain Low Density Polyethylene (pula nurse Polymer Company manufacture, エ Port リ ユ-SP1540) 50 weight parts and straight-chain Low Density Polyethylene (LLDPE) (Sumitomo Chemical manufacture, ス ミ カ セ Application EFV402) 50 weight parts total and containing polyoxyethylene styryl phenyl ether (the first industrial pharmaceutical manufacture of 0.06 weight part, ノ イ ゲ Application EA-177) binder layer (thickness: 4 μm), by have employed the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μm) of two-layer structure.
Embodiment 8
Except making the addition of polyoxyethylene styryl phenyl ether be except 0.18 weight part, utilize the method identical with embodiment 7, obtained surface protection film (thickness: 30 μm).
Embodiment 9
Except making the addition of polyoxyethylene styryl phenyl ether be except 0.36 weight part, utilize the method identical with embodiment 7, obtained surface protection film (thickness: 30 μm).
Embodiment 10
Use ethylene-vinyl alcohol copolymer (EVA) (the JPE manufacture relative to 100 weight parts; ノ バ テ Star Network LV440) and containing polyoxyethylene polyoxypropylene glycol (the first industrial pharmaceutical manufacture of 1.2 weight parts; エ パ Application 485) the simple layer of binder layer, obtained the surface protection film (thickness: 35 μm) of single structure by T-die head legal system.
Embodiment 11
Use comprises ethylene-vinyl alcohol copolymer (EVA), and (JPE manufactures, ノ バ テ Star Network LV440) substrate layer (thickness is 26 μm), and relative to 100 weight parts styrene-ethylene butylene-ethylene block copolymer (SEBC) (JSR manufacture, DYNARON4600P) polyoxyethylene polyoxypropylene glycol (the first industrial pharmaceutical manufacture of 1.8 weight parts is contained, エ パ Application 485) binder layer (thickness: 4 μm), by have employed the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μm) of two-layer structure.
Comparative example 1
Use comprises the substrate layer (thickness: 26 μm) of Low Density Polyethylene (LDPE) (Dong Cao Inc., ペ ト ロ セ Application 183); and comprise straight-chain Low Density Polyethylene (LLDPE) (Sumitomo Chemical manufacture; ス ミ カ セ Application EFV402) binder layer (thickness: 4 μm); by have employed the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μm) of two-layer structure.
Comparative example 2
Use comprises the substrate layer (thickness: 26 μm) of Low Density Polyethylene (LDPE) (Dong Cao Inc., ペ ト ロ セ Application 183); and (JPE manufactures to comprise ethylene-vinyl alcohol copolymer (EVA); ノ バ テ Star Network LV440) binder layer (thickness: 4 μm); by have employed the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μm) of two-layer structure.
Comparative example 3
Comprising the one side of substrate layer (thickness: 26 μm) of Low Density Polyethylene (LDPE) (Dong Cao Inc., ペ ト ロ セ Application 183); coating be polymerized the vinylformic acid butene esters of 94 weight parts, the vinylformic acid of 6 weight parts and 30 weight parts isocyanate-based linking agent (Japanese polyurethane manufacture, コ ロ ネ mono-ト L) and formed binder solution; form binder layer (thickness: 4 μm), obtain the surface protection film (thickness: 30 μm) of two-layer structure thus.
Comparative example 4
Comprising Low Density Polyethylene (LDPE) (Dong Cao Inc., ペ ト ロ セ Application 183) the one side of substrate layer (thickness: 26 μm), use straight-chain Low Density Polyethylene (LLDPE) (the pula nurse Polymer Company manufacture relative to 50 weight parts, エ Port リ ユ-SP1540) and straight-chain Low Density Polyethylene (LLDPE) (Sumitomo Chemical system, ア ミ カ セ Application EFV402) 50 weight parts and containing 2.5 weight parts polyoxyethylene styryl phenyl ether (first industrial pharmaceutical company manufacture, ノ イ ゲ Application EA-17 7) binder layer (thickness: 4 μm), by have employed the blow moulding of above-mentioned condition of molding, obtain the surface protection film (thickness: 30 μm) of two-layer structure.But for this surface protection film, there occurs masking bad, uneven thickness degree is large, can not carry out evaluating characteristics.As the reason that masking is bad, think that the content of above-mentioned polyoxyethylene styryl phenyl ether is too much, cause the mobility heterogeneity with thermoplastic resin.
Measure obtained surface protection film and evaluate according to the method described above, the result obtained is as shown in table 1.Table 1
Note) A in 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 in the embodiment of the surface protection film using the present invention to obtain, suppress the strip operation of peeling force all good under all situations, cleaning performance (cleaning rate) is also very good.
On the other hand, confirm and do not have to use in the comparative example containing the compound of alkylene oxide group, peeling force is high, strip operation is poor, and cleaning performance is also poor.
According to the above, can confirm surface protection film of the present invention, after being attached at glass surface, surface protection film is easily peeled off, and the residue afterwards caused by surface protection film also easily can be cleaned, remove.
Claims (5)
1. a surface protection film, is characterized in that, uses following binder composition to be formed,
Described binder composition only containing thermoplastic resin and relative to described thermoplastic resin 100 weight part be 0.1 ~ 1 weight part containing the compound of alkylene oxide group,
Described thermoplastic resin is density is 0.880 ~ 0.950g/cm
3low Density Polyethylene system resin.
2. surface protection film as claimed in claim 1, is characterized in that, the above-mentioned compound containing alkylene oxide group is tensio-active agent.
3. a flat-panel monitor mother glass surface protection film, is characterized in that, is the surface protection film described in claim 1 or 2, and its single layer formed by using described binder composition is formed.
4. a flat-panel monitor mother glass surface protection film, is characterized in that, is the surface protection film described in claim 1 or 2, and it is one side by described binder composition being formed at base material or is two-sidedly formed.
5. a flat-panel monitor mother glass, is characterized in that, is to have attached surface protection film according to any one of Claims 1 to 4.
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| JP2008-099596 | 2008-04-07 | ||
| JP2008099596 | 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 CN101970593A (en) | 2011-02-09 |
| CN101970593B true CN101970593B (en) | 2015-09-02 |
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| KR (1) | KR101553090B1 (en) |
| CN (1) | CN101970593B (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 |
| WO2012169482A1 (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 |
| WO2012169481A1 (en) * | 2011-06-10 | 2012-12-13 | 住友化学株式会社 | Aqueous adhesive and laminate structure |
| WO2012169479A1 (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 |
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| 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 |
| CN1816603A (en) * | 2003-06-30 | 2006-08-09 | 综研化学株式会社 | Pressure-sensitive adhesive for surface-protective film and surface-protective film |
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| JP4138098B2 (en) * | 1998-10-01 | 2008-08-20 | コニシ株式会社 | One-part aqueous adhesive composition |
| JP2001066430A (en) * | 1999-08-25 | 2001-03-16 | Nitto Denko Corp | Surface protective film, optical member and liquid crystal display device |
| 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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| CN1816603A (en) * | 2003-06-30 | 2006-08-09 | 综研化学株式会社 | Pressure-sensitive adhesive for surface-protective film and surface-protective film |
| 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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| JP2009270092A (en) | 2009-11-19 |
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| KR20100134096A (en) | 2010-12-22 |
| CN101970593A (en) | 2011-02-09 |
| KR101553090B1 (en) | 2015-09-14 |
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| TWI434909B (en) | 2014-04-21 |
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