CN101668795B - Antistatic film, polyester film for surface-protecting film, and polyester film for protecting surface of optical member - Google Patents
Antistatic film, polyester film for surface-protecting film, and polyester film for protecting surface of optical member Download PDFInfo
- Publication number
- CN101668795B CN101668795B CN2008800108786A CN200880010878A CN101668795B CN 101668795 B CN101668795 B CN 101668795B CN 2008800108786 A CN2008800108786 A CN 2008800108786A CN 200880010878 A CN200880010878 A CN 200880010878A CN 101668795 B CN101668795 B CN 101668795B
- Authority
- CN
- China
- Prior art keywords
- film
- static electricity
- electricity resistance
- coating layer
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
An antistatic film excellent in antistatic properties, water resistance, and durability. The antistatic film is characterized by comprising a polyester film and, formed on one side thereof, a coating layer comprising an antistatic polymer having constituent elements represented by the following structural formulae (1) and (2) as repeating units. (In the formula, R<1> and R<2> each independently is hydrogen or C1-3 alkyl, and X<-> is a monovalent anion).
Description
Technical field
The present invention relates to the static electricity resistance film.Further in detail, the present invention relates to have the excellent static electricity resistance polyester film of water tolerance of excellent antistatic performance and antistatic performance.The invention still further relates to and be suitable as the film that polaroid, polarizer or visual angle enlarge the surface protection film of film, relate in friction or when peeling off charged less, film that outward appearance is excellent.
Background technology
It with polyethylene terephthalate or PEN the excellence such as physical strength, dimensional stability, flatness, thermotolerance, resistance to chemical reagents, optical characteristics of the polyester film of representative; The ratio of performance to price is also excellent; So, be used as base material use in film, film for packaging, the various uses of optical film using as representative with plate-making.
But the common issue with of plastic film is, exists to be easy to generate static and charged shortcoming.Therefore, cause film add the movability of man-hour or fabricated product bad or attract around the problem of dust etc.
On the surface of the polaroid (or polarizer etc.) or the opticses such as multilayer body of taking this as the standard, be purpose to protect the surface to avoid damage, pollute, on the polyester film base material, attach the protective membrane that is coated with tackiness agent.Polyester film is in friction or charged easily when parts are peeled off etc.; After each operation and optics assembling completion that the protective membrane as optics uses; When removing through peeling off these protective membranes; Produce frictional electrification or stripping charge, problems such as foreign matter or dust adhere to, static discharge obstacle occur.
Usually, as the method for the anti-electrostatic of polyester film, have as the method for the surface coated static electricity resistance resin of the film of base material be coated with the method (for example, with reference to patent documentation 1) of various static electricity resistance compounds.
Particularly about the coating on polyester film, the method (so-called real-time coating, in-line coating) that in film manufacturing process, is coated with the coating fluid that contains coating composition can access economy and good characteristic, thereby is widely used.Typical example has behind longitudinal stretching and is coated with, and carries out the method for cross directional stretch and heat setting afterwards.
In addition, as the static electricity resistance compound, the characteristic of the cationic compound of known higher molecular weight relatively good (patent documentation 2, patent documentation 3).
But, attaching a little less than the common thermotolerance of the quaternary ammonium hydroxide on the polymer side chain as patent documentation 2 is enumerated, when the real-time coating that is used for above-mentioned that kind, because the temperature of this moment is very high, so, cause decomposition easily, static electricity resistance is worsened.
On the other hand, the compound as patent documentation 3 is enumerated is because this quaternary ammonium hydroxide is positioned at macromolecular scaffold, so excellent heat resistance can access very good anti-static property.But, because such compound itself is very hydrophilic, so the water tolerance of the coating layer that obtains is not enough.Particularly, if through operations such as washings, cause antistatic performance to worsen sometimes.In addition, if in the high humidity held, albefaction can take place in the surface.In the optics purposes, the inspection of optics is carried out being pasted with under the state of surface protection film usually.Therefore,, require not hinder the outward appearance of inspection for surface protection film, so, also exist problem when using such compound.
In addition, in the manufacturing procedure of optics since with the contacting of processor or carrying roller etc., produce damage at the protective membrane upper layer, can bring obstacle to inspection, therefore, need have weather resistance to this.But, adopt existing static electricity resistance resin, scarcely have enough this weather resistance.
In addition, for the protective membrane that attaches, in manual operation such as overburden operation operation, inspection operation again, the protective membrane surface easily by grease, extrude or the pollutions such as tackiness agent of transfer printing, also require to have the surface property of stain resistance sometimes.
Patent documentation 1: japanese kokai publication hei 7-26223 communique
Patent documentation 2: TOHKEMY 2004-123932 communique
Patent documentation 3: japanese kokai publication hei 1-146931 communique
Summary of the invention
The present invention accomplishes in view of above-mentioned practical situation, and it solves problem and is to provide a kind of static electricity resistance film with excellent static electricity resistance, water tolerance and weather resistance.Particularly the present invention provides and shows excellent static electricity resistance and the coated film of excellent characteristic when using as the protective membrane of optics.
Contrivers of the present invention etc. further investigate above-mentioned problem repeatedly, and the result finds: contain the coating layer of the compound of particular types through setting, can solve above-mentioned problem, thereby accomplish the present invention.
Promptly; Main points of the present invention are a kind of static electricity resistance film, it is characterized in that: on a face of polyester film, have the coating layer that contains the static electricity resistance macromolecular compound, wherein; This static electricity resistance macromolecular compound has the textural element shown in following structural formula 1 and 2 as repeating unit
(in the above-mentioned formula, R
1And R
2Independent respectively, be that Wasserstoffatoms or carbonatoms are 1～3 alkyl, X
-Be the negatively charged ion of 1 valency),
(in the above-mentioned formula, R
3Be that Wasserstoffatoms or carbonatoms are 1～3 alkyl, R
4Be-O-or-NH-, R
5Be that carbonatoms is 1～6 alkylidene group).
The surface protection film that second main points of the present invention constitute for the static electricity resistance film by first main points.
The 3rd main points of the present invention are that a kind of protecting surface of optical member is used polyester film, it is characterized in that: on the face of the opposite side of the coating layer of the described polyester film of first main points, have little adhesion layer.
According to the present invention, a kind of coated film can be provided, it has excellent static electricity resistance and weather resistance, for example, as the optics protective membrane, in particular as protective film for polarizing plate the time, shows excellent characteristic, and its commercial value is high.
Embodiment
Below, specify the present invention.The employed polyester of polyester film of the present invention is to make terephthalic acid, m-phthalic acid, 2; 6-naphthalene dicarboxylic acids, hexanodioic acid, sebacic acid, 4; 4 '-diphenyldicarboxylic acid, 1; The dicarboxylicacid that the 4-cyclohexyl dicarboxylic acid is such or its ester and terepthaloyl moietie, glycol ether, Tri Ethyleneglycol, Ucar 35,1,4-butyleneglycol, season pentanediol, 1,4 cyclohexane dimethanol that kind glycol melt phase polycondensation and the polyester that makes.The polyester that is made up of these sour compositions and diol component can use the method manufacturing of common employing arbitrarily.
For example; Can adopt following method: between the lower alkyl esters of aromatic dicarboxylic acid and glycol, carry out transesterification reaction; Perhaps make aromatic dicarboxylic acid and glycol direct esterification; Form two diol esters or its oligopolymer of aromatic dicarboxylic acid in fact, then under reduced pressure it is heated and make its polycondensation.According to its purpose, also can make the aliphatic dicarboxylic acid copolymerization.
As polyester of the present invention; Can enumerate polyethylene terephthalate typically or gather 2; 6-(ethylene naphthalate), poly terephthalic acid-1,4-hexamethylene dimethyl ester etc., in addition; Also can be to make above-mentioned sour composition or diol component copolymerization and the polyester that obtains, can also contain other composition or additive as required.
With the movability of guaranteeing film, to prevent to sustain damage etc. be purpose, can in polyester film of the present invention, contain particle.As such particle; For example can use inorganic particles such as silicon-dioxide, lime carbonate, magnesiumcarbonate, calcium phosphate, kaolin, talcum, aluminum oxide, titanium oxide, vanadine (alumina), permanent white, Calcium Fluoride (Fluorspan), lithium fluoride, zeolite, moly-sulfide; Organic granulars such as cross-linked polymer particle, caoxalate are separated out particle etc. in the time of can also using polyester manufacturing process.
Particle grain size of using and content are selected according to the purposes and the purpose of film, and median size is the scope of 0.01～5.0 μ m normally.If median size surpasses 5.0 μ m, the roughness on film surface will become thick, and perhaps particle comes off from the film surface easily.If median size is less than 0.01 μ m, it is too small that surfaceness will become, and can't obtain enough easy to be sliding property sometimes.With respect to polyester, granule content is generally the scope of 0.0003～1.0 weight %, is preferably the scope of 0.0005～0.5 weight %.During less than 0.0003 weight %, easy the to be sliding property of film is insufficient sometimes at granule content; On the other hand, if when addition surpasses 1.0 weight %, film is transparent insufficient sometimes.In addition, can in film, suitably add various stablizers, lubricant, antistatic agent etc.
As the film-forming method of film of the present invention, can adopt common known film-forming method, not special restriction.For example; At first, adopt the roller stretching method to be stretched as 2～6 times at 70～145 ℃, obtain the uniaxial extension polyester film through melt extruding the sheet that obtains; Then; In tenter machine with 80～160 ℃ being stretched as 2～6 times with the rectangular direction of previous draw direction, with 150～250 ℃ of thermal treatments of carrying out 1～600 second, can obtain film thus again.And preferred this moment is in the heat-treatment zone and/or the cooling zone of thermal treatment outlet, in method vertical and/or transverse relaxation 0.1～20%.
Polyester film of the present invention is the single or multiple lift structure.Under the situation that is multilayered structure, can be according to purpose, making top layer and internal layer or two top layers or each layer is different polyester.
Polyester film of the present invention can be arranged on the coating layer of static electricity resistance the single face of film, also can be arranged on the two sides, and other coating layer perhaps is set at another face, and this is also included within the notion of the present invention certainly.In addition, with static electricity resistance film of the present invention as protecting surface of optical member when using polyester film, have the coating layer of static electricity resistance at single face, and have little adhesion layer at its opposing face.
The surperficial intrinsic resistance that static electricity resistance coating layer of the present invention is specially coating layer is low, have the coating layer of sewing the electric charge function.Surperficial intrinsic resistance that we can say coating layer is low more, and static electricity resistance is just good more.We can say if surperficial intrinsic resistance is 1 * 10
13Below the Ω, just has static electricity resistance; If be 1 * 10
11Below the Ω, just has good anti-static property.
In the present invention, must contain the static electricity resistance macromolecular compound in the static electricity resistance coating layer, this static electricity resistance macromolecular compound has the textural element shown in following structural formula 1 and 2 as repeating unit.
In the above-mentioned formula, R
1And R
2Independent respectively, be that Wasserstoffatoms or carbonatoms are 1～3 alkyl, X
-It is the negatively charged ion of 1 valency.
In the above-mentioned formula, R
3Be that Wasserstoffatoms or carbonatoms are 1～3 alkyl, R
4Be-O-or-NH-, R
5Be that carbonatoms is 1～6 alkylidene group.
Wherein, X
-Can in the scope of not damaging main points of the present invention, suitably select.As in industry, obtain easily, form easy to manufacture, can enumerate halogen ion, nitrate ion, alkylsulphonic acid ion etc.
In the present invention, the formula 1 in such macromolecular compound does not limit with the ratio of the textural element shown in the formula 2 is special, but the part by weight of the textural element of preferred formula 2 in macromolecular compound is more than 1%, more preferably more than 5%.There is the trend of the weather resistance variation of coating layer in the textural element of formula 2 during less than this scope.
On the other hand, the textural element of formula 1 shared ratio in macromolecular compound is unqualified.This ratio is more little, and the antistatic performance of coated film just worsens more, but through increasing the thickness of coating layer, can improve antistatic performance.But the thickness of the coating layer that in industry, can realize is limited, and if coating layer blocked up, can cause the deterioration of adhesion and outward appearance, cost rising etc., so must suitably select as required.Particularly, in weight ratio, be preferably 70～99%.
In addition, static electricity resistance macromolecular compound of the present invention in the scope of not damaging main points of the present invention, can have above-mentioned formula 1 and 2 composition in addition as textural element.As such composition, as long as in the scope of not damaging main points of the present invention, not special the qualification, but because the such easy polymerization of the compound that contains vinyl or other carbon-to-carbon double bond of vinyl compound, thereby preferred.Example as the compound of that kind; Can enumerate vinylformic acid, methylacrylic acid, butenoic acid, methylene-succinic acid, fumaric acid, toxilic acid, such various monomer class and the salt thereof that contain carboxyl of citraconic acid; 2-hydroxyethyl (methyl) propenoate, 2-hydroxypropyl (methyl) propenoate, 4-hydroxyl butyl (methyl) propenoate, monobutyl hydroxyfumaric acid ester, the such various monomer classes that contain hydroxyl of monobutyl hydroxyl itaconic ester; (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) Bing Xisuandingzhi, such various (methyl) esters of acrylic acid of (methyl) dodecylacrylate, the various nitrogenous ethene base system monomer class that (methyl) acrylic amide, diacetone-acryloamide(DAA), N hydroxymethyl acrylamide or (methyl) vinyl cyanide etc. are such.And, can with these compounds and usefulness, make polymerizable monomer copolymerization as follows.Promptly; Can enumerate vinylbenzene, alpha-methyl styrene, Vinylstyrene, the such various styrene derivativess of Vinyl toluene; Vinyl acetate, the such various vinyl esters of propionate; Such various siliceous polymerizable monomer classes such as " SILAPLANE FM-07 " (methacryloyl silicon macromonomer) that gamma-methyl allyl acyloxypropyl trimethoxysilane, vinyltrimethoxy silane, chisso Co., Ltd. produce; Phosphorous ethene base system monomer class; Vinylchlorid, vinylidene chloride, vinyl fluoride, vinylidene, trifluorochloroethylene, tetrafluoroethylene, chlorotrifluoroethylene, the such various vinyl halides classes of R 1216, the various conjugated dienes that divinyl is such etc.
The molecular weight of static electricity resistance macromolecular compound, preferred number average molecular weight are 5000～500000 scope, more preferably 8000～100000 scope.Number-average molecular weight is not enough easily less than the antistatic performance of the coated film that 5000 compound obtains; In addition, if surpass 500000, the excess stickiness of coating fluid rises, and causes being coated with uniform coating layer easily and becomes difficult.
For repeating unitary macromolecular compound, can carry out free-radical polymerized obtaining with such textural element through the formula 1 that makes above-mentioned that kind, the monomer of formula 2.Like this free-radical polymerized can be used known method.For example, the monomer of each textural element is processed the aqueous solution, mix to regulate making that adding up to concentration is 10～50 weight %; Under nitrogen atmosphere; Drip simultaneously in reactor drum with the radical initiator aqueous solution, simultaneously to stirring in the reactor drum, and at 50 ℃～80 ℃; For because heating or the temperature that causes of reaction heat rise cools off, polyase 13～8 hour simultaneously.And, further adding under the situation of other composition, if, can easily regulate mixed aqueous solution simultaneously, and carry out free-radical polymerized like the above-mentioned compound that contains carbon-to-carbon double bond.Wherein, can make with extra care, utilize reactant
1H-NMR or GPC (gel permeation chromatography) etc. analyze, and obtain each monomer component ratio and molecular weight in the copolymerized macromolecule that obtains.
In addition, preferably contain thermosetting resin in the static electricity resistance coating layer of the present invention.If particularly for having the reactive resin with the compound shown in the formula 2, the weather resistance of coating layer will improve, thereby preferred.Resin as that kind can use various known resins, for example, can enumerate isocyanates 、 oxazoline class, epoxies, oxalic dialdehyde class etc.Also comprise the polymer-type crosslinking reaction property compound that has reactive base in other the polymer backbone.As preferred especially form among the present invention, linking agent that can illustration aminoresin class.As the linking agent of aminoresin class, melamine class, benzoguanamine class, urea class of alkanolization etc. are for example arranged.Particularly amino is carried out methylolation and the part of this methylol methylated after the product that obtains have water-solublely, the property handled is good, reactivity is also high, thereby is fit to use.In addition, more preferably and use crosslinking catalyst.
The combination of the such aminoresin class linking agent and the static electricity resistance macromolecular compound of said structure, the static electricity resistance of the coating layer that obtains, weather resistance etc. are extremely excellent.
In addition, in static electricity resistance coating layer of the present invention, can contain more than one the compound or derivatives thereof that is selected from alkyls compound, fluorine cpd, the organosilicon compound.Through containing such composition, when film of the present invention was used as protective membrane, the soil release characteristics on surface was improved.
So-called alkyls compound be meant have polyolefine, the compound of the repeating unit of the alkene shown in the formula of polyolefins wax, alkyl graftomer etc.
-(CH
2-CH
2)
n-(CH
2-CHR)
m-
In the above-mentioned formula, R representes that hydrogen or carbonatoms are 1～6 alkyl, and n representes the integer more than 1, and m representes the integer more than 0 or 1.
Fluorine cpd among the present invention are meant the compound with the low fluorine-containing functional group of polarity especially, specifically can enumerate polymkeric substance that contains fluoroolefins or perfluoroalkyl etc.Particularly from the affinity of polyester film and with the aspects such as intermiscibility of other composition that constitutes coating layer, the preferred ethylene unsaturated monomer that contains perfluoroalkyl that uses reacts the polymkeric substance that obtains with other ethylene unsaturated monomer.As the ethylene unsaturated monomer that contains perfluoroalkyl, not special the qualification for example, can be enumerated the compound shown in the formula.
In the above-mentioned general formula, R
1Be H or CH
3, R
2Be that carbonatoms is 1～10 alkylidene group or CON (R
3)-R
4-, SO
2N (R
3)-R
4-, Rf is that carbonatoms is 4～20 perfluoroalkyl.R
3Be that carbonatoms is 1～4 alkyl, R
4Be that carbonatoms is 1～10 alkylidene group.
As the organosilicon compound among the present invention, refer in particular to compound with the low organosilicon chain of polarity, object lesson can illustration (modification) silicone oil, curing type silicone resin etc.As (modification) silicone oil, can enumerate have methylpropenyl, the modified silicon oil of epoxy group(ing), methyl alcohol isoreactivity organic radical etc.On the other hand; As the object lesson of curing type silicone resin, can use with the curing type silicone resin as the type of staple, also can use through with organosilicon type of the modifications such as graft polymerization of organic resins such as vinyl resin, urethane resin, epoxy resin, Synolac etc.Particularly from the affinity of polyester film and with the aspects such as intermiscibility of other composition that constitutes coating layer, the preferred use through with the graft polymerization of organic resin etc. and the organosilicon type of modification.
Through the coated film that the present invention makes, the weight that the static electricity resistance macromolecular compound is occupied in coating layer, the unit surface of preferred coated film is 5mg/m
2More than, 10mg/m more preferably
2More than.If the amount of static electricity resistance macromolecular compound is measured less than this, it is insufficient that static electricity resistance becomes mostly.
In addition, static electricity resistance macromolecular compound shared ratio in coating layer is unqualified, but upper limit weight ratio is generally 90%, is preferably 80%, and more preferably 60%.If the ratio of static electricity resistance macromolecular compound is higher than this value, cause the transparency of the coating layer weather resistance insufficient, coating layer that becomes to become insufficient mostly.In addition, lower limit is generally 10%, is preferably 20%.If the ratio of static electricity resistance macromolecular compound is lower than this value, possibly cause antistatic performance to become insufficient, perhaps become extremely thick in order to have filming of sufficient antistatic performance.Thicken if film, cause the adhesion of outward appearance, transparency deterioration or film, cost to rise easily, thus not preferred.
The static electricity resistance macromolecular compound in the coating layer and the ratio of thermosetting resin, in weight ratio, common preferred 5/1～1/5 scope, more preferably 4/1～1/2 scope.
If depart from this scope, there are the weather resistance of antistatic performance and coating layer, the trend that outward appearance worsens easily.
The contained ratio that is selected from the compound or derivatives thereof in alkyls compound, fluorine cpd, the organosilicon compound in the coating layer; Finally should determine by balance with other characteristic; As illustration; Can more preferably below 20%, further be preferably below 10% for below 30% of integral body of filming.If greater than this ratio, cause outward appearance to worsen easily and coating strength decline.In addition, preferably contain more than 1% of integral body of filming.Less than 1% o'clock that films, mostly the soil release characteristics of situation lower surface did not have marked difference sometimes with not containing at content.
Static electricity resistance coating layer of the present invention, the coating fluid that contains specific compound through coating on film is provided with, and especially preferably is provided with through the real-time coating that in film system film, is coated with among the present invention.
As required, can contain the composition beyond the mentioned component in the coating fluid of this moment.For example be tensio-active agent, tackiness agent, skimmer, coating activator, tackifier, organic system lubricant, releasing agent, organic granular, inorganic particle, inhibitor, UV light absorber, whipping agent, dyestuff, pigment etc.These compositions can use separately, also can be as required and with more than two kinds.
In addition; From the processing aspect, the stable aspect of operating environment aspect and coating fluid compsn, the coating fluid of this moment is preferably the aqueous solution or aqueous dispersions, but as long as in the scope that does not surmount main points of the present invention; Can be main medium with water, contain organic solvent.
Applying in real time is the method that the in-process in the polyester film manufacturing applies, particularly, and after melt extruding polyester, at biaxial stretch-formed back heat setting and the method that applies of any stage before rolling.Usually, can be to fusion, chilling and any one of the not drawing sheet that is essentially noncrystalline state that obtains, the monadic stretching membrane that is stretched at length direction (vertically) thereafter, the biaxially-stretched film before the heat setting apply.Wherein, preferably after monadic stretching membrane is applied, in tenter machine, carry out drying and, the method for heat-treating jointly with base material film again to horizontal stretching.According to such method, can make film simultaneously and coating layer is coated with, thereby have the advantage of manufacturing cost aspect; Because after coating, stretch, so carry out thin film cladding easily, the thermal treatment of after coating, implementing can reach adopts the unapproachable high temperature of other coating method, so the film-forming properties of coating layer improves, and coating layer and polyester film connect airtight securely.In addition, in coating layer, contain under the situation of crosslinking reaction property compound, have owing to the pyritous thermal treatment that applies in real time, the advantage that reaction residue is difficult to exist.Have reaction residue in the coating layer, when film is rolled into the roller shape, stick together sometimes etc., thus not preferred.Particularly in the present invention, containing under the situation of thermosetting resin,, greatly improving the weather resistance of coating layer because the high temperature that applies in real time carries out crosslinking reaction.
In addition, if the static electricity resistance compound of poor heat resistance, because the pyroprocessing of this method can cause decomposition, antistatic performance is not enough sometimes, but the excellent heat resistance of static electricity resistance macromolecular compound of the present invention is difficult for taking place the problems referred to above.
As the method for coating coating fluid on polyester film, for example, can use the coating technique shown in former rugged brave work, mould bookstore, distribution in 1979, " コ one テ イ Application グ mode " (" application pattern ").Can enumerate specifically that the coating of airblade coating, scraper plate, rod are coated with, scraper be coated with, technology such as compacting coating, impregnation coating, contrary roller coat cloth, transfer roller coating, photogravure coating, touch roll coating, casting are coated with, spray, the coating of curtain formula, calendering are coated with, extrusion coated, bar coating.
In addition, in order to improve coating, the binding property of coating agent on film, before coating, can implement chemical treatment or Corona discharge Treatment, plasma treatment etc. to film.
When observing as finally filming, the coating amount of static electricity resistance coating layer is generally 0.005～1.5g/m
2, be preferably 0.01～1.0g/m
2, 0.02～0.5g/m more preferably
2If coating amount is less than 0.005g/m
2, can not obtain sufficient performance sometimes; Surpass 1.5g/m
2Coating layer cause the adhesion, cost of outward appearance, transparency deterioration and film to be risen easily.
With electrostatic prevention film of the present invention when the protecting surface of optical member film, at the opposing face of static electricity resistance coating layer little adhesion layer is set.
Little adhesion of this moment is meant that the protective membrane that can be not cause damage and tackiness agent on optics, will temporarily not fit to optics peels off residually.For example, with this laminating be combined in stainless steel plate (SUS304) go up, 23 ℃ through after more than 6 hours, the peeling force when peeling off with 180 degree angles with 300mm/ minute speed is 2～60g/25mm.
As the type of tackiness agent, can enumerate thermofixation type, UV curing type, EB curing type, hot melt type etc., and, in order to suppress moving of weather resistance and tackiness agent, can suitably use the linking agent of isocyanates or epoxies.
As so little adhesion layer, can use acrylic adhesives or common known tackiness agents such as silicone based tackiness agent, rubber adhesive.Wherein, from viewpoints such as thermotolerances, preferred acrylic adhesives.Acrylic adhesives for example mostly uses with various propenoate or methacrylic ester and is staple, material that various monomers and its copolymerization are obtained, can be cured processing and forms through adding isocyanates solidifying agent etc. therein.
In the present invention, the thickness of little adhesion layer is preferably 3～100 μ m, more preferably 5～50 μ m.If thickness less than 3 μ m, can not get sufficient little adhesiving effect sometimes; On the other hand, the layer that surpasses 100 μ m is an extra quality and uneconomical, also impairs the transparency of protective membrane.
As required, can fit on little adhesion layer surface and peeled off (demoulding) film with what releasing agent was handled.
Embodiment
Below, enumerate embodiment the present invention is described in further detail, but the present invention is only otherwise surmount its main points, is not limited to following embodiment.Wherein, the evaluation method in embodiment and the comparative example and the treatment process of sample are described below.
(1) surperficial intrinsic resistance (Ω)
The high resistance tester that uses Japanese Hewlett-Packard Company to produce: HP4339B with measure electrode: HP16008B, in 23 ℃, the mensuration atmosphere of 50%RH, sample carried out 30 minutes moisture control after, measure surperficial intrinsic resistance value.
(2) scuff resistance
Use the friction testing machine and the special-purpose felt of peaceful physics and chemistry industry society, surperficial reciprocal 3 times of static electricity resistance coating layer.After this, the position that visual observations is nuzzled up is estimated with following benchmark.
Zero: the cosmetic variation of not observing the position of nuzzling up
△: the only visible vestige that nuzzles up
*: static electricity resistance coating layer cutting becoming powder
(3) wet fastness
Film was preserved cosmetic variation, the evaluation of visual assessment static electricity resistance coating layer 3 days in 40 ℃, the thermostatic bath of 90%RH.
Zero: the outward appearance no change
△: observe cosmetic variation such as albefaction slightly
*: observe cosmetic variation such as albefaction
(4) water tolerance of antistatic performance
Sample film was flooded 24 hours in 40 ℃ of warm water, use qualitative filter paper (TOYOADVANTEC produces " No2 ") to clamp gently then, remove the moisture of attachment removal, behind the drying at room temperature diel, adopt the method shown in above-mentioned (1) to measure surperficial intrinsic resistance.With the measured value of the measured value behind the warm water immersion before divided by warm water immersion, obtaining becomes several times value, estimates according to following benchmark.We can say the deterioration fewer (variation of the value before and after the warm water immersion is little) behind the warm water immersion, water tolerance is good more.
Zero: extremely good, the deterioration of the value before the warm water immersion is in 10 times
△: good, the deterioration of the value before the warm water immersion is between 10 times～20 times
*: bad, the deterioration of the value before the warm water immersion is more than 20 times
The polyester raw material that uses in following embodiment, the comparative example is described below.
(polyester 1): do not contain particle, limiting viscosity in fact and be 0.66 polyethylene terephthalate
(polyester 2): contain amorphous silica, limiting viscosity that 0.6 weight part median size is 2.5 μ m and be 0.66 polyethylene terephthalate
In addition, the compsn below coating composition uses.
(A1): the number-average molecular weight that the structural unit of structural unit and the following formula 5 of following formula 4 is obtained with the ratio copolymerization of weight ratio 95/5 is 20000 macromolecular compound
(A2): the number-average molecular weight that the structural unit that makes the structural unit of above-mentioned formula (4), the structural unit of above-mentioned formula (5), following formula (6) obtains with the ratio copolymerization of weight ratio 90/8/2 is 33000 macromolecular compound
(A3): the number-average molecular weight that the structural unit that makes the structural unit of above-mentioned formula (4), the structural unit of above-mentioned formula (5), above-mentioned formula (6) obtains with the ratio copolymerization of weight ratio 80/10/10 is 21000 macromolecular compound
(A4): the number-average molecular weight that the structural unit that makes the structural unit of above-mentioned formula (4), the structural unit of above-mentioned formula (5), above-mentioned formula (6) obtains with the ratio copolymerization of weight ratio 98/1/1 is 12000 macromolecular compound
(A5): the number-average molecular weight that the structural unit that makes the structural unit of above-mentioned formula (4), the structural unit of above-mentioned formula (5), following formula (7) obtains with the ratio copolymerization of weight ratio 85/10/5 is 18000 macromolecular compound
(B1) number-average molecular weight that is made up of the structural unit of above-mentioned formula (4) is 30000 macromolecular compound
(B2) number-average molecular weight that the structural unit of structural unit and the above-mentioned formula (6) of above-mentioned formula (4) is obtained with the ratio copolymerization of weight ratio 95/5 is 23000 macromolecular compound
(C1) the methylate crosslinkable resin of hexamethylolmelamine, the BECKAMINE J-101 that big Japanese ink chemical industry is produced
(C2) crosslinkable resin of methoxylation hexamethylolmelamine/urea copolymerization, the BECKAMINE MA-S that big Japanese ink chemical industry is produced
(D1) OPE water dispersion, the Ha イ テ Star Network E-8000 that eastern nation chemical industry is produced
(D2) in the reaction vessel of glass, add 80g as the CF that contains the propenoate of perfluoroalkyl
3(CF
2)
nCH
2CH
2OCOCH=CH
2(MV of n=5～11, n=9), 20.0g AAEM, 0.8g dodecyl mercaptans, 354.7g deoxidation pure water, 40.0g acetone, 1.0g C
16H
33N (CH
3)
3Cl and 3.0g C
8H
17C
6H
4O (CH
2CH
2O)
nH (n=8) adds 0.5g azo diisobutyl amidine dihydrochloride again, in nitrogen atmosphere, stirs, simultaneously 60 ℃ of fluorine resin emulsions of carrying out copolyreaction in 10 hours and obtaining
(E1) crosslinking catalyst of aminoresin class linking agent, the Catalyst O that big Japanese ink chemical industry is produced
(F1) polyoxyethylene lauryl ether (tensio-active agent: wherein, the mean polymerisation degree of ethylene oxide is 4)
Embodiment 1
Weight ratio mixed polyester 1 and polyester 2 according to 80/20; After the thorough drying; At 280～300 ℃ of heating and meltings, extrude by the T tube head and to be sheet, Yi Bian adopt the static adhesion method to make on its minute surface cooling drum that sticks to 40～50 ℃ of surface temperatures; Carry out cooling curing on one side, process not tensile polyethylene terephthalate film.Make this film pass through 85 ℃ warming mill group on one side, at length direction stretch 3.7 times on one side, the uniaxial orientation film obtained.At the coating composition shown in the single spreading below table 1 of this uniaxial orientation film.Then; This film is imported the tentering drawing machine, Yi Bian utilize its heat that coating composition is carried out drying, Yi Bian stretch 4.0 times at width with 100 ℃; Implement thermal treatment with 230 ℃ again, the biaxial orientation polyethylene glycol terephthalate's film that obtains thickness 38 μ m is provided with 0.03g/m
2The coated film of the static electricity resistance coating layer of amount.The characteristic of this film of expression in below table 2.
Embodiment 2～6
With the same operation of embodiment 1 in, change coating fluid as shown in table 1 obtains having at the base material film superimposed layer of thickness 38 μ m the coated film of the static electricity resistance coating layer of amount shown in the table 1.The characteristic of this film of expression in table 2.
Comparative example 1～3
With the same operation of embodiment 1 in, change coating fluid as shown in table 1 obtains having at the base material film superimposed layer of thickness 38 μ m the coated film of the static electricity resistance coating layer of amount shown in the table 1.The characteristic of this film of expression in table 2.
[table 1]
| Coating layer is formed | The solids component weight ratio | Glue spread (g/m 2) | |
| Embodiment 1 | A1/C1/E1/F1 | 60/40/2/5 | 0.03 |
| Embodiment 2 | A3/C1/E1/F1 | 60/40/2/5 | 0.03 |
| Embodiment 3 | A3/C1/E1/F1 | 40/50/2/5 | 0.05 |
| Embodiment 4 | A3/C2/E1/F1 | 40/30/2/5 | 0.03 |
| Embodiment 5 | A4/C2/E1/F1 | 40/30/2/5 | 0.03 |
| Embodiment 6 | A5/C2/E1/F1 | 40/30/2/5 | 0.03 |
| Comparative example 1 | B1/C1/E1/F1 | 60/40/2/5 | 0.03 |
| Comparative example 2 | B2/C1/E1/F1 | 60/40/2/5 | 0.03 |
| Comparative example 3 | B2/C2/E1/F1 | 40/30/2/5 | 0.03 |
The solids component weight of the coating layer compsn of the unit surface of the coated film that the glue spread in the above-mentioned table 1 is represented finally to obtain.
[table 2]
| Surface intrinsic resistance (Ω) | Water tolerance is estimated | |
| Embodiment 1 | 2×10 10 | ○ |
| Embodiment 2 | 5×10 10 | ○ |
| Embodiment 3 | 5×10 10 | ○ |
| Embodiment 4 | 4×10 10 | ○ |
| Embodiment 5 | 2×10 10 | △ |
| Embodiment 6 | 3×10 10 | ○ |
| Comparative example 1 | 1×10 10 | × |
| Comparative example 2 | 1×10 10 | × |
| Comparative example 3 | 3×10 10 | × |
Embodiment 7
Weight ratio mixed polyester 1 and polyester 2 according to 80/20; After the thorough drying; At 280～300 ℃ of heating and meltings, extrude by the T tube head and to be sheet, Yi Bian adopt the static adhesion method to make on its minute surface cooling drum that sticks to 40～50 ℃ of surface temperatures; Carry out cooling curing on one side, process not tensile polyethylene terephthalate film.Make this film pass through 85 ℃ warming mill group on one side, at length direction stretch 3.7 times on one side, the uniaxial orientation film obtained.At the coating composition shown in the single spreading below table 3 of this uniaxial orientation film.Then; This film is imported the tentering drawing machine, Yi Bian utilize its heat that coating composition is carried out drying, Yi Bian stretch 4.0 times at width with 100 ℃; Implement thermal treatment with 230 ℃ again, the biaxial orientation polyethylene glycol terephthalate's film that obtains thickness 38 μ m is provided with 0.03g/m
2The coated film of the static electricity resistance coating layer of amount.The characteristic of this film of expression in below table 4.
Then; As little adhesion layer; Add 10 parts of (solids component weight part) isocyanate curing agents (Japanese Polyurethane Co., Ltd. produces, CORONATE HL) with respect to the acrylic adhesives of 100 parts (solids component weight parts) (Imperial Chemical Industries Co., Ltd. produces, SG-800) and obtain coating fluid; Use excellent coating machine face coating this coating fluid opposite, make and film, little adhesion layer of thickness 20 μ m is set with 100 ℃ of dryings, curing 2 minutes with coating layer at above-mentioned film.Cover from it and be coated with organosilyl demoulding polyester film, process surface protection film.The film that obtains of operation has the excellent specific property shown in the table 4 like this, so, being attached on the optics when using actual as protective membrane, the identification when operability, inspection is good, thereby is suitable for use.
Embodiment 8～16
With the same operation of embodiment 1 in, change coating fluid as shown in table 1 obtains having at the base material film superimposed layer of thickness 38 μ m the coated film of the static electricity resistance coating layer of amount shown in the table 3.The characteristic of this film of expression in table 4.Further operate equally, obtain the surface protection film that the face relative with coating layer is provided with little adhesion layer with embodiment 7.The film that obtains has the excellent specific property shown in the table 4, so, being attached on the optics when using actual as protective membrane, the identification when operability, inspection is good, thereby is suitable for using.
Comparative example 4
With the same operation of embodiment 7 in, change coating fluid as shown in table 3 obtains at the base material film superimposed layer of thickness 38 μ m 0.03g/m being arranged
2The coated film of the static electricity resistance coating layer of amount.The characteristic of this film of expression in table 2.Further operate equally, obtain the surface protection film that the face relative with coating layer is provided with little adhesion layer with embodiment 7.The scuff resistance of the protective membrane that obtains is poor, so, being attached on the optics when using actual as protective membrane, surperficial existence can be thought and the damage of in attaching operation or conveyance operation etc., bringing into brings obstacle to inspection.In addition, because wet fastness is poor, so, also bring obstacle in the inspection after the high humidity held.
Comparative example 5
With the same operation of embodiment 7 in, change coating fluid as shown in table 3 obtains at the base material film superimposed layer of thickness 38 μ m 0.05g/m being arranged
2The coated film of the static electricity resistance coating layer of amount.The characteristic of this film of expression in table 4.Further operate equally, obtain the surface protection film that the face opposite with coating layer is provided with little adhesion layer with embodiment 7.The wet fastness of the film that obtains is poor, so, be attached on the optics when using actual as protective membrane, after the high humidity held, the whole surface gonorrhoea that becomes is brought obstacle to inspection.
Comparative example 6
With the same operation of embodiment 1 in, change coating fluid as shown in table 3 obtains at the base material film superimposed layer of thickness 38 μ m 0.05g/m being arranged
2The coated film of the static electricity resistance coating layer of amount.The characteristic of this film of expression in table 4.Further operate equally, obtain the surface protection film that the face opposite with coating layer is provided with little adhesion layer with embodiment 7.The wet fastness of the film that obtains is poor, so, be attached on the optics when using actual as protective membrane, after the high humidity held, the whole surface gonorrhoea that becomes is brought obstacle to inspection.
Comparative example 7
With the same operation of embodiment 7 in, except not being coated with, same operation obtains the polyester film of thickness 38 μ m.The characteristic of this film of expression in table 4.Further operate equally, obtain being provided with the surface protection film of little adhesion layer at single face with embodiment 7.The surperficial intrinsic resistance of the protective membrane that obtains is high, antistatic performance is poor, so, be attached on the optics when using actual as protective membrane, adhere to twining on hand when peeling off, absorption dirt on every side, operability worsens significantly.
[table 3]
The solids component weight of the coating layer compsn of the unit surface of the coated film that the glue spread in the table 3 is represented finally to obtain.
[table 4]
| Surface intrinsic resistance (Ω) | Scuff resistance | Wet fastness | Situation as the protective membrane use | |
| Embodiment 7 | 3×10 10 | ○ | ○ | Well |
| Embodiment 8 | 9×10 9 | △ | ○ | Well |
| Embodiment 9 | 4×10 10 | ○ | ○ | Well |
| Embodiment 10 | 4×10 10 | ○ | ○ | Well |
| Embodiment 11 | 4×10 10 | ○ | ○ | Well |
| Embodiment 12 | 2×10 10 | △ | ○ | Well |
| Embodiment 13 | 2×10 10 | ○ | ○ | Well |
| Embodiment 14 | 5×10 10 | ○ | ○ | Well |
| Embodiment 15 | 2×10 10 | ○ | ○ | Well |
| Embodiment 16 | 3×10 10 | ○ | ○ | Well |
| Comparative example 4 | 9×10 9 | × | × | Obstacle is arranged |
| Comparative example 5 | 3×10 10 | △ | × | Obstacle is arranged |
| Comparative example 6 | 3×10 10 | △ | × | Obstacle is arranged |
| Comparative example 7 | 6×10 14 | ○ | ○ | Obstacle is arranged |
More than; Use embodiment that the present invention has been described in further detail; But in the scope that does not break away from main points of the present invention; Numerical range of the present invention regulation also comprises all scope dictates that the numerical value with above-mentioned any embodiment uses as threshold value certainly, should be considered to record in this manual.
Utilizability on the industry
Film of the present invention can be applicable to the various uses that requires antistatic performance.
Claims (3)
1. static electricity resistance film is characterized in that:
On a face of polyester film, has the coating layer that contains the static electricity resistance macromolecular compound; Wherein, This static electricity resistance macromolecular compound has the textural element shown in following structural formula 1 and 2 as repeating unit, and the shared ratio in said macromolecular compound of the textural element shown in the said structural formula 1 is in weight ratio; Be 70～99%
In the above-mentioned formula (1), R
1And R
2Independent respectively, be that Wasserstoffatoms or carbonatoms are 1～3 alkyl, X
-It is the negatively charged ion of 1 valency;
In the above-mentioned formula (2), R
3Be that Wasserstoffatoms or carbonatoms are 1～3 alkyl, R
4Be-O-or-NH-, R
5Be that carbonatoms is 1～6 alkylidene group.
2. static electricity resistance film as claimed in claim 1 is characterized in that:
The static electricity resistance film is used for surface protection film.
3. a protecting surface of optical member is used polyester film, it is characterized in that:
On the face of the opposite side of the coating layer of the described polyester film of claim 1, has little adhesion layer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007097361A JP5376770B2 (en) | 2007-04-03 | 2007-04-03 | Polyester film for surface protection film and polyester film for surface protection of optical member |
| JP2007097182A JP5376769B2 (en) | 2007-04-03 | 2007-04-03 | Antistatic film |
| JP097182/2007 | 2007-04-03 | ||
| JP097361/2007 | 2007-04-03 | ||
| PCT/JP2008/000708 WO2008120465A1 (en) | 2007-04-03 | 2008-03-25 | Antistatic film, polyester film for surface-protecting film, and polyester film for protecting surface of optical member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101668795A CN101668795A (en) | 2010-03-10 |
| CN101668795B true CN101668795B (en) | 2012-07-18 |
Family
ID=39979086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800108786A Active CN101668795B (en) | 2007-04-03 | 2008-03-25 | Antistatic film, polyester film for surface-protecting film, and polyester film for protecting surface of optical member |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5376769B2 (en) |
| CN (1) | CN101668795B (en) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4306996A (en) * | 1980-05-05 | 1981-12-22 | Calgon Corporation | Electroconductive polymer composition |
| JPH0725914B2 (en) * | 1987-12-04 | 1995-03-22 | ダイアホイルヘキスト株式会社 | Antistatic polyester film |
| JPH01174539A (en) * | 1987-12-28 | 1989-07-11 | Diafoil Co Ltd | Production of antistatic polyester film |
| JPH06160327A (en) * | 1992-11-24 | 1994-06-07 | Tdk Corp | Humidity sensor element and manufacture thereof |
| JPH0726223A (en) * | 1993-07-08 | 1995-01-27 | Dainippon Printing Co Ltd | Highly transparent and slightly sticky antistatic protective film |
| JP3749555B2 (en) * | 1995-07-24 | 2006-03-01 | 帝人株式会社 | Easy-adhesive water-based coating and polyester film coated with the same |
| JP2003292654A (en) * | 2002-04-04 | 2003-10-15 | Teijin Dupont Films Japan Ltd | Antistatic laminated polyester film |
| JP4101602B2 (en) * | 2002-10-03 | 2008-06-18 | 帝人デュポンフィルム株式会社 | Antistatic polyester film |
| JP2004149653A (en) * | 2002-10-30 | 2004-05-27 | Teijin Dupont Films Japan Ltd | Antistatic laminated polyester film |
| TW200420633A (en) * | 2003-03-25 | 2004-10-16 | Teijin Dupont Films Japan Ltd | Antistatic layered polyester film |
| JP2007118224A (en) * | 2005-10-25 | 2007-05-17 | Mitsubishi Polyester Film Copp | Decorative sheet and polyester film therefor |
-
2007
- 2007-04-03 JP JP2007097182A patent/JP5376769B2/en active Active
-
2008
- 2008-03-25 CN CN2008800108786A patent/CN101668795B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101668795A (en) | 2010-03-10 |
| JP5376769B2 (en) | 2013-12-25 |
| JP2008255177A (en) | 2008-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103476890B (en) | Adhesive sheet | |
| CN102869738B (en) | Water-dispersed acrylic system binder composition and adhesive sheet | |
| JP6249617B2 (en) | Surface protection film | |
| CN104342052A (en) | Surface protective film and optical component | |
| JP5174303B2 (en) | the film | |
| JPH10298539A (en) | Antistatic agent, and coating and adhesive agent containing the same | |
| KR101981503B1 (en) | Release film for surface-protective film | |
| JP2003154616A (en) | Laminated film and surface protective film | |
| CN104342054A (en) | Surface protective film and optical component | |
| CN104342053A (en) | Surface protective film and optical component | |
| JP5313455B2 (en) | Surface protection film | |
| JP2002060707A (en) | Surface protective film and its laminate | |
| CN104099047A (en) | Black silane primers for improving the adhesion of adhesive tapes on glass surfaces | |
| KR100688256B1 (en) | Pressure sensitive adhesive film for protection of surface and manufacturing method thereof | |
| CN101668795B (en) | Antistatic film, polyester film for surface-protecting film, and polyester film for protecting surface of optical member | |
| KR101985178B1 (en) | Surface-protective film and optical component attached with the same | |
| KR20060009640A (en) | Surface protective film | |
| JP5376770B2 (en) | Polyester film for surface protection film and polyester film for surface protection of optical member | |
| KR20070082728A (en) | Composition of coating for surface protection and protective film using same | |
| JP6532177B2 (en) | Release film for antistatic surface protection film, and antistatic surface protection film for optical film to which it is laminated | |
| JPH06344514A (en) | Release film | |
| WO2015120018A1 (en) | Antistatic coated polyester film | |
| KR20100014984A (en) | Antistatic film, polyester film for surface-protecting film, and polyester film for protecting surface of optical member | |
| JP7345955B2 (en) | Adhesive composition for protective film, adhesive containing the same, and adhesive sheet using the same | |
| KR101460524B1 (en) | Manufacturing method of anti-static polyester film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: MITSUBISHI CHEMICAL Corp. Address before: Tokyo, Japan Patentee before: MITSUBISHI RAYON Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170930 Address after: Tokyo, Japan Patentee after: MITSUBISHI RAYON Co.,Ltd. Address before: Tokyo, Japan Patentee before: MITSUBISHI PLASTICS, Inc. |
|
| TR01 | Transfer of patent right |