CN101184619A - Mold release film - Google Patents
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- CN101184619A CN101184619A CNA2006800190090A CN200680019009A CN101184619A CN 101184619 A CN101184619 A CN 101184619A CN A2006800190090 A CNA2006800190090 A CN A2006800190090A CN 200680019009 A CN200680019009 A CN 200680019009A CN 101184619 A CN101184619 A CN 101184619A
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- mold release
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Abstract
A mold release film comprising a coating layer and a mold release layer provided in this order on one surface of a polyester film which is stretched at least in the monoaxial direction, the coating layer comprising an aluminum chelate compound and/or a zirconium chelate compound, the mold release film having a critical destruction load (CDC) on the mold release side of 40 mN or higher, and the quantity of an oligomer extracted with dimethylformamide from the surface of the mold release layer after treatment at 180 DEG for 10 minutes being 1.5 mg/m<SUP>2</SUP> or less. In the mold release film, the quantity of an oligomer precipitated therefrom is quite small and the adhesion of the mold release layer to a coating film is good.
Description
Technical field
The present invention relates to mold release film, be specifically related to the oligomer amount of separating out few, remove for example be suitable for LCD (below, sometimes LCD be in brief note) in employed Polarizer, phasic difference plate etc. the manufacturing of LCD member with, plasma display plate (below, sometimes PDP be in brief note) the member manufacturing with, organic electroluminescent (below, sometimes organic EL be in brief note) the member manufacturing with wait, various display member manufacturing with beyond, also be suitable for the mold release film of various optical applications etc.
Background technology
Up to now, with the polyester film be the mold release film of base material be applied to liquid crystal Polarizer, the manufacturing of phasic difference board member with, PDP member manufacturing with, organic electroluminescent member manufacturing use etc., various display member manufacturing is used etc., various optical applications etc.The problem of using as mold release film can be set forth in and separate out the variety of issue that brings to the oligomer on release layer surface in the manufacturing process under the high temperature.
In recent years, along with developing by leaps and bounds of IT (Information Technology) field, in the quality of the mold release film of when improving display members such as making LCD, PDP, organic EL, using, separate out the situation that variety of issue together is in obviousization with oligomer.
For being suitable for above-mentioned various uses, expect that not only release property is good, and the foreign matter on film surface is few.That is, pay attention to seeing promptly so-called visual purposes through light owing to particularly also exist, so, even the foreign matter on not debatable film surface also can become big problem in common film purposes.
For example, the manufacturing process of enumerating the liquid crystal Polarizer is as an example, this manufacturing process is by by batching behind adhesive phase applying mold release film and the Polarizer to roll-shaped operation etc. constitutes again, and it is generally acknowledged that oligomer separates out through the drying process after the adhesive coating time.Separate out to the oligomer on release layer surface then attached to the surface of the object adhesive phase of its applying, fit together when making LCD problems such as the brightness step-down of the LCD that obtains sometimes at the Polarizer that the adhesive phase that has adhered to oligomer will be housed and glass substrate.
In recent years, exist for the purpose of the visuality that improves LCD and further improve the tendency of the brightness of display screen, the problems referred to above promptly become a serious problem.
On the other hand, also exist the purpose that reduces production cost for improving productivity, be accompanied by the high speed of manufacturing process and improve the tendency of the baking temperature in the drying process especially, above-mentioned oligomer is in a kind of easier situation of separating out.
Though sneak into etc. in the inspection operation of optical assessment at the display capabilities that carries out the liquid crystal Polarizer, tone, contrast, foreign matter, taked the measure to prevent that defective work from dispatching from the factory with visual method or lens examination goods, but when use is attached with the mold release film of oligomer of crystallization, still exist to sneak into and be judged as defective work, make the problem of the decrease in yield etc. of goods because of foreign matter.
Patent documentation 1: Japanese patent laid-open 6-16941 communique
Patent documentation 2: Japanese patent laid-open 7-3215 communique
Patent documentation 3: the Japan Patent spy opens the 2000-44904 communique
Patent documentation 4: the Japan Patent spy opens the 2000-238441 communique
Summary of the invention
The present invention promptly is the invention of In view of the foregoing making, solution as this problem, a kind of mold release film is provided, the oligomer amount of separating out of this mold release film is few, the film adhesive of release layer is good, except be suitable for for example liquid crystal member such as liquid crystal Polarizer, phasic difference plate manufacturing with, PDP member manufacturing with, organic EL member manufacturing use etc., various display member manufacturing with, also be suitable for various optical applications etc.
The present inventor addresses the above problem to have carried out deep research, found that, the mold release film that has specific coating layer and release layer by use can address the above problem, thereby has finished the present invention.
Promptly, of the present inventionly to be intended to a kind of mold release film, it is characterized in that: it is at least along the mold release film that is provided with coating layer, release layer on the one side of the polyester film of uniaxial tension successively, above-mentioned coating layer contains aluminium chelate compound and/or zirconium chelate, the critical destruction load (CDL) of the stripping surface of mold release film is more than the 40mN, is 1.5mg/m by dimethyl formamide from the amount with the oligomer of the release layer surface extraction of 180 ℃ of heat treatments after 10 minutes
2Below.
The effect of invention
According to the present invention, can provide that the oligomer amount of separating out is few, the good mold release film of film adhesive of release layer, have very high industrial value.
The specific embodiment
Below, describe the present invention in detail.The polyester film that constitutes mold release film of the present invention both can constitute by individual layer, but also lamination constitutes, and for example, except 2 layers, 3 layers formation, only otherwise exceed main idea of the present invention, also can be the multilayer more than 4 layers or 4 layers, and there is no particular limitation.
In the present invention, the polyester that is used for polyester film both can be the homopolymerization polyester, also can be copolyester.Under situation about constituting by the homopolymerization polyester, the homopolymerization polyester that optimization aromatic dicarboxylic acids and aliphatic diol polycondensation obtain.As aromatic dicarboxylic acid, can enumerate terephthalic acid (TPA), 2,6-naphthalene dicarboxylic acids etc.As aliphatic diol, can enumerate ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol etc.As representational polyester, can enumerate PETG (PET) etc.On the other hand,, can enumerate M-phthalic acid, phthalic acid, terephthalic acid (TPA), 2, one or more of 6-naphthalene dicarboxylic acids, adipic acid, decanedioic acid, hydroxycarboxylic acid (for example, P-hydroxybenzoic acid etc.) etc. as the dicarboxylic acids composition of copolyester; As diol component, can enumerate ethylene glycol, diethylene glycol, propane diols, butanediol, 1,4-cyclohexanedimethanol, season pentanediol etc. one or more.No matter use which kind of polyester, the polyester that the present invention mentions is meant that the ethylene glycol terephthalate unit is generally the polyester that 60 moles of % are above, be preferably the above PETG of 80 moles of % etc.
In the present invention, preferably in polyester layer, cooperate main purpose for the particle of easy sliding property is provided.For the kind that cooperates particle, so long as the particle of easy sliding property can be provided, then there is no particular limitation.As concrete example, can enumerate the particle of silica, calcium carbonate, magnesium carbonate, brium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminium oxide, titanium oxide etc.In addition, also can use the special public clear 59-5216 communique of Japan Patent, Japan Patent spy to open the hear resistance organic granular that clear 59-217755 communique etc. is put down in writing.As other the example of hear resistance organic granular, can enumerate thermosetting urea resin, thermosetting phenolic resin, thermosetting epoxy resin, benzoguanamine resin etc.Can also use in the production of polyester operation part precipitation, differential with the metallic compound of catalyst etc. to loose and obtain separate out particle.
Coating of particles is not particularly limited, and can adopt Any shape such as spherical, block, bar-shaped, flat.In addition, also be not particularly limited for its hardness, proportion, color etc.As required, can be also with two or more these a series of particles.
The average grain diameter of particle is generally 0.01～3 μ m, is preferably 0.01～1 μ m.Under the situation of average grain diameter less than 0.01 μ m, the easy aggegation of particle sometimes, dispersed insufficient; On the other hand, under the situation of average grain diameter greater than 3 μ m, the surface roughness of film is too high, sometimes coating generation problem such as during release layer in subsequent handling.
The content of the above-mentioned particle in the polyester layer is generally 0.001～5 weight %, is preferably 0.005～3 weight %.Under the situation of granule content less than 0.001 weight %, easy the to be sliding property of film is insufficient sometimes; On the other hand, add above under the situation of 5 weight %, film is transparent insufficient sometimes.
Method as add above-mentioned particle in polyester layer is not particularly limited, and can adopt known method in the past.For example, though all can add this particle in any stage of the polyester that make to constitute each layer, preferably add this particle after stage of esterification step or ester exchange reaction operation finish, the promotion polycondensation reaction gets final product.In addition, can adopt following method etc. to carry out: to utilize the mixing extruder that passage is housed, will be dispersed in the slurry of the particle in ethylene glycol or the water etc. and the method that polyester raw material mixes; Perhaps, utilize mixing extruder, the method that dried granules and polyester raw material are mixed.
In addition, in polyester film of the present invention, as required, except that above-mentioned particle, can add known in the past antioxidant, antistatic additive, heat stabilizer, lubricant, dyestuff, pigment etc.
Constitute the thickness of the polyester film of mold release film of the present invention,, then be not particularly limited, be generally 5～250 μ m, be preferably 12～188 μ m as long as making in the scope of film as film.
Below, the Production Example of polyester film of the present invention is specifically described, but the present invention is not limited to following Production Example.At first, preferably use above-mentioned polyester film raw material, the fusion sheet material that utilizes the chill roll cooling curing to extrude from the mouth mould obtains not stretched sheet.At this moment,, need to improve sheet material and the adhesive force that rotates drum cooler, preferably adopt static to apply attachment method and/or liquid coating attachment method for improving the flatness of sheet material.Then, the not stretched sheet that obtains along biaxial stretching.At this moment, at first, utilize the stretching-machine of roller or stenter mode, along the above-mentioned not stretched sheet of simple tension.Draft temperature is generally 70～120 ℃, is preferably 80～110 ℃; Stretching ratio is generally 2.5～7 times, is preferably 3.0～6 times.Then, stretch along direction perpendicular to the 1st draw direction.Draft temperature is generally 70～170 ℃; Stretching ratio is generally 3.0～7 times, is preferably 3.5～6 times.Then, the state or 30% of tension with interior lax state under, heat-treat with 180～270 ℃ temperature, obtain the biaxial stretching film.In above-mentioned stretching, also can adopt the method for carrying out the stretching more than two stages along unidirectional.At this moment, preferably under the condition that finally is in above-mentioned scope respectively, carry out along two-way stretching ratio.
In addition, about the manufacturing of polyester film of the present invention, also can adopt biaxial stretch-formed method simultaneously.Biaxial stretch-formed method is being generally 70～120 ℃, being preferably under 80～110 ℃ simultaneously, under the controlled state of temperature, along the method for operating direction and the above-mentioned not stretched sheet of width while stretch orientation.Stretching ratio is 4～50 times with the area dynameter, is preferably 7～35 times, more preferably 10～25 times.Then, then, the state or 30% of tension with interior lax state under, heat-treat with 170～250 ℃ temperature, obtain the biaxial stretching film.The biaxial stretching device can adopt known in the past drawing process such as spiral way, scalable manner, linear drive mode when adopting above-mentioned stretching mode.
In the stretching process of above-mentioned polyester film, can also implement the what is called coating pulling method (online coating) that the film surface is handled.Adopting the coating pulling method under the situation that coating layer is set on the polyester film, stretching and coating can be carried out simultaneously, and can corresponding stretching ratio and reduce the thickness of coating layer, therefore, can make suitable film as polyester film.
Below, the formation of the coating layer that constitutes mold release film of the present invention is described.For coating layer, can adopt above-mentioned coating pulling method (online coating), also can adopt the so-called off-line coating on the film that coating outside the system formerly makes.Can adopt any method in two kinds of methods.
In mold release film of the present invention, because the amount (OL) of the oligomer of separating out after the heat treatment (180 ℃, 10 minutes) need be 1.5mg/m
2Below, so, need coating to contain the coating layer of aluminium chelate compound and/or zirconium chelate (A) as necessary condition.Can and use aluminium chelate compound and zirconium chelate.
As the object lesson of aluminium chelate compound, can the illustration aluminium tris(acetylacetonate), two (ethyl acetoacetate) aluminium of single acetyl acetone, two n-butoxy single acetyl ethyl acetate aluminium, diisopropoxy single acetyl methyl acetate aluminium etc.In addition, (editor: Shanxi three, gold east help under the mountain at " frame Bridge agent Ha Application De Block Star Network "; (strain) great achievement society equals into 2 years versions) in, also record object lesson.As above-mentioned aluminium chelate compound, can only use a kind of, also can be suitably and with two or more.
As the object lesson of zirconium chelate, can the illustration zirconium acetate, n Propanoic acid zirconium, n-butyric acie zirconium, tetrem acyl acetone zirconium, single acetyl acetone zirconium, bis-acetylacetonate zirconium etc.In addition, (editor: Shanxi three, gold east help under the mountain at " frame Bridge drug Ha Application De Block Star Network "; (strain) great achievement society equals into 2 years versions) in, also record object lesson.As above-mentioned zirconium chelate, can only use a kind, also can be suitably also with more than 2 kinds.
Mold release film of the present invention for preventing to make the film adhesive of release layer and polyester film good when oligomer from separating out well, preferably also contains alkoxysilane oligomer in above-mentioned coating layer.
Alkoxysilane oligomer is represented with a following average group accepted way of doing sth (1).For example, can illustration Japan Patent spy open 2002-88155 number open communique, Japan Patent spy and open the compound that 2005-8755 number open communique put down in writing.
R
kR
1 mSi(OR
2)
nO
(4-k-m-n)/2 (1)
In the above-mentioned formula, R represents to be selected from and does not replace or the alkyl of replacement and the base more than a kind or 2 kinds in the aryl; R
1Expression contains the base of aliphatic unsaturated double-bond; R
2The expression carbon number is that 1～3 alkyl, carbon number are that 2 or 3 acyl group or carbon number are 3～5 alkoxyalkyl; K, m and n are for satisfying the number of relational expression 0≤k＜1.5,0.01≤m≤1,0.5≤k+m≤1.8,0.01≤n≤2.5,1≤k+m+n≤3 simultaneously.
As the object lesson of R, can the illustration methyl, alkyl such as ethyl, propyl group, butyl, hexyl, octyl group, decyl; Cycloalkyl such as cyclohexyl; Thiazolinyl such as vinyl, pi-allyl; Aryl such as phenyl, tolyl; Perhaps replace chloromethyl, chloropropyl, trifluoro propyl of the part or all of hydrogen atom of these bases etc. with halogen atom; The cyanoethyl that replaces with cyano group etc.; The glycidoxy propyl group that replaces with epoxy radicals, epoxycyclohexyl ethyl etc.; The metacryloxy propyl group that replaces with (methyl) acrylic, propenyloxy group propyl group etc.; The aminopropyl that replaces with amino, aminoethyl aminopropyl etc.; The sulfydryl propyl group that replaces with sulfydryl etc.
As R
1Object lesson, can illustration contain aliphatic categories such as vinyl, pi-allyl, isopropenyl, 1-cyclobutenyl, 2-cyclobutenyl, 3-cyclobutenyl; Ester ring type classes such as 2-cyclohexenyl group, 3-cyclohexenyl group, 2-VCH base; The fragrant same clans such as 2-ethenylphenyl, 3-ethenylphenyl, 2-allyl phenyl; Substituting groups such as 3-(methyl) propenyloxy group propyl group etc.
As R
2Object lesson, can illustration be selected from the alkyl of methyl, ethyl, propyl group, isopropyl; Acyl groups such as acetyl group; Alkoxyalkyls such as methoxy ethyl, ethoxyethyl group, propoxyl group ethyl, methoxy-propyl, ethoxycarbonyl propyl.
As the object lesson of commercial articles, can enumerate " KR-401N ", " X-40-9227 " that chemical industrial company of SHIN-ETSU HANTOTAI produces, " X-40-9247 ", " KR-510 ", " KR-9218 ", " KR-213 ", " KR-217 ", " X-41-1053 ", " X-40-1056 ", " X-41-1805 ", " X-41-1810 ", " X-40-2651 ", " X-40-2652B ", " X-40-2655A ", " X-40-2761 ", " X-40-2672 " etc.
For the aluminium chelate compound in the coating layer that constitutes mold release film of the present invention and/or the content (weight %) of zirconium chelate and alkoxysilane oligomer, separate out for preventing oligomer more well, preferably it satisfies following formula (1) and formula (2) simultaneously.
1≤W(A)≤70 (1)
20≤W(B)≤99 (2)
In the following formula, aluminium chelate compound and/or the content (weight %) of zirconium chelate and the content (weight %) of alkoxysilane oligomer in the coating layer of W (A) and W (B) expression formation mold release film.In addition,, bring in the scope of negative effect for effect of the present invention, can in coating layer, contain aluminium chelate compound, zirconium chelate and alkoxysilane oligomer composition in addition for suppressing the oligomer amount of separating out and improving film adhesive.
More preferably the scope of W (A) is that the scope of 2～50 weight %, W (B) is 30～99 weight %.Arbitrary content exceeds under the situation of above-mentioned scope in the content of aluminium chelate compound and/or zirconium chelate and alkoxysilane oligomer, sometimes be difficult to guarantee simultaneously to suppress the amount of separating out of the oligomer of separating out and the demoulding adhesive force of release layer by the release layer surface of (180 ℃, 10 minutes) after the heat treatment.
The organic solvent of the coating fluid that uses when in the present invention, being formed in the formation coating layer is not particularly limited.Can use known in the past organic solvents such as toluene, MEK (MEK), ethyl acetate, hexane, methyl iso-butyl ketone (MIBK), 2-propyl alcohol.The organic solvent that uses both can only use a kind of, also can be used in combination (for example, toluene/MEK).
In addition, in the scope that does not influence effect of the present invention, can and use crosslinking agent (C) in coating layer.As the object lesson of crosslinking agent (C), can enumerate the urea class, melamine class, guanamine class, acrylic amide, polyamide-based compound, epoxide, aziridines compound, block polyisocyanate, silane coupler, titanium coupling agent, zircoaluminate coupling agent etc. of methylolation or alkyl alcoholization.
Be adherence and the slickness of further improving coating layer, can also add mineral-type particle (D).As the object lesson of mineral-type particle (D), can enumerate silica, aluminium oxide, kaolin, calcium carbonate, titanium oxide, barium salt etc.
Moreover, as required, also can add defoamer, coating performance improver, thickener, organic series lubricant agent, organic family macromolecule particle, antioxidant, ultra-violet absorber, blowing agent, dyestuff etc.
Under the situation of coating pulling method (online coating),, preferably make polyester film: the coating fluid that is about the benchmark modulation about 0.1 weight %～50 weight % in coating on the polyester film by solid constituent according to following coating main points for above-mentioned a series of compound.
The coating weight (dry back) that constitutes coating layer set on the polyester film of mold release film of the present invention is generally 0.005～1g/m
2, be preferably 0.005～0.5g/m
2At the not enough 0.005g/m of coating weight
2Situation under, the uniformity of coating thickness is insufficient sometimes, after heat treatment, the amount of the oligomer of being separated out by painting layer surface increases sometimes.On the other hand, surpass 1g/m in coating weight
2Situation under, produce the problem of slickness reduction etc. sometimes.
In the present invention, as the method that coating layer is set, can adopt known in the past coating process such as reverse intaglio plate rubbing method, direct intaglio plate rubbing method, roller rubbing method, mouthful mould rubbing method, scraper rubbing method, curtain coating method.About coating process, example on the books in " コ one テ イ Application グ mode " (distribution in 1979 of former rugged brave the work of Omaki bookstore).
Condition of cure when in the present invention, forming coating layer on polyester film is not particularly limited.For example, adopting coating pulling method (online coating) to be provided with under the situation of coating layer, usually according to 170～280 ℃ 3～40 seconds down, be preferably 200～280 ℃ down 3～40 seconds benchmark heat-treat.On the other hand, adopting the off-line coating to be provided with under the situation of coating layer, usually according to 80～200 ℃ 3～40 seconds down, be preferably 120～180 ℃ down 3～40 seconds benchmark heat-treat.
In addition, no matter be coating pulling method (online coating) or off-line coating, all can as required and use heat treatment and the irradiation of ultraviolet ray irradiation isoreactivity energy-ray.
Below, the formation of release layer of the present invention is described.Constitute the release layer of mold release film of the present invention, both can in the film manufacturing process of above-mentioned coating pulling method (online coating) etc., be arranged on the polyester film, also can outside system, be coated with the surface of the film of formerly making, adopt so-called off-line coating, can adopt any method.For coating pulling method (online coating), be not limited to following operation, for example, in biaxial stretching one by one, especially stretch for the first time finish after, for the second time stretch before, implement coating and handle.Adopting the coating pulling method under the situation that release layer is set on the polyester film, can when stretching, be coated with, and can reduce the thickness of coating layer according to stretching ratio, make suitable mold release film.
In addition, for improving release property, preferably in the release layer that constitutes mold release film of the present invention, contain the curing type silicone resin.Can use with the type of curing type silicone resin, also can use type by the modified organic silicon that obtains with organic resin glycerol polymerizations such as polyurethane resin, epoxy resin, alkyd resins etc. as main component.
As the kind of curing type silicone resin, can use any curing reaction types such as add-on type, condensed type, ultraviolet hardening, electron ray curing type, no-solvent type.If enumerate concrete example, " KS-774 " that then can chemical industrial company of illustration SHIN-ETSU HANTOTAI produces, " KS-775 ", " KS-778 ", " KS-779H ", " KS-847H ", " KS-856 ", " X-62-2422 ", " X-62-2461 ", " X-62-1387 ", " KNS-3051 ", " X-62-1496 ", " KNS320A ", " KNS316 ", " X-62-1574A/B ", " X-62-7052 ", " X-62-7028A/B ", " X-62-7619 ", " X-62-7213 ", " YSR-3022 " that organosilicon company of GE Toshiba produces, " TPR-6700 ", " TPR-6720 ", " TPR-6721 ", " TPR6500 ", " TPR6501 ", " UV9300 ", " UV9425 ", " XS56-A2775 ", " XS56-A2982 ", " UV9430 ", " TPR6600 ", " TPR6604 ", " TPR6605 ", " SM3200 ", " SM3030 ", " DKQ3-202 " that Dong Li Dow Corning Corporation produces, " DKQ3-203 ", " DKQ3-204 ", " DKQ3-205 ", " DKQ3-210 ", " SRX357 ", " SRX211 ", " SD7220 ", " LTC750A ", " LTC760A ", " SP7259 ", " BY24-468C ", " SP7248S ", " BY24-452 ", " SP7268S ", " SP7265S ", " LTC1000M ", " LTC1050L ", " SYLOFF7900 ", " SYLOFF7198 ", " SYLOFF22A " etc.For the fissility of regulating release layer etc., can also be also with peeling off conditioning agent.
In the present invention, as the method that release layer is set, can adopt known in the past coating process such as reverse intaglio plate rubbing method, direct intaglio plate rubbing method, roller rubbing method, mouthful mould rubbing method, scraper rubbing method, curtain coating method on polyester film.About coating process, example on the books in " コ one テ イ Application グ mode " (distribution in 1979 of former rugged brave the work of Omaki bookstore).
In the present invention, the condition of cure during for formation release layer on polyester film is not particularly limited.For example, adopting coating pulling method (online coating) to be provided with under the situation of release layer, usually according to 170～280 ℃ 3～40 seconds down, preferred 200～280 ℃ down 3～40 seconds benchmark heat-treat.On the other hand, adopting the off-line coating to be provided with under the situation of release layer, usually according to 80～200 ℃ 3～40 seconds down, preferred 100～180 ℃ down 3～40 seconds benchmark heat-treat.In addition, no matter adopt any method in coating pulling method (online coating) or the off-line coating, all can be as required, and shine with heat treatment and ultraviolet ray irradiation isoreactivity energy-ray.In addition, the energy as being used for by active energy beam irradiation causing curing can use known in the past energy source device.
Release layer be coated with loading amount, consider from the aspect of coating, be generally 0.005～1g/m
2, be preferably 0.005～0.5g/m
2At application quantity not sufficient 0.005g/m
2Situation under, consider from the aspect of coating, unstable sometimes, and be difficult to be filmed uniformly.On the other hand, be coated with loading amount above 1g/m
2And carry out under the thick situation about being coated with reduction such as the film adhesive of release layer self, curing property sometimes.
In the present invention, when on coating layer, release layer being set, after can be after coating layer is set film being batched earlier release layer is set again, perhaps also can release layer be set on coating layer continuously after coating layer is set, can adopt arbitrary method.
In the mold release film of the present invention, in the scope that does not influence purport of the present invention, can tack coat, antistatic additive layer, oligomer are set on the face of release layer separate out coating layers such as preventing layer not being provided with.
Moreover, for the polyester film that constitutes mold release film, can implement surface treatments such as sided corona treatment, plasma treatment in advance.
After mold release film of the present invention heat-treated (180 ℃, 10 minutes), need be 1.5mg/m from the amount (OL) of the oligomer of release layer surface extraction by dimethyl formamide
2Below, be preferably 1.0mg/m
2Below, 0.5mg/m more preferably
2Below.Surpass 1.5mg/m at OL
2Situation under, for example, when making liquid crystal member, be used under the situation of adhesive phase protection purposes, the transparency that adhesive takes place reduces, the problems such as bonding force reduction of adhesive phase.In addition, " oligomer " among the present invention is defined as: after the heat treatment because of the cyclic trimer in the low-molecular-weight thing that crystallization separated out by the surface takes place.
By having the coating layer that contains aluminium chelate compound and/or zirconium chelate, can reach the amount (OL) of above-mentioned oligomer.
According to the viewpoint that prevents that oligomer from separating out, in mold release film of the present invention, the amount (Al) of the aluminium element that is detected from the release layer surface by the fluorescent X-ray determinator and the amount (Zr) of zr element are generally more than the 1.0kcps, are preferably more than the 2.0kpcs.In addition, contain at the same time under the situation of these two kinds of compounds of aluminium chelate compound and zirconium chelate, the total amount of preferred aluminium element amount (Al) and zr element amount (Zr) is above-mentioned scope.Under the situation of aluminium element amount (Al) and the not enough 1.0kcps of zr element amount (Zr), it is not enough that the oligomer of the mold release film that obtains is sometimes separated out preventing property.
And then, mold release film of the present invention, for improving the film adhesive of release layer, the critical destruction load (CDL) on release layer surface need be preferably more than the 45mN for more than the 40mN, more preferably more than the 50mN.Under the situation of the not enough 40mN of CDL, release layer is not enough with respect to the film adhesive of polyester film, is difficult to tackle the purposes of the film adhesive of special requirement release layer.
For example contain alkoxysilane oligomer and aluminium chelate compound and/or contain aluminium chelate compound and/or the coating layer of zirconium chelate by having, can reach above-mentioned critical destruction load (CDL).As concrete method, can enumerate the coupling agent that makes coating layer contain ormal weight.In addition, preferably also and use chelate.
Embodiment
Below, by embodiment, the present invention is illustrated in further detail.But only otherwise exceed main idea of the present invention, be not limited to following embodiment.The assay method that adopts among the present invention is as described below.
(1) mensuration of the inherent viscosity of polyester:
Precision weighing has been removed and immiscible other component of polymer of polyester and the polyester 1g of pigment, adds the mixed solvent 100ml of phenol/tetrachloroethanes=50/50 (weight ratio), makes its dissolving, measures down at 30 ℃.
(2) average grain diameter (d
50: mensuration μ m):
The numerical value of the accumulative total (weight basis) 50% that the equivalent grain size of using centrifugal type particle size distribution device (the SA-CP3 type that Shimadzu Scisakusho Ltd produces) to measure distributes is as average grain diameter.
(3) to the mensuration of the Al amount of element of the stripping surface side of mold release film:
Extract the face that is provided with release layer 24 hours of test portion sample in advance with the 2-propyl alcohol, use filter paper (Toyo Roshi Kaisha, Ltd. company produces, pattern: " 5C ") to filter extract then.After the air dry, utilize fluorescent X-ray determinator (Shimadzu Scisakusho Ltd produces, pattern " XRF-1500 "), adopt FP (Fundamental Parameter Method) method, measure the Al amount of element of the filter paper face that filters the extract side.Condition determination is as described below.
The target of X-ray tube: Rh4.0kW
Analyzing crystal: pentaerythrite
2θ：144.58°
Detector: SC
Tube current: 95mA
Tube voltage: 40kv
(4) to the mensuration of the Zr amount of element of the stripping surface side of mold release film:
Extract the face that is provided with release layer 24 hours of test portion sample in advance with the 2-propyl alcohol, use filter paper (Tokyo Roshi Kaisha, Ltd. company produces, pattern: " 5C ") to filter extract then.After the air dry, utilize fluorescent X-ray determinator (Shimadzu Scisakusho Ltd produces, pattern " XRF-1500 "), adopt FP (Fundamental Parameter Method) method, measure the Zr amount of element of the filter paper face that filters the extract side.Condition determination is as described below.
The target of X-ray tube: Rh4.0kW
Analyzing crystal: LiF
2θ：22.550
Detector: SC (scintillation counter)
Tube current: 95mA
Tube voltage: 40kv
(5) mensuration of the amount (OL) of the oligomer that extracts by the stripping surface side of mold release film:
In advance in air with 180 ℃ of heating without heat treated mold release film 10 minutes.The length and width that then this film after the heat treatment are close to as far as possible opened upper end are 10cm, and height is the inside of the chest of 3cm, is the shape of box-shaped.Be provided with under the situation of coating layer, making the coating aspect for inboard.Then, in the chest made from said method, add DMF (N, dinethylformamide) 4ml, place after 3 minutes, reclaim DMF.The DMF that reclaims is offered liquid chromatograph (Shimadzu Scisakusho Ltd produces, pattern " LC-7A "), try to achieve the amount of the oligomer among the DMF, with the area of this value, as the amount (mg/m of film surface oligomer divided by the film of DMF contact
2).
The amount of the oligomer among the DMF is tried to achieve (absolute standard curve method) according to the peak area ratio of the peak area of the peak area of standard specimen and test samples.Standard specimen is following to make: accurately weighing divides the oligomer of getting (cyclic trimer) in advance, it is dissolved among the DMF of accurate weighing and makes.The concentration of standard specimen is preferably the scope of 0.001～0.01mg/ml.The condition determination of liquid chromatograph is as described below.
Mobile phase A: acetonitrile
Mobile phase B:2% acetic acid aqueous solution
Post: Mitsubishi Chemical Ind produces " MCI GEL ODS 1HU "
Column temperature: 40 ℃
Flow velocity: 1ml/ branch
Detect wavelength: 254nm
(6) evaluation of the critical destruction load (CDL) of the stripping surface of mold release film:
The scraping experiment machine (CSR-02 type) that utilizes LESCA company to produce is measured 12 times the stripping surface of test portion film, casts out maximum and minimum of a value then, and the mean value of getting remaining 10 determination datas is as critical destruction load (CDL).Condition determination is as described below.
Sensor: No.1
Load (9/mm): 238.75
Contact pilotage diameter (μ m): 15
Excitation level (μ m): 80
Load Rate (mN/mm): calculate automatically
Gain＝1000
Stage Angle(deg)：12.00
Stage Speed(μm/s)：10.0
(7) promote the evaluation (practical characteristic substitute evaluation) of the film adhesive of mold release film:
In constant temperature and humidity cabinet, under 60 ℃, the atmosphere of 70%RH, place test portion film 48 hours (2 days) afterwards, take out sample film.Then, with the stripping surface of hand friction test portion film 5 times, judge the degree that comes off of release layer according to following determinating reference.
Zero: do not see come off (the actual degree of using no problem) of filming
△: filming bleaches, but do not come off (the actual degree of using no problem)
*: confirming films comes off (the problematic degree of actual use)
Adopt following method, be modulated at the polyester film that uses in embodiment and the comparative example.
Production Example 1 (PETG P1)
100 parts of dimethyl terephthalate (DMT)s, 60 parts of ethylene glycol and four water magnesium acetates are added in the reactor for 0.09 part, and in heat temperature raising, distillation for removing methanol carries out ester exchange.Begin to need 4 hours to be warming up to 230 ℃ from reaction, finish ester exchange reaction in fact.Then, add 0.01 part of the silica dioxide granule that 0.04 part in acid phosphate ester ethylene glycol slurry, 0.03 part of antimony trioxide, average grain diameter are 1.5 μ m.Then, make temperature reach 280 ℃ with 100 minutes, pressure reaches 15mmHg, after this, reduces pressure gradually, finally reduces to 0.3mmHg.After 4 hours, internal system is recovered normal pressure, obtains inherent viscosity and be 0.61 PETG P1.Production Example 2 (PETG P2)
Add average grain diameter and be 0.1 part of the silica dioxide granule of 1.5 μ m,, in addition, operate equally, obtain PETG P2 with Production Example 1 to replace in Production Example 1, adding 0.01 part of the silica dioxide granule that average grain diameter is 1.5 μ m.
Production Example 3 (PETG P3)
Add average grain diameter and be 0.01 part of the titan oxide particles of 1.5 μ m, to replace in Production Example 1, adding 0.01 part of the silica dioxide granule that average grain diameter is 1.5 μ m.In addition, operate equally, obtain PETG P3 with Production Example 1.
The compound that uses in the formation of coating layer is as described below.
Aluminium chelate compound (A1): aluminium tris(acetylacetonate)
Aluminium chelate compound (A2): two (ethyl acetoacetate) aluminium of single acetyl acetone
Zirconium chelate (A3): tri acetylacetonato zirconium
Zirconium chelate (A4): two (ethyl acetoacetate) zirconiums of single acetyl acetone
Alkoxysilane oligomer (B1): X-41-1056 (SHIN-ETSU HANTOTAI's chemical production)
Alkoxysilane oligomer (B2): X-40-2652B (SHIN-ETSU HANTOTAI's chemical production)
Crosslinking agent (C): γ-glycidoxypropyltrime,hoxysilane
Particle (D): Ludox (average grain diameter 60nm)
Embodiment 1:
In inactive gas atmosphere, with the PETG P1 that makes in the Production Example 1 with 180 ℃ of dryings 4 hours, utilization melt extrudes machine 290 ℃ of following fusions, and extrude from the mouth mould, employing applies the electrostatic adherence method, be set at cooling curing on 40 ℃ the chill roll in surface temperature, obtain not stretched sheet.
At first, the not stretched sheet that obtains is carried out biaxial stretching one by one, that is, 95 ℃ longitudinally (MD direction) stretch by 3.6 times stretching ratio, again it is imported stenter, stretch along laterally (TD direction) stretching ratio by 4.3 times.Then, with 230 ℃ of heat fixations that carried out for 3 seconds, obtaining thickness is the PET film of 38 μ m.
Then, with the aluminium chelate compound (A1) of toluene/MEK mixed solvent (blending ratio is 1: 1 (weight ratio)) dilution 30 weight % and the alkoxysilane oligomer (B1) of 70 weight %, making concentration is the coating fluid of 3 weight %.Then, adopt reverse intaglio plate rubbing method to be coated with above-mentioned coating fluid, make coating weight (dry back) be 0.05g/m
2, then with 120 ℃ of heat treatments of carrying out for 10 seconds.
Then, with the curing type silicone resin (" KS-774 " that chemical company of SHIN-ETSU HANTOTAI produces) of MEK/ toluene mixed solvent (blending ratio is 1: 1 (weight ratio)) dilution 99 weight % and the curing agent (" PL-3 " that chemical company of SHIN-ETSU HANTOTAI produces) of 1 weight %, making concentration is the releasing agent coating fluid of 2 weight %.Then, adopt reverse intaglio plate rubbing method on above-mentioned coating layer, to be coated with the releasing agent coating fluid, make coating weight (dry back) be 0.1g/m
2,, obtain mold release film with 120 ℃ of heat treatments of carrying out for 10 seconds.
Embodiment 2～4:
In embodiment 1, coating fluid is formed the coating fluid composition that changes to shown in the following table 1, in addition,, obtain mold release film according to making with embodiment 1 identical operations.
Embodiment 5:
In embodiment 1, PETG P1 is changed to PETG P2.In addition, according to making, obtain mold release film with embodiment 1 identical operations.
Embodiment 6:
As the releasing agent coating fluid, with the curing type silicone resin (" KS-772 " that chemical industrial company of SHIN-ETSU HANTOTAI produces) of MEK/ toluene mixed solvent (blending ratio is 1: 1 (weight ratio)) dilution 98 weight %, the silicone oil (" KF-353 " that chemical company of SHIN-ETSU HANTOTAI produces) of 1 weight % and the curing agent (" PL-3 " that chemical company of SHIN-ETSU HANTOTAI produces) of 1 weight %, making concentration is the releasing agent coating fluid of 2 weight %.Then, except that using above-mentioned releasing agent coating fluid,, obtain mold release film according to making with embodiment 1 identical operations.
Embodiment 7:
In embodiment 1, PETG P1 is changed to PETG P3, in addition,, obtain mold release film according to making with embodiment 1 identical operations.
Embodiment 8:
In embodiment 1, the drying condition when coating layer is set changes to the drying condition shown in the following table 1, in addition, according to making with embodiment 1 identical operations, obtains mold release film.
Embodiment 9～13 and comparative example 1～3:
In embodiment 1, the smears composition that changes to shown in the following table 1 is formed in the smears, in addition,, obtain mold release film according to making with embodiment 1 identical operations.
The property list of each mold release film that obtains in the foregoing description and the comparative example is shown in the following table 1.
[table 1]
| The drying condition of coating layer | (weight %) A1/A2/B1/B2/C/D is formed in the smears | OL (mg/m 2) | CDL (mN) | Film adhesive | ||
| Baking temperature (℃) | Drying time (second) | |||||
| Embodiment 1 | 120 | 10 | 30/0/70/0/0/0 | 0.2 | 55 | ○ |
| Embodiment 2 | 120 | 10 | 0/30/70/0/0/0 | 0.3 | 52 | ○ |
| Embodiment 3 | 120 | 10 | 30/0/0/70/0/0 | 0.4 | 50 | ○ |
| Embodiment 4 | 120 | 10 | 0/30/0/70/0/0 | 0.6 | 51 | ○ |
| Embodiment 5 | 120 | 10 | 30/0/0/70/0/0 | 0.4 | 55 | ○ |
| Embodiment 6 | 120 | 10 | 30/0/70/0/0/0 | 0.2 | 55 | ○ |
| Embodiment 7 | 120 | 10 | 30/0/70/0/0/0 | 0.2 | 54 | ○ |
| Embodiment 8 | 80 | 10 | 30/0/70/0/0/0 | 0.8 | 48 | ○ |
| Embodiment 9 | 120 | 10 | 1/0/99/0/0/0 | 1.3 | 50 | ○ |
| Embodiment 10 | 120 | 10 | 85/0/15/0/0/0 | 0.1 | 45 | ○ |
| Embodiment 11 | 120 | 10 | 80/0/15/0/5/0 | 0.1 | 48 | ○ |
| Embodiment 12 | 120 | 10 | 83/0/15/0/0/2 | 0.2 | 45 | ○ |
| Embodiment 13 | 120 | 10 | 78/0/15/0/5/2 | 0.2 | 46 | ○ |
| Comparative example 1 | 120 | 10 | 100/0/0/0/0/0 | 0.1 | 30 | × |
| Comparative example 2 | 120 | 10 | 0/0/100/0/0/0 | 2.3 | 48 | △ |
| Comparative example 3 | 120 | 10 | Be not coated with | 3.8 | 30 | × |
Embodiment 14:
In inactive gas atmosphere, with the PETG P1 that makes in the Production Example 1 with 180 ℃ of dryings 4 hours, utilization melt extrudes machine 290 ℃ of fusions, and extrude from the mouth mould, employing applies the electrostatic adherence method, be set at cooling curing on 40 ℃ the chill roll in surface temperature, obtain not stretched sheet.
At first, the not stretched sheet that obtains is carried out biaxial stretching one by one, that is, stretch along the stretching ratio of MD direction, again it is imported stenter, stretch along the stretching ratio of TD direction by 4.3 times by 3.6 times at 95 ℃.Then, with 230 ℃ of heat fixations that carried out for 3 seconds, obtaining thickness is the PET film of 38 μ m.
Secondly, with the zirconium chelate (A3) of MEK/ toluene mixed solvent (blending ratio is 1: 1 (weight ratio)) dilution 30 weight % and the alkoxysilane oligomer (B1) of 70 weight %, making concentration is the coating fluid of 3 weight %.Then, adopt reverse intaglio plate rubbing method to be coated with above-mentioned coating fluid, make coating weight (dry back) be 0.05g/m
2, then with 120 ℃ of heat treatments of carrying out for 10 seconds.
Then, with the curing type silicone resin (" KS-774 " that chemical company of SHIN-ETSU HANTOTAI produces) of MEK/ toluene mixed solvent (blending ratio is 1: 1 (weight ratio)) dilution 99 weight % and the curing agent (" PL-3 " that chemical company of SHIN-ETSU HANTOTAI produces) of 1 weight %, making concentration is the releasing agent coating fluid of 2 weight %.Then, adopt reverse intaglio plate rubbing method on above-mentioned coating layer, to be coated with the releasing agent coating fluid, make coating weight (dry back) be 0.1g/m
2,, obtain mold release film with 120 ℃ of heat treatments of carrying out for 10 seconds.
Embodiment 15～17
In embodiment 14, coating fluid is formed the coating fluid composition that changes to shown in the following table 2, in addition,, obtain mold release film according to making with embodiment 14 identical operations.
Embodiment 18:
In embodiment 14, PETG P1 is changed to PETG P2, in addition,, obtain mold release film according to making with embodiment 14 identical operations.
Embodiment 19:
As the releasing agent coating fluid, with the curing type silicone resin (" KS-772 " that chemical industrial company of SHIN-ETSU HANTOTAI produces) of MEK/ toluene mixed solvent (blending ratio is 1: 1 (weight ratio)) dilution 98 weight %, the silicone oil (" KF-353 " that chemical company of SHIN-ETSU HANTOTAI produces) of 1 weight % and the curing agent (" PL-3 " that chemical company of SHIN-ETSU HANTOTAI produces) of 1 weight %, making concentration is the releasing agent coating fluid of 2 weight %.Then, except that using above-mentioned releasing agent coating fluid,, obtain mold release film according to making with embodiment 14 identical operations.
Embodiment 20:
In embodiment 14, PETG P1 is changed to PETG P3.In addition, according to making, obtain mold release film with embodiment 14 identical operations.
Embodiment 21:
In embodiment 14, the drying condition when coating layer is set changes to the drying condition shown in the following table 2, in addition, according to making with embodiment 14 identical operations, obtains mold release film.
Embodiment 22～26 and comparative example 4:
In embodiment 14, the smears composition that changes to shown in the following table 2 is formed in the smears, in addition,, obtain mold release film according to making with embodiment 14 identical operations.
The property list of each mold release film that obtains in the foregoing description and the comparative example is shown in the following table 2.
[table 2]
| The drying condition of coating layer | (weight %) A3/A4/B1/B2/C/D is formed in the smears | OL (mg/m 2) | CDL (mN) | Film adhesive | ||
| Baking temperature (℃) | Drying time (second) | |||||
| Embodiment 14 | 120 | 10 | 30/0/70/0/0/0 | 0.2 | 54 | ○ |
| Embodiment 15 | 120 | 10 | 0/30/70/0/0/0 | 0.3 | 52 | ○ |
| Embodiment 16 | 120 | 10 | 30/0/0/70/0/0 | 0.4 | 50 | ○ |
| Embodiment 17 | 120 | 10 | 0/30/0/70/0/0 | 0.6 | 51 | ○ |
| Embodiment 18 | 120 | 10 | 30/0/0/70/0/0 | 0.4 | 54 | ○ |
| Embodiment 19 | 120 | 10 | 30/0/70/0/0/0 | 0.2 | 54 | ○ |
| Embodiment 20 | 120 | 10 | 30/0/70/0/0/0 | 0.2 | 54 | ○ |
| Embodiment 21 | 80 | 10 | 30/0/70/0/0/0 | 0.8 | 48 | ○ |
| Embodiment 22 | 120 | 10 | 1/0/99/0/0/0 | 1.3 | 50 | ○ |
| Embodiment 23 | 120 | 10 | 85/0/15/0/0/0 | 0.1 | 45 | ○ |
| Embodiment 24 | 120 | 10 | 80/0/15/0/5/0 | 0.1 | 48 | ○ |
| Embodiment 25 | 120 | 10 | 83/0/15/0/0/2 | 0.2 | 45 | ○ |
| Embodiment 26 | 120 | 10 | 78/0/15/0/5/2 | 0.2 | 46 | ○ |
| Comparative example 4 | 120 | 10 | 100/0/0/0/0/0 | 0.1 | 30 | × |
Embodiment 27
In embodiment 14, the coating fluid composition is changed to A1/A3/B1/B2/C/D=15/15/70/0/0/0 (weight %), in addition,, obtain mold release film according to making with embodiment 14 identical operations.The OL of the mold release film that obtains is 0.3 (mg/m
2), CDL is 52 (mN), film adhesive is zero.
Though more than illustrated and related to the present invention who is considered to up to now tool practicality and preferred embodiment, but the present invention is not limited to disclosed embodiment in the patent specification, it must be understood that for, can in the scope of the main idea of not violating the invention of understanding according to the integral body of claims and specification or thought, carry out suitable change, also be in the technical scope of the present invention with the situation of this change.Also it must be understood that into, also put down in writing any combination the various embodiments described above mode of (also comprising comparative example).For example, it must be understood that into, the combination of numerical value that obtains in each embodiment and the scope of each embodiment is also within the scope of the invention.In addition, the Japanese patent application that the application proposed based on May 31st, 2005 (special hope 2005-159049 number and 2005-159050 number), and quote in full above-mentioned patent.
Industrial applicibility
Mold release film of the present invention except being suitable for optical applications that the manufacturing such as the display member such as LCD, PDP, organic electroluminescent uses etc., also is suitable for not wishing to exist on the film surface especially the purposes of the foreign matter that produces because of oligomer.
Claims (6)
1. mold release film is characterized in that:
It is at least along the mold release film that is provided with coating layer, release layer on the one side of the polyester film of uniaxial tension successively, described coating layer contains aluminium chelate compound and/or zirconium chelate, the critical destruction load (CDL) of the stripping surface of mold release film is more than the 40mN, is 1.5mg/m by dimethyl formamide from the amount with the oligomer of the release layer surface extraction of 180 ℃ of heat treatments after 10 minutes
2Below.
2. mold release film as claimed in claim 1 is characterized in that:
Coating layer also contains alkoxysilane oligomer.
3. mold release film as claimed in claim 2 is characterized in that:
Alkoxysilane oligomer is the compound shown in the following average group accepted way of doing sth (1),
R
kR
1 mSi(OR
2)
nO
(4-k-m-n)/2 (1)
In the formula, R represents to be selected from and does not replace or the alkyl of replacement and the base more than a kind or 2 kinds in the aryl; R
1Expression contains the base of aliphatic unsaturated double-bond; R
2The expression carbon number is that 1～3 alkyl, carbon number are that 2 or 3 acyl group or carbon number are 3～5 alkoxyalkyl; K, m and n are for satisfying the number of relational expression 0≤k＜1.5,0.01≤m≤1,0.5≤k+m≤1.8,0.01≤n≤2.5,1≤k+m+n≤3 simultaneously.
4. as claim 2 or 3 described mold release film, it is characterized in that:
The aluminium chelate compound in setting coating layer and/or the content of zirconium chelate (A) are the content of W (A) (weight %), alkoxysilane oligomer when being W (B) (weight %), satisfy following formula (1) and (2) simultaneously,
1≤W(A)≤70 (1)
20≤W(B)≤99 (2)。
5. as each described mold release film in the claim 1～4, it is characterized in that:
Coating layer also contains crosslinking agent (C).
6. as each described mold release film in the claim 1～5, it is characterized in that: coating layer also contains mineral-type particle (D).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP159049/2005 | 2005-05-31 | ||
| JP2005159049A JP4916131B2 (en) | 2005-05-31 | 2005-05-31 | Release film |
| JP159050/2005 | 2005-05-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101184619A true CN101184619A (en) | 2008-05-21 |
Family
ID=37555767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800190090A Pending CN101184619A (en) | 2005-05-31 | 2006-05-24 | Mold release film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4916131B2 (en) |
| CN (1) | CN101184619A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762367A (en) * | 2010-02-23 | 2012-10-31 | 三菱树脂株式会社 | Biaxially oriented polyester film and release film comprising same |
| CN104781359A (en) * | 2012-11-22 | 2015-07-15 | 三菱树脂株式会社 | Substrate-less double-sided adhesive sheet |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4916132B2 (en) * | 2005-05-31 | 2012-04-11 | 三菱樹脂株式会社 | Release film |
| JP4993484B2 (en) * | 2007-04-11 | 2012-08-08 | 三菱樹脂株式会社 | Release film |
| JP5026843B2 (en) * | 2007-04-11 | 2012-09-19 | 三菱樹脂株式会社 | Release film |
| JP2009196176A (en) * | 2008-02-20 | 2009-09-03 | Mitsubishi Plastics Inc | Mold release film |
| JP2009196178A (en) * | 2008-02-20 | 2009-09-03 | Mitsubishi Plastics Inc | Mold release film |
| JP5322675B2 (en) * | 2009-02-02 | 2013-10-23 | 株式会社きもと | Sheet, laminate and touch panel |
| JP2012232495A (en) * | 2011-05-02 | 2012-11-29 | Mitsubishi Plastics Inc | Release polyester film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2854330B2 (en) * | 1989-07-14 | 1999-02-03 | キヤノン株式会社 | Tunable optical filter |
| JP3993373B2 (en) * | 2000-09-14 | 2007-10-17 | 信越化学工業株式会社 | Polyorganosiloxane compound and coating composition containing the same |
| JP2004177719A (en) * | 2002-11-28 | 2004-06-24 | Mitsubishi Polyester Film Copp | Mold releasing film |
| JP2004188814A (en) * | 2002-12-12 | 2004-07-08 | Mitsubishi Polyester Film Copp | Release film |
| JP4150922B2 (en) * | 2003-10-10 | 2008-09-17 | Ｊｓｒ株式会社 | Method for forming laminate |
| JP4916132B2 (en) * | 2005-05-31 | 2012-04-11 | 三菱樹脂株式会社 | Release film |
-
2005
- 2005-05-31 JP JP2005159049A patent/JP4916131B2/en active Active
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2006
- 2006-05-24 CN CNA2006800190090A patent/CN101184619A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762367A (en) * | 2010-02-23 | 2012-10-31 | 三菱树脂株式会社 | Biaxially oriented polyester film and release film comprising same |
| CN104781359A (en) * | 2012-11-22 | 2015-07-15 | 三菱树脂株式会社 | Substrate-less double-sided adhesive sheet |
| CN104781359B (en) * | 2012-11-22 | 2017-04-05 | 三菱树脂株式会社 | Without base material double-sided adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006334806A (en) | 2006-12-14 |
| JP4916131B2 (en) | 2012-04-11 |
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