CN104395077A

CN104395077A - Biaxially stretched polyester film for mold release

Info

Publication number: CN104395077A
Application number: CN201380034394.6A
Authority: CN
Inventors: 南條一成
Original assignee: Unitika Ltd
Current assignee: Unitika Ltd
Priority date: 2012-07-02
Filing date: 2013-07-01
Publication date: 2015-03-04
Anticipated expiration: 2033-07-01
Also published as: KR20150035549A; WO2014007187A1; JPWO2014007187A1; TWI541124B; KR101816619B1; CN104395077B; TW201406525A; JP6165141B2; HK1207035A1

Abstract

A biaxially stretched polyester film which has a mold release layer on at least one surface of a polyester film base. This biaxially stretched polyester film for mold release is characterized in that: the mold release layer contains 100 parts by mass of an acid-modified polyolefin resin, wherein the ratio of the acid-modified component is 1-10% by mass, and 1-50 parts by mass of a crosslinking agent; the biaxially stretched polyester film has an elongation at break of 350-500% and a breaking stress of 10-30 MPa at 120 DEG C; and the biaxially stretched polyester film has a thickness unevenness of 5% or less.

Description

Demoulding biaxially oriented polyester film

Technical field

The present invention relates to demoulding biaxially oriented polyester film, more specifically relate to the demoulding biaxially oriented polyester film as the useful release property excellence of the process paper of shaping rear stripping.

Background technology

The polyester film taking PETG as representative owing to having excellent mechanical property, heat resistance, chemical resistance, so be widely used in industrial field and industrial circle.Wherein, the film that can use as release materials is as process materials, protective material, and demand significantly expands in recent years, particularly widely uses in electronic motor field.

As the purposes of release materials; the protective material for the adhesion bonding plane of the sticky material such as adhesive sheet, adhesive tape or process materials can be enumerated; for the manufacture of the process materials of printing distributing board, flexible printing patch panel, multi-layer printed circuit board etc.; as the polarizer of liquid crystal display parts, the protective material of polarizer; further, release materials is also in the shaping middle use of structure.

The structure enumerated as the purposes of above-mentioned release materials shaping, such as can enumerate the film implementing to print insert mould and injection moulding carry out decorating simultaneously in-molded, this forming method due to beautiful decoration can be carried out with low cost, so the inside components, electronic equipment etc. of automobile housing etc. shaping in widely use.

In-moldedly roughly be divided into two kinds of modes, a kind of is the mode of stripping film after injection moulding, and another kind becomes to be integrated with products formed and film stays the mode of formed body at injection moulding caudacoria.When the mode of the latter, film owing to needing to follow complicated 3D shape, so use the acrylic film that molding processibility is very high.

On the other hand, in the former mode, because the stretched film heat resistance of polyester, dimensional stability, printing, thickness and precision are high and cheap, so widely use.But molding processibility, the release property of the stretched film of polyester are sometimes insufficient.Therefore, in patent document 1, disclose containing stretching agent, under the atmosphere of 120 DEG C, extend 400% time stress be the non-oriented polyester film of the scope of 2 ~ 20MPa.

In order to use polyester film as release materials, generally, taking polyester film as base material, giving release property by carrying out the release layer containing releasing agent stacked to film.And, carry out stacked method as to release layer, propose the method much carrying out on film surface being coated with.The stacked viewpoint such from the filming of release layer of being undertaken by coating is effective method.

Such as, use the smears of solvent system, Patent Document 2 discloses the method for the stacked dimethyl silicone polymer containing vinyl, Patent Document 3 discloses the method for stacked fluorine compounds in addition.

In addition, also can enumerate the smears using water system, stacked wax class (patent document 4), low-molecular-weight organo-silicon compound, fluorine system surfactant are as the method for release layer, but the release materials obtained exists these releasing agents when peeling off is transferred to and is reduced by adhesion by such problem such as the function of adhesion such as adherence.

Therefore, disclose the method for stacked organic siliconresin in patent document 5,6, Patent Document 7 discloses the method for stacked fluorine resin in addition, patent document 8,9 discloses the method for the vistanex of stacked special composition in addition.

Prior art document

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2010-070581 publication

Patent document 2: Japanese Unexamined Patent Publication 2002-182037 publication

Patent document 3: Japanese Unexamined Patent Publication 2007-002066 publication

Patent document 4: Japanese Patent Publication 05-062897 publication

Patent document 5: Japanese Unexamined Patent Publication 07-196984 publication

Patent document 6: Japanese Unexamined Patent Publication 2005-125656 publication

Patent document 7: Japanese Unexamined Patent Publication 2004-114620 publication

Patent document 8: Japanese Unexamined Patent Publication 2007-031639 publication

Patent document 9: Japanese Unexamined Patent Publication 2002-265719 publication

Summary of the invention

In above-mentioned patent document 1, the polyester film of record is owing to being unstretching film, so do not have sufficient thickness and precision.

The release layer recorded in patent document 2, in order to carry out stacked, solidification, needs process at high temperature.In addition, in patent document 3,7 record resin not only price is high, and use after discarded burning disposal in be difficult to burning and produce toxic gas.All have in addition in order to coated release agent equably and the problem using a large amount of organic solvents such.

Use the stacked in fact low-molecular-weight olefin-based wax of olefin-based waterborne liquid recorded in the patent document 4 of the smears of water system to form, and containing surfactant, therefore may pollute by adhesion.The adaptation deficiency of the release layer recorded in patent document 5,6 and base material, and release properties etc. are also insufficient.

Actual not to the evaluation of release sheet material in patent document 8.And because smears contains surfactant, so may pollute by adhesion.In addition, the resin price used in patent document 9 is high, and fusing point is also high, therefore in order to form the process at high temperature of release sheet material needs.

The present invention in order to solve the problem, in order to obtain sufficient thickness and precision, even if the shaping demoulding biaxially oriented polyester film being suitable as release materials with large deformation also can be implemented after wanting to provide a kind of stretching.

The present inventor etc. conduct in-depth research to solve above-mentioned problem, found that by having specific elongation at break, at least one side of biaxially oriented polyester film of fracture strength arranges the release layer containing the vistanex of specific composition and the crosslinking agent of specified quantitative, above-mentioned problem can be solved, thus complete the present invention.

That is, purport of the present invention is as follows.

(1) demoulding biaxially oriented polyester film, is characterized in that, is the biaxially oriented polyester film having release layer at least one mask of polyester film base material,

The ratio that release layer contains sour altered contents is acid-modified polyolefin resin 100 mass parts and crosslinking agent 1 ~ 50 mass parts of 1 ~ 10 quality %,

Biaxially oriented polyester film elongation at break at 120 DEG C is 350 ~ 500%, and fracture strength is 10 ~ 30MPa,

The uneven thickness rate (thick body spot) of biaxially oriented polyester film is less than 5%.

(2) demoulding biaxially oriented polyester film Gen Ju (1), it is characterized in that, the ratio that polyester film base material contains diethylene glycol composition is copolymerization PETG layer (A layer) and at least each 1 layer of the amorphous polyester resin layer (B layer) of 4 ~ 12mol%.

(3) demoulding biaxially oriented polyester film Gen Ju (1), is characterized in that, release layer is further containing polyvinyl alcohol, and its content is 5 ~ 200 mass parts relative to acid-modified polyolefin resin 100 mass parts.

(4) demoulding biaxially oriented polyester film Gen Ju (2), is characterized in that, A layer contains antioxidant 0.1 ~ 1 quality %.

(5) demoulding biaxially oriented polyester film Gen Ju (2), is characterized in that, the copolymerization PETG forming A layer utilizes germanium catalyst to be polymerized.

(6) according to the demoulding biaxially oriented polyester film according to any one of (1) ~ (5), it is characterized in that, biaxial stretch-formed face multiplying power is 9.0 ~ 12.3 times.

Demoulding biaxially oriented polyester film of the present invention is good due to thickness and precision, and has specific elongation at break and fracture strength, in-moldedly also possesses good mouldability and release property, can carry out implementing the shaping of beautiful decoration so be namely used in.In addition, demoulding biaxially oriented polyester film of the present invention is owing to must not contain the releasing agents such as wax class, low-molecular-weight organo-silicon compound, surfactant, so can not pollute by adhesion when peeling off, in addition, due to not containing the releasing agent comprising the halogens such as fluorine, so also few to the load of environment when discarding.

Detailed description of the invention

Demoulding biaxially oriented polyester film of the present invention is the polyester film having release layer at least one mask of polyester film base material, and at 120 DEG C, elongation at break is 350 ~ 500%, and fracture strength is 10 ~ 30MPa, and uneven thickness rate is less than 5%.

For demoulding biaxially oriented polyester film of the present invention, be required to be 350 ~ 500% as mentioned above at the elongation at break of 120 DEG C, be preferably 370 ~ 500%, be more preferably 400 ~ 500%.Elongation at break lower than 350% when, do not follow film when implementing in-molded, sometimes break, sometimes damage the attractive in appearance of products formed.Preferred elongation at break is high, but sometimes can not get thickness and precision with the film that the mode of elongation at break more than 500% manufactures.

For demoulding biaxially oriented polyester film of the present invention, be required to be 10 ~ 30MPa as mentioned above at the fracture strength of 120 DEG C, be preferably 10 ~ 25MPa, be more preferably 10 ~ 20MPa.When fracture strength is lower than 10MPa, when implementing in-molded, film ruptures sometimes, sometimes damages the attractive in appearance of products formed.When fracture strength is more than 30MPa, the resin of injection when implementing shaping can not throughout each corner to mould, and the products formed obtained easily becomes shape defect.

The uneven thickness rate of demoulding biaxially oriented polyester film of the present invention is required to be less than 5%, is preferably less than 4%.If uneven thickness rate is more than 5%, then when implementing in-molded, film deforms inequality (distortion spot), and the appearance design pattern be printed on film also can deform, and sometimes damages and carries out transfer printing to it and the products formed obtained attractive in appearance.The assay method of uneven thickness rate describes later.

In order to make uneven thickness rate be less than 5%, polyester film is required to be biaxial stretch-formed film.Carry out biaxial stretch-formed method as to polyester film, biaxial stretching process, tentering formula simultaneously biaxial stretching process, the expansion type known method such as biaxial stretching process simultaneously can be selected successively.

In biaxial stretch-formed, face multiplying power is preferably 9.0 ~ 12.3 times, is more preferably 9.7 ~ 10.0 times.If face multiplying power is lower than 9.0 times, then be sometimes difficult to make uneven thickness rate be less than 5%.On the other hand, if face multiplying power is more than 12.3 times, then be sometimes difficult to make the elongation at break at 120 DEG C be more than 350%.

In addition, in biaxial stretch-formed, longitudinally (MD) is preferably 0.8 ~ 1.2 with the ratio of the stretching ratio of horizontal (TD).If depart from this scope, then become large in the elongation at break of 120 DEG C, the anisotropy of fracture strength, when implementing in-molded, because film deforms inequality, the appearance design pattern of printing also deforms, so the products formed obtained is attractive in appearance impaired.

Draft temperature in biaxial stretch-formed is set to the temperature higher than the glass transition temperature (Tg) of polyester, if but make uneven thickness rate become less than 5%, from the viewpoint of the elongation at break that can improve at 120 DEG C, preferred draft temperature is as far as possible high.If draft temperature exceedes (Tg+30 DEG C), be then difficult to make uneven thickness rate be less than 5%.

To demoulding biaxially oriented polyester film of the present invention 160 DEG C process 15 minutes time dry-hot shrinkage be preferably-0.5 ~ 1.0%, be more preferably-0.3 ~ 0.5%.The dry-hot shrinkage of preferred film is all in above-mentioned scope in longitudinal direction (MD), laterally (TD).If depart from above-mentioned scope, then when implementing in-molded, because film deforms inequality, the appearance design of printing also deforms, so the products formed obtained is attractive in appearance impaired.

Demoulding biaxially oriented polyester film of the present invention has base material and release layer.Base material is required to be the film be made up of mylar, for this polyester film base material, in order to make its elongation at break at 120 DEG C be 350 ~ 500%, ratio preferably containing diethylene glycol composition is at least 1 layer, the copolymerization PETG layer (A layer) of 4 ~ 12mol%, in order to make fracture strength be 10 ~ 30MPa, preferably containing at least 1 layer, amorphous polyester resin layer (B layer).

Form in the copolymerization PETG of A layer, the ratio of diethylene glycol composition is 4 ~ 12mol% relative to whole glycol component, is preferably 6 ~ 10mol%.If the ratio of diethylene glycol composition is lower than 4mol%, then the biaxially oriented polyester film sometimes obtained becomes difficulty at the elongation at break of 120 DEG C more than 350%.On the other hand, if the ratio of diethylene glycol composition is more than 12mol%, then the heat endurance of the polyester film base material sometimes obtained is low, foams during masking because of thermal decomposition gas.

The copolymerization PETG forming A layer uses known polymerization catalyst to be polymerized, but preferably uses germanium catalyst to be polymerized.Owing to using the crystallizing polyester of germanium catalyst polymerization low, so the biaxially oriented polyester film that obtains can be improved at the elongation at break of 120 DEG C.

The copolymerization of diethylene glycol composition obtains by copolymerization PETG, in the scope not hindering effect of the present invention, and can by other monomer component copolymerization.

Such as, as sour composition, M-phthalic acid, phthalic acid, 2 can be enumerated, the dicarboxylic acids such as 6-naphthalene dicarboxylic acids, 5-sodium sulfo isophthalate, oxalic acid, butanedioic acid, adipic acid, decanedioic acid, azelaic acid, dodecanedioic acid, dimeric dibasic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexane dicarboxylic acid, 4-HBA, 6-caprolactone, lactic acid etc.

In addition, as alcohol composition, 1,3-PD, 1 can be enumerated, the ethylene oxide adduct etc. of 4-butanediol, neopentyl glycol, 1,6-hexylene glycol, cyclohexanedimethanol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ethylene glycol, bisphenol-A and bisphenol S.

In addition, the trifunctional compounds etc. such as trimellitic acid, trimesic acid, Pyromellitic Acid, trimethylolpropane, glycerine, pentaerythrite can be used on a small quantity.

Two or more kinds may be used for these copolymer compositions.

For A layer, in order to improve heat endurance, preferably containing antioxidant 0.1 ~ 1 quality %.Due to the generation utilizing antioxidant to suppress bubble, so the elongation at break of result film uprises, the upper limit of the ratio of diethylene glycol composition can be improved.

As antioxidant, hindered phenol system antioxidant preferably can be used.Such as, N can be enumerated, N '-hexamethylene two (3, 5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 3, 5-di-tert-butyl-4-hydroxyl benzyl phosphonate ester-diethylester, 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-t-butyl-4-Hydroxy-benzvl) benzene, pentaerythrite base-four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], four (2, 4-di-tert-butyl-phenyl)-4, 4 '-Ya biphenyl-two-phosphinate, triethylene glycol-bis--3-(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionic ester etc., particularly preferably be selected from N, N '-hexamethylene two (3, 5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 3, 5-di-t-butyl-4-Hydroxy-benzvl phosphonate ester-diethylester, 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-t-butyl-4-Hydroxy-benzvl) benzene and pentaerythrite base-four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] at least a kind of compound.

The amorphous polyester resin forming B layer refers to and does not show crystalline mylar in fact.Namely refer in the arbitrary temperature province from glass transition temperature to fusing point, when its resin is placed the long enough time, degree of crystallinity is the resin of less than 5%.Degree of crystallinity is tried to achieve by the X-ray diffraction intensity of crystallization unit and the X-ray diffraction intensity in amorphous portion.

As amorphous polyester resin, such as, preferably to the polyalkylene terephthalates terephthalate resin such as PETG or poly-2, the poly-NDA such as 6-(ethylene naphthalate) alkylene glycol ester resin etc. carries out sour modification and/or glycol modification and the amorphism copolyester obtained.

As the sour altered contents used in amorphous polyester resin, M-phthalic acid, phthalic acid, 2 can be enumerated, 6-naphthalene dicarboxylic acids, 1, the dicarboxylic acids such as 4-naphthalene dicarboxylic acids, 5-sodium sulfo isophthalate, oxalic acid, butanedioic acid, adipic acid, decanedioic acid, dodecanedioic acid, dimeric dibasic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexane dicarboxylic acid, the oxycarboxylic acids such as 4-HBA, 6-caprolactone, lactic acid, the polyfunctional compound etc. of trimellitic acid, trimesic acid, Pyromellitic Acid etc.These sour altered contents can be used alone, and also can mix two or more and use.

In addition, as the glycol modification composition used in amorphous polyester resin, can 1 be enumerated, ammediol, BDO, neopentyl glycol, 1,4-CHDM, 1,3-cyclohexanedimethanol, 1, the dihydroxylic alcohols such as the ethylene oxide adduct of 2-cyclohexanedimethanol, 1,6-hexylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ethylene glycol, bisphenol-A and bisphenol S, the polyfunctional compounds etc. such as trimethylolpropane, glycerine, pentaerythrite.These glycol modification compositions can be used alone, and also can mix two or more and use.

For amorphous polyester resin, consider from viewpoints such as heat resistance, mechanical characteristic, the transparencys, preferably by PETG with 1, the modification of 4-cyclohexanedimethanol and the amorphism copolyester obtained, the ratio of 1,4-CHDM composition is preferably 10 ~ 70mol% relative to whole glycol component.

The glass transition temperature forming the amorphous polyester resin of B layer is preferably low than " forming the glass transition temperature+10 DEG C of the copolymerization PETG of A layer ".If the glass transition temperature of amorphous polyester resin is higher than it, then to the stacked film containing A layer and B layer carry out biaxial stretch-formed become difficulty.The glass transition temperature of amorphous polyester resin can be regulated by the ratio adjusting copolymer composition, as copolymer composition, preferably uses decanedioic acid.

B layer contains amorphous polyester resin, in the scope not damaging necessary characteristic, and can containing other macromolecule component.Consider from molecular theory, other macromolecule component can mix with amorphous polyester resin, also can be immiscible.

For the thickness of polyester film base material, from easy angle fracture strength being controlled the scope in regulation, be preferably 30 ~ 200 μm, be more preferably 40 ~ 150 μm.

Polyester film base material contains above-mentioned A layer and at least each 1 layer of B layer.

The thickness (when B layer is multilayer, the thickness of total) of B layer is preferably 50 ~ 95% relative to the ratio of the thickness of polyester film base material, is more preferably 65 ~ 85%.If the thickness proportion of B layer is more than 95%, then the action effect of the A layer containing copolymerization PETG reduces, and obtained biaxially oriented polyester film can not get heat resistance, mechanical characteristic, elongation at break and thickness and precision sometimes.On the other hand, if the thickness proportion of B layer is lower than 50%, then obtained biaxially oriented polyester film can not get the fracture strength of above-mentioned scope.

Concrete layer as polyester film base material is formed, and with A layer/B layer, A layer/B layer/A layer for representative, can enumerate B layer/A layer/B layer, A layer/B layer/A layer/B layer/A layer etc.Layer is configured to the formation on the non-top layer of B layer, and the formation being namely top layer with A layer can prevent amorphous polyester resin layer (B layer) mould of adhering, and thus preferably, what particularly preferably formed by A layer/B layer/A layer is formed.

In addition, for polyester film base material, as the layer beyond A layer, B layer, can the stacked bond layer etc. for giving adhesiveness between layers.

Demoulding biaxially oriented polyester film of the present invention has release layer at least one mask of above-mentioned polyester film base material.

As long as release layer is formed at least one side of polyester film base material, when the polyester film base material that both A layer and B layer are exposed in surface forms 1 pull-up mold layer, preferably form release layer on the surface of B layer.If form the release layer with release property on the surface of A layer, then configure because the surface of B layer time shaping connects with mould, so when B layer softens, the surface of B layer may be merged with mould.

The thickness of release layer is not particularly limited, and makes film, economy during the liquid formed from the viewpoint of coated release layer, preferably 0.01 ~ 1.0 μm, is more preferably 0.05 ~ 0.5 μm.

In the present invention, release layer contains acid-modified polyolefin resin and crosslinking agent.

Acid-modified polyolefin resin need containing olefinic component as principal component.Olefinic component is not particularly limited, the carbon numbers such as optimal ethylene, propylene, isobutene, 2-butylene, 1-butylene, 1-amylene, 1-hexene are the alkene of 2 ~ 6, it can be their mixture, wherein, more preferably the carbon number such as ethene, propylene, isobutene, 1-butylene is the alkene of 2 ~ 4, further optimal ethylene, propylene, most preferably ethene.

In acid-modified polyolefin resin, the ratio of sour altered contents is required to be 1 ~ 10 quality %, is more preferably 2 ~ 10 quality %, more preferably 2 ~ 9 quality %.

When the ratio of acid altered contents is lower than 1 quality %, the ratio of the polar group contained by release layer tails off, so sometimes can not get the sufficient adaptation between release layer and polyester film base material, may pollute by adhesion.Further, in the preparation of the liquid of release layer formation described later, the trend being difficult to acid-modified polyolefin resin stably be carried out aqueous dispersion is had.On the other hand, when the ratio of acid altered contents is more than 10 quality %, the ratio of the polar group contained by release layer becomes many, so the adaptation of release layer and polyester film base material becomes abundant, but due to release layer with also improved by the adaptation of adhesion, so have and the trend reduced by the release property of adhesion simultaneously.

As the sour altered contents forming acid-modified polyolefin resin, unsaturated carboxylic acid composition can be enumerated.As unsaturated carboxylic acid composition, except acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid etc., also can enumerate the half ester of unsaturated dicarboxylic, half amide etc.Wherein, from the viewpoint of the dispersion stabilization of resin, preferred acrylic acid, methacrylic acid, maleic acid, maleic anhydride, particularly preferably acrylic acid, methacrylic acid, maleic anhydride.These sour altered contents can be contained two or more in acid-modified polyolefin resin.

In addition, for acid-modified polyolefin resin, consider from the reason of the cementability improving itself and polyester film base material further, preferably containing the ethylenic unsaturated composition of side chain containing oxygen atom.

Side chain is identical with sour altered contents containing the unsaturated composition of ethylenic of oxygen atom, has polar group in molecule.Therefore by making containing the ethylenic unsaturated composition of side chain containing oxygen atom in acid-modified polyolefin resin, thus the adaptation of release layer and polyester film base material improves.On the other hand, if side chain is too much containing the unsaturated component amount of ethylenic of oxygen atom, then lose the character of the resin from alkene, release layer with may be reduced by the release property of adhesion.Side chain contained in acid-modified polyolefin resin is preferably 1 ~ 40 quality % containing the ratio of the unsaturated composition of ethylenic of oxygen atom, is more preferably 2 ~ 35 quality %, more preferably 3 ~ 30 quality %, is particularly preferably 6 ~ 18 quality %.

As the ethylenic unsaturated composition of side chain containing oxygen atom, the carboxylate that (methyl) acrylic acid and carbon number are the alcohol of 1 ~ 30 can be enumerated, wherein from the viewpoint of easily obtaining, preferably (methyl) acrylic acid and carbon number are the carboxylate of the alcohol of 1 ~ 20.As the concrete example of such compound, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate etc. can be enumerated.Their mixture can be used.Wherein, from the viewpoint of the cementability with base material film, more preferably (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, Hexyl 2-propenoate, 2-ethyl hexyl acrylate, preferred ethyl acrylate, butyl acrylate, particularly preferably ethyl acrylate further." (methyl) acrylic acid ~ " refers to " acrylic acid ~ or methacrylic acid ~ ".

In acid-modified polyolefin resin, other monomer can copolymerization on a small quantity.As other monomer, such as, dienes, (methyl) acrylonitrile, halogen vinyl, vinylidene halide class, carbon monoxide, sulfur dioxide etc. can be enumerated.

As long as form each composition copolymerization in acid-modified polyolefin resin of acid-modified polyolefin resin, its mode does not limit.As the mode of copolymerization, such as, random copolymerization, block copolymerization can be enumerated, graft copolymerization (graft modification) etc.

The fusing point of acid-modified polyolefin resin is preferably 80 ~ 150 DEG C, is more preferably 90 ~ 130 DEG C.In addition, the Vicat softening point of acid-modified polyolefin resin is preferably 50 ~ 130 DEG C, is more preferably 53 ~ 110 DEG C, more preferably 55 ~ 90 DEG C.

If the fusing point of acid-modified polyolefin resin, Vicat softening point exceed above-mentioned scope separately, then, when polyester film substrate surface forms resin bed, sometimes need high-temperature process.On the other hand, if the fusing point of acid-modified polyolefin resin, Vicat softening point are separately lower than above-mentioned scope, are then formed at the easy melting of release layer on polyester film base material, improve with by the adaptation of adhesion, release property reduces.

The melt flow rate (MFR) of acid-modified polyolefin resin 190 DEG C, be preferably 1 ~ 1000g/10 minute under 2160g load, be more preferably 1 ~ 500g/10 minute, more preferably 1 ~ 100g/10 minute.If the melt flow rate (MFR) of acid-modified polyolefin resin is lower than 1g/10 minute, then the manufacture of the water-borne dispersions of dispersion stabilization excellence described later becomes difficulty.On the other hand, if melt flow rate (MFR) is more than 1000g/10 minute, then the adaptation of resin bed and polyester film base material reduces sometimes.

As the acid-modified polyolefin resin that can use in the present invention, the REXPEARL series (trade name) as acid modified polyvinyl resin of the NEWCREL series (trade name) as acid-modified polyolefin resin of DUPONT-MITSUI POLYCHEMICALS Inc., Japan Polyethylene Inc. can be enumerated.As concrete trade name, there are " AN42115C ", " N1050H ", " N1110H " of NEWCREL series, " A210K " of REXPEARL series etc.

In addition, as the acid-modified polyolefin resin containing the unsaturated composition of ethylenic of oxygen atom containing side chain that can use in the present invention, the BONDINE series (trade name) as maleic anhydride modified vistanex of Arkema Inc. can be enumerated.As concrete trade name, there are " LX-4110 ", " HX-8210 ", " HX-8290 ", " TX-8030 ", " AX-8390 " etc.

Release layer also needs containing crosslinking agent except containing except acid-modified polyolefin resin.

By containing crosslinking agent, the various performance such as cohesiveness, resistance to water of release layer can be improved further.The addition of crosslinking agent is required to be 1 ~ 50 mass parts relative to acid-modified polyolefin resin 100 mass parts, is more preferably 2 ~ 40 mass parts, more preferably 2 ~ 30 mass parts.

As crosslinking agent, can use to have in self-crosslinking crosslinking agent, molecule and there is compound etc. that the is multiple and functional group of carboxyl reaction, wherein preferred isocyanate compound, melamine compound, urea compounds, epoxide, carbodiimide compound, contain the compound etc. of azoles quinoline base, especially effectively carbodiimide compound, isoxazoline compound.These crosslinking agents can combinationally use.

As long as the carbodiimide in carbodiimide compound molecule with more than 1 is just not particularly limited.2 carboxyls of carbodiimide compound in the sour modifying moieties of 1 carbodiimide part and acid-modified polyolefin resin form ester, realize crosslinked.

As the concrete example of carbodiimide compound, such as, can enumerate phenylene-bis-(2,6-xylyl carbodiimide), tetramethylene-bis-(tert-butylcarbodiimide), cyclohexane-1,4-two (methylene-tert-butylcarbodiimide) etc. has the compound of carbodiimide, as the poly-carbodiimide of polymer with carbodiimide.Can use in them a kind or two or more.Wherein, from maneuverable angle, preferably poly-carbodiimide.

As the commercially available product of poly-carbodiimide, the CARBODILITE series of Nisshinbo Inc. can be enumerated, more specifically, " SV-02 ", " V-02 ", " V-02-L2 " of water-soluble type, " V-04 " can be enumerated; " E-01 ", " E-02 " of emulsion types; " V-01 ", " V-03 ", " V-07 " of organic solution type, " V-09 "; " V-05 " of solventless type.

as long as have more than 2 in isoxazoline compound molecule azoles quinoline base is just not particularly limited. isoxazoline compound is at 2 azoles quinoline part forms carboxylic acid amide esters with 1 carboxyl in the sour modifying moieties of acid-modified polyolefin resin respectively, realizes crosslinked.

As the concrete example of isoxazoline compound, such as, can enumerate 2,2 '-bis-(2- azoles quinoline), 2,2 '-ethylidene-bis-(4,4 '-dimethyl-2- azoles quinoline), 2,2 '-to phenylene-bis-(2- azoles quinoline), two (2- azoles quinoline butylcyclohexane) thioether etc. has the compound of azoles quinoline base, contains the polymer of azoles quinoline base.Can use in them a kind or two or more.Wherein, from maneuverable angle, preferably contain the polymer of azoles quinoline base.

As containing the commercially available product of the polymer of azoles quinoline base, can enumerate the EPOCROS series of NIPPONSHOKUBAI Inc., more specifically, can enumerate " WS-500 ", " WS-700 " of water-soluble type; " K-1010E ", " K-1020E ", " K-1030E ", " K-2010E ", " K-2020E ", " K-2030E " etc. of emulsion types.

In the present invention, release layer is preferably containing polyvinyl alcohol.Polyvinyl alcohol by being scattered in acid-modified polyolefin resin, suitably reducing fissility that acid-modified polyolefin resin brings and playing a role, playing the adaptation self brought simultaneously in release layer.In addition, because polyvinyl alcohol forms microspike on the surface of release layer together with crosslinking agent also, so the easy slip of release layer can be significantly improved, the carrying of the film for demoulding obtained, windability raising.

The content of polyvinyl alcohol, relative to acid-modified polyolefin resin 100 mass parts, is preferably 5 ~ 200 mass parts, is more preferably 10 ~ 100 mass parts, more preferably 20 ~ 50 mass parts.Content as pectin/polyvinyl alcohol is more than 5 mass parts, then can reduce the impact that the heat treatment temperature (baking temperature) when release layer is formed causes fissility further, on the other hand, if be below 200 mass parts, then can keep the stability of release layer formation liquid well, can be difficult in addition crawling occurs.

Polyvinyl alcohol is not particularly limited, and can enumerate the material etc. of the polymer of vinyl esters completely or partially gelation.

The average degree of polymerization of polyvinyl alcohol is not particularly limited, and such as, can be 300 ~ 5000, from the viewpoint of the stability improving release layer formation liquid, is preferably 300 ~ 2000.

As described below, in order to use liquid in the formation of release layer, preferably polyethylene alcohol has water-soluble.

As commercially available polyvinyl alcohol, if commodity in use name is described, then can enumerate the concrete trade name " JC-05 " of " J-POVAL " of JAPANVAM & POVAL company, " VC-10 ", " ASC-05X ", " UMR-10HH "; The concrete trade name " PVA-103 " of " the KURARAY POVAL " of KURARAY company, " PVA-105 ", the concrete trade name " AQ4104 " of " EXCEVAL ", " HR3010 "; The concrete trade name " PC-1000 ", " PC-2000 " etc. of " the DENKA POVAL " of Denki Kagaku Kogyo kabushiki.

In the present invention, release layer containing inorganic particulate and/or organic filler as roughened material, but not necessarily must be able to contain.Usually, in order to give slipping to film, the inorganic particulates such as such as calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesia, silica, sodium metasilicate, aluminium hydroxide, iron oxide, zirconia, barium sulfate, titanium oxide, tin oxide, antimony trioxide, carbon black, molybdenum bisuphide are added, the organic fillers etc. such as acrylic acid series cross-linked polymer, polystyrene cross-linked polymer, organic siliconresin, fluororesin, benzoguanamine resin, phenolic resins, nylon resin, Tissuemat E under most cases.

But, in inorganic particulate, stay and in aqueous dispersions, condense the generation of the oversize grain caused, sedimentation and particle from problems such as release layer surface come off by particle.Inorganic particulate is preferably below 0.5 mass parts relative to acid-modified polyolefin resin 100 mass parts, is more preferably below 0.1 mass parts, does not particularly preferably contain.

On the other hand, in organic filler, interpolation due to organo-silicon compound, fluorine compounds, wax class, surfactant makes the slipping of film significantly improve, but there are the following problems: ooze out at the interface of polyester film base material and release layer and at release layer surface low molecular weight compositions, the adaptation of polyester film base material and release layer reduces, or peel off time contaminated by adhesion.Therefore, organic filler is preferably below 0.5 mass parts relative to acid-modified polyolefin resin 100 mass parts, is more preferably below 0.1 mass parts, does not particularly preferably contain.

Above-mentioned wax class to be number average molecular be less than 10000 vegetable wax, animal wax, mineral wax, petrochemistry wax etc.Specifically, candelila wax, Brazil wax, rice bran wax, haze tallow, fruit wax (ベリーワッ Network ス can be enumerated), Jojoba wax, shea butter, beeswax, shellac wax, lanolin wax, spermaceti, montan wax, ceresin, paraffin, microwax, synthetic polyethylene waxes, synthesis polypropylene wax, synthesizing ethylene-vinyl acetate copolymer waxes etc.

In addition, as above-mentioned surfactant, cationic surfactant, anionic surfactant, nonionic (non-ionic) surfactant, amphoteric surfactant, fluorine system surfactant, reactive surfactant etc. can be enumerated.General except the material used in emulsion polymerisation, also comprise emulsifying agent class.

Such as, as anionic surfactant, the sulfuric acid of higher alcohol, senior alkyl sulfonic acid and salt, alkyl benzene sulphonate and salt thereof, polyoxyethylene alkyl sulfate salt, polyoxyethylene alkyl phenyl ether sulfuric acid, vinyl sulfosuccinate etc. can be enumerated.

As nonionic surfactant, the Sorbitan 01 derivatives etc. such as compound, polyoxyethylene sorbitan fatty acid ester that polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, cithrol, ethylene oxide-propylene oxide block copolymer, Polyoxyethylene fatty acid amides, PEP-101 etc. have polyoxyethylene structure can be enumerated.

As amphoteric surfactant, empgen BB, lauryl dimethyl amine oxide etc. can be enumerated.

As reactive surfactant, alkyl base phenol polyoxyethylene addition product (ア Le キ Le プロペニ Le Off ェノー Le Port リエチレ Application オキサイ De is paid and added thing) and their sulfuric acid can be enumerated, allyl alkyl phenol polyoxyethylene addition product (アリ Le ア Le キ Le Off ェノー Le Port リエチレ Application オキサイ De is paid and added thing) and their sulfuric acid, pi-allyl dialkyl benzene phenol polyethenoxy addition product (アリ Le ジア Le キ Le Off ェノー Le Port リエチレ Application オキサイ De is paid and added thing) and their sulfuric acid etc. have the compound of reactive double bond.

In the present invention, release layer industrially can be formed by carrying out dry such method after the liquid containing acid-modified polyolefin resin, crosslinking agent and liquid medium is coated on polyester film base material easily.

The liquid medium forming above-mentioned liquid is preferably aqueous medium.

In the present invention, aqueous medium refers to containing water and amphipathic organic solvent and the content of water is the solvent of more than 2 quality %, can be only water.

Amphipathic organic solvent refers to that water dissolubility is in organic solvent the organic solvent (water dissolubility in organic solvent is such as recorded in the documents such as " solvent handbook " (Kodansha Scientific, nineteen ninety the 10th edition) at 20 DEG C) of more than 5 quality % at 20 DEG C.As the concrete example of amphipathic organic solvent, alcohols, oxolane, the Isosorbide-5-Nitraes-two such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol can be enumerated the ester classes such as the ketones such as the ethers such as alkane, acetone, MEK, methyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, other, also can enumerate diethylamine, triethylamine, diethanol amine, triethanolamine, the N containing ammonia, the lactams etc. such as organic amine compound, 2-Pyrrolidone, METHYLPYRROLIDONE such as N-dimethylethanolamine, N, N-diethyl ethylene diamine, N-diethanol amine.

For liquid, not damaging in the scope of its performance, antioxidant, ultra-violet absorber, lubricant, colouring agent etc. can also be added.

Liquid by acid-modified polyolefin resin, crosslinking agent and liquid medium being obtained by mixing, during this mixing, can using the liquid of previously prepared acid-modified polyolefin resin, also can use the water-borne dispersions of acid-modified polyolefin resin.The method that acid-modified polyolefin resin carries out aqueous dispersion is not particularly limited, such as, the method recorded in No. WO02/055598, International Publication can be enumerated.In addition, as the aqueous medium of the water-borne dispersions of formation acid-modified polyolefin resin, illustrative aqueous medium in above-mentioned liquid can be enumerated.

For the dispersion particle diameter of the acid-modified polyolefin resin in aqueous medium, from the viewpoint of stability when mixing with other composition and mixed storage stability, number average bead diameter is preferably less than 1 μm, is more preferably less than 0.8 μm.Such dispersion particle diameter utilizes the method for making recorded in No. WO02/055598 to realize.Should illustrate, the number average bead diameter of acid-modified polyolefin resin utilizes dynamic light scattering determination.

The solid constituent containing ratio of the water-borne dispersions of acid-modified polyolefin resin is not particularly limited, and in order to appropriateness keeps the viscosity of water-borne dispersions, is preferably 1 ~ 60 quality %, is more preferably 5 ~ 30 quality %.

The solid constituent containing ratio of the liquid that the water-borne dispersions of acid-modified polyolefin resin and crosslinking agent are obtained by mixing suitably can be selected according to stacked condition, target thickness or performance etc., is not particularly limited.But in order to appropriateness keeps the viscosity of liquid, and form uniform release layer, the solid constituent containing ratio of liquid is preferably 2 ~ 30 quality %, is more preferably 3 ~ 20 quality %.

As method liquid is coated on polyester film base material, known method can be enumerated, such as gravure roll rubbing method, reverse roll rubbing method, line rod rubbing method, die lip rubbing method, air knife coating method, curtain flowing rubbing method, spraying process, dip coating, spread coating etc.

Release layer can be formed by the method also dry at biaxial stretch-formed polyester film base material coated release layer formation liquid.As the drying means of the liquid after coating liquid, the method for the hot blast of 40 ~ 180 DEG C that blow 3 ~ 60 seconds can be enumerated.

In the present invention, after the polyester film base material of the unstretched state of preferred utilization in the stretching process of polyester film base material or the polyester film base material of uniaxial tension are coated with above-mentioned liquid, carry out stretching, dry and so-called online rubbing method (イ Application ラインコート method) that is that form release layer manufactures.Utilize instant rubbing method to form release layer, the heat treated temperature after film can be utilized to stretch promotes the crosslinked of release layer.

Embodiment

Next, embodiment is utilized to be specifically described the present invention.

The raw material of the film in embodiment and comparative example and the determination method of characteristic value as follows.

The copolymerization PETG that 1.A layer is formed

(1)DEG10

Using the ethylene glycol as glycol component be the diethylene glycol of 9.5mol% relative to whole dihydroxylic alcohols and drop into esterification groove as the terephthalic acid (TPA) of sour composition, react 3 hours at 275 DEG C, obtain carboxylate.Next, using pentaerythrite base-four [3-(3 as antioxidant, 5-di-tert-butyl-hydroxy phenyl) propionic ester] (BASF AG Irganox1010) add in the mode becoming 0.6 quality % relative to the polyester after polymerization, under germanium catalyst, under the decompression of 1.3hPa, at 300 DEG C, carry out melt polymerization, obtain the copolymerization PETG (DEG10) of relative viscosity 1.38, fusing point 238 DEG C, glass transition temperature 70 DEG C.Diethylene glycol composition is 9.5mol% relative to the ratio of whole glycol component.

(2)DEG14、DEG12、DEG8、DEG4、DEG2

In above-mentioned (1), diethylene glycol is changed to 13.5mol%, 11.5mol%, 7.5mol%, 3.5mol%, 1.5mol% respectively relative to the input ratio of whole glycol component, in addition, carry out the operation same with (1), obtain copolymerization PETG (DEG14, DEG12, DEG8, DEG4, DEG2).

Fusing point is respectively 234 DEG C, 236 DEG C, 241 DEG C, 248 DEG C, 252 DEG C, glass transition temperature is respectively 67 DEG C, 68 DEG C, 70 DEG C, 74 DEG C, 76 DEG C, and diethylene glycol composition is respectively 14.2mol%, 12.1mol%, 8.1mol%, 3.7mol%, 2.2mol% relative to the ratio of whole glycol component.

(3)DEG8-2

In above-mentioned (2), do not add Irganox1010, in addition, carry out in the same manner as DEG8, obtain the copolymerization PETG (DEG8-2) of relative viscosity 1.38, fusing point 240 DEG C, glass transition temperature 70 DEG C.Diethylene glycol composition is 8.1mol% relative to the ratio of whole glycol component.

The amorphous polyester resin (PETG) that 2.B layer is formed

Using the ethylene glycol as glycol component be the cyclohexanedimethanol of 34.5mol% relative to whole glycol component and drop into esterification groove as the terephthalic acid (TPA) of sour composition, react 3 hours at 275 DEG C, obtain carboxylate.Next, Irganox1010 (BASF AG's system) is added in the mode becoming 0.6 quality % relative to the polyester after polymerization, under germanium catalyst, under the decompression of 1.3hPa, at 300 DEG C, carry out melt polymerization, obtain the amorphous polyester resin (PETG) of relative viscosity 1.38, glass transition temperature 75 DEG C.Cyclohexanedimethanol composition is 30mol% relative to the ratio of whole glycol component.

3. acid-modified polyolefin resin water-borne dispersions

(1)O-1

Use and be with heater and the mixer possessing the withstand voltage 1 liter capacity glass container that can seal, the distilled water of " BONDINE LX-4110 " (Arkema Inc., maleic anhydride modified vistanex) of 60.0g, the isopropyl alcohol (IPA) of 90.0g, the triethylamine (TEA) of 3.0g and 147.0g is dropped in glass container.Then, make the rotary speed of stirring vane be 300rpm, temperature in system is remained on 140 ~ 145 DEG C, stir 30 minutes.Thereafter, immerse in water-bath, under the state keeping rotary speed 300rpm, be cooled to room temperature (about 25 DEG C) while stirring.The distilled water of 180g and the N of 3.0g, N-dimethylethanolamine (DMEA) are dropped into two mouthfuls of round-bottomed flasks of 0.5L, mechanical agitator and Li Bixi type cooler are set, and heat flask with oil-bath, heat up in a steamer water medium.After the water heating up in a steamer about 180g and IPA, heating terminates, and is cooled to room temperature.After cooling, with stainless steel filter (the linear diameter 0.035mm of 300 object, plain weave) pressure filtration (air pressure 0.2MPa) is carried out to the liquid parts in flask, obtain milky acid-modified polyolefin resin water-borne dispersions (O-1).The content of the organic solvent in this aqueous medium is 1.0 quality %.

(2)O-2

Use " BONDINE HX-8210 " (Arkema Inc., maleic anhydride modified vistanex) as acid-modified polyolefin resin, carry out the operation same with during manufacture water-borne dispersions (O-1), obtain acid-modified polyolefin resin water-borne dispersions (O-2).

(3)O-3

Use " BONDINE AX-8390 " (Arkema Inc., maleic anhydride modified vistanex) as acid-modified polyolefin resin, carry out the operation same with during manufacture water-borne dispersions (O-1), obtain acid-modified polyolefin resin water-borne dispersions (O-3).

(4)O-4

Use and be with heater and the mixer possessing the withstand voltage 1 liter capacity glass container that can seal, by " REXPEARLEAA A210K " (Japan Polyethylene Inc. of 30.0g, acrylic acid modified polyvinyl resin), the distilled water of the normal propyl alcohol (NPA) of 105.0g, TEA and 157.2g of 7.8g drops in glass container, makes the rotary speed of stirring vane be 300rpm.Then temperature in system is remained on 170 DEG C to stir 30 minutes.Room temperature (about 25 DEG C) is cooled under the state keeping rotary speed 300rpm.The DMEA of the distilled water of 180g and 3.0g is dropped in 2 mouthfuls of round-bottomed flasks of 0.5L, mechanical agitator and Li Bixi type cooler is set, and heats flask with oil-bath, heat up in a steamer water medium.After the water heating up in a steamer about 180g and NPA, heating terminates, and is cooled to room temperature.After cooling, with stainless steel filter (the linear diameter 0.035mm of 300 object, plain weave) pressure filtration (air pressure 0.2MPa) is carried out to the liquid parts in flask, obtain milky acid-modified polyolefin resin water-borne dispersions (O-4).The content of the organic solvent in this aqueous medium is 1.0 quality %.

(5)O-5

Use and be with heater and the mixer possessing the withstand voltage 1 liter capacity glass container that can seal, the distilled water of " PRIMACOR 5980I " (Dow Chemical Inc., acrylic acid modified polyolefins resin) of 60.0g, TEA and 223.2g of 16.8g is dropped in glass container.Then, make the rotary speed of stirring vane be 300rpm, temperature in system is remained on 140 ~ 145 DEG C, stir 30 minutes.Thereafter, immerse in water-bath, under the state keeping rotary speed 300rpm, be cooled to room temperature (about 25 DEG C) while stirring.Further, undertaken filtering (air pressure 0.2MPa) by the stainless steel filter of 300 object (linear diameter 0.035mm, plain weave), obtain the water-borne dispersions (O-5) of micro-gonorrhoea.Now, filter almost do not have cull.

The composition transitivity of acid-modified polyolefin resin and the physical property of the water-borne dispersions obtained are shown in table 1.

[table 1]

4. assay method

(1) composition of acid-modified polyolefin resin

Analyze (Varian Inc. GEMINI2000/300,300MHz) by 1H-NMR to try to achieve.Using o-dichlorohenzene (d4) as solvent, measure at 120 DEG C.

(2) melt flow rate (MFR) (MFR) of acid-modified polyolefin resin

The method recording (190 DEG C, 2160g load) with JIS K6730 measures.

(3) fusing point of acid-modified polyolefin resin

Using resin 10mg as sample, use means of differential scanning calorimetry determinator (Perkinelmer Inc. DSC7) to measure under the condition of programming rate 10 DEG C/min, obtain fusing point by the heating curve obtained.

(4) Vicat softening point of acid-modified polyolefin resin

Measure by the method that JIS K7206 records.

(5) the solid constituent containing ratio of water-borne dispersions

Weigh appropriate water-borne dispersions, the quality it being heated at 150 DEG C residue (solid constituent) reaches constant, obtains solid constituent containing ratio.

(6) organic solvent content of water-borne dispersions

Use Inc. of Shimadzu Seisakusho Ltd. gas-chromatography GC-8A, in Direct material input device water-borne dispersions or dilute with water water-borne dispersions obtained, obtain the content of organic solvent.Detectable limit is 0.01 quality %.

The detailed conditions of gas-chromatography is as follows.

Detector: FID, carrier gas: nitrogen, column packing (GL Sciences Inc.): PEG-HT (5%)-Uniport HP (60/80 order), column dimension: diameter 3mm × 3m, sample drops into temperature (implantation temperature): 150 DEG C, column temperature: 60 DEG C, internal standard compound: n-butanol.

(7) number average bead diameter of acid-modified polyolefin resin particle

Use Ji Zhuan Inc. Microtrac Particle Size Analyzer UPA150 (MODELNo.9340, dynamic light scattering method), obtain number average bead diameter.The refractive index of the resin used during particle diameter calculates is 1.50.

(8) uneven thickness rate

To the demoulding biaxially oriented polyester film obtained in transverse direction (TD) with 5mm measuring space thickness, use the mean value (Tave), maximum (Tmax), the minimum of a value (Tmin) that obtain, and utilize following formula to calculate uneven thickness rate.

Uneven thickness rate (%)=(Tmax-Tmin)/Tave × 100

(9) elongation at break, fracture strength

Elongation at break and fracture strength use cupping machine (Inc. of Shimadzu Seisakusho Ltd.) mensuration covering clamp portion with heating clamber.Take the sample of MD100mm × TD10mm as the assess sample of longitudinal direction (MD) from the demoulding biaxially oriented polyester film obtained, take the sample of TD100mm × MD10mm as the assess sample of transverse direction (TD), be held on interval and be set to that the fixture of 50mm is fixed.Then, utilize the heating clamber being arranged at the holder part of cupping machine, sample is remained on the atmosphere of 120 DEG C.Sample is stretched with the speed of 200mm/ minute, with the force cell measuring load being installed on testing machine.

Read the load during fracture of load-elongation curve (lotus stretches bent Line), long-pending except this load by the sample in cross section before stretching, calculate fracture strength (MPa).

In addition, use following formula by the grip separation (L1) when initial grip separation (L0) and fracture, calculate elongation at break (%).

Elongation at break (%)=(L1-L0)/L0 × 100

The each sample of longitudinal direction (MD) and laterally (TD) is measured to test number n=5, the mean value of stress when obtaining fracture and whole measurement results of percentage elongation.

(10) mouldability

After in the chamber demoulding biaxially oriented polyester film obtained being arranged on the lower cavity die of differential pressure forming mould in the mode that the face, chamber in the face with mould that do not form release layer connects, attract to be fixed on mould inner wall by mould, then to the top injection acrylic resin of lower cavity die, by parts-moulding.The diameter making the shape of parts become bottom surface is 50mm, the diameter of opening surface is 60mm, degree of depth 30mm cup-shaped.Film and parts are taken out, film from parts stripping from mould.Observe the release layer of film peeled off, by with or without film fracture, have flawless to evaluate the mouldability of demoulding biaxially oriented polyester film.

(11) peel strength

At the polyester adhesive tape (Dong electrician Inc. No.31B/ acrylic acid series sticker) of the release layer side rubber rollers crimping width 50mm of the demoulding biaxially oriented polyester film obtained, length 150mm as sample.Clamped in the mode of metallic plate/rubber slab/sample/rubber slab/metallic plate by sample, place 20 hours under 2kPa load, the atmosphere of 70 DEG C, cooling thereafter turns back to normal temperature for more than 30 minutes and obtains peel strength measurement sample.The adhesive tape of peel strength measurement sample and the peel strength of mold release film is measured with cupping machine (accurate universal testing machine 2020 type of Intesco Inc.) in the thermostatic chamber of 25 DEG C.Make peel angle be 180 degree, peeling rate is 300mm/ minute.

(12) residual bonding rate

By utilizing above-mentioned peeling strength test to be attached to biaxially stretched polyester resin molding from the polyester adhesive tape that demoulding biaxially oriented polyester film sur-face peeling gets off, (You Niji can Inc. " EmbletPET-12 ", thickness 12 μm) sided corona treatment face, put 20 hours at 2kPa load, ambient temperatare.Thereafter, in the thermostatic chamber of 25 DEG C, the peel strength of polyester adhesive tape and film is measured with cupping machine (accurate universal testing machine 2020 type of Intesco Inc.).Make peel angle be 180 degree, peeling rate is 300mm/ minute.The peel strength obtained by this mensuration is designated as F1.

On the other hand, at biaxially stretched polyester resin molding, (You Niji can Inc. " EmbletPET-12 ", thickness 12 μm) sided corona treatment face attach the polyester adhesive tape (Dong electrician Inc. No.31B/ acrylic acid series sticker) of width 50mm, length 150mm, put 20 hours at 2kPa load, ambient temperatare.Thereafter, in the thermostatic chamber of 25 DEG C, the peel strength of polyester adhesive tape and film is measured with cupping machine (accurate universal testing machine 2020 type of Intesco Inc.).Make peel angle be 180 degree, peeling rate is 300mm/ minute.The peel strength obtained by this mensuration is designated as F2.

Utilize the peel strength F1, the F2 that obtain, obtain residual bonding rate according to following formula.

Residual bonding rate (%)=(F1/F2) × 100

When the sticker surface of adhesive tape is polluted by the release layer of mold release film, the adherence again of adhesive tape reduces, and damages the performance as adhesive tape.Therefore, residual bonding rate is more high better.

Embodiment 1

Be used as the DEG10 of the resin forming A layer, it is utilized extruder melting at temperature 270 DEG C, be used as the PETG of the resin forming B layer in addition, it is also utilized at temperature 270 DEG C other extruder melting, each molten mass is extruded by T-shaped mould behind compound engagement device interflow, cools fast with drum cooler and obtain the unstretched layer that A layer/these 3 layers, B layer/A layer forms and fold film.Now, the mode being 1/4/1 with thickness constituent ratio adjusts the spray volume of each extruder.

Using acid-modified polyolefin resin water-borne dispersions (O-1), as crosslinking agent aqueous solution (the NIPPON SHOKUBAI Inc. " EPOCROS WS-700 " of isoxazoline compound, solid component concentration 25 quality %) and polyvinyl alcohol water solution (JAPAN VAM & POVAL Inc. " VC-10 ", the degree of polymerization 1000, solid component concentration 10 quality %) mode that becomes the value shown in table 2 with the solid constituent ratio of each composition mixes, thereafter, dilute with water obtains the liquid (E-3) that solid constituent containing ratio is 8 quality %.

First unstretched layer is folded film utilizes roller pulling method to be longitudinally stretched to 3.0 times at 80 DEG C, by liquid (E-3) by 120 object gravure roll to become 5g/m ²mode be coated on after on this longitudinal stretching film, make it by the hot-air drying stove of 50 DEG C 20 seconds.

Next, after by liquid, the longitudinal stretching film of applied and drying utilizes tenter stretching method to be transversely stretched to 3.3 times at 100 DEG C, while heat-treat in the temperature of the slack side laterally carrying out 3% at 225 DEG C.After further film being cooled, utilize up-coiler wound into rolls, obtain the demoulding biaxially oriented polyester film that thickness is 50 μm.

[table 2]

Embodiment 2 ~ 6, comparative example 1 ~ 2

The formation of polyester film base material is pressed shown in table 3 and change, in addition, carry out similarly to Example 1 and obtain demoulding biaxially oriented polyester film.

Comparative example 3

Be used as the DEG8 of the resin forming A layer, at temperature 270 DEG C, utilize extruder to carry out melting it, this molten mass is extruded from T-shaped mould, cools fast and the monofilm that do not stretched with drum cooler.By liquid (E-3) with Meyer coiling rod (マイヤーバー) to become 4.5g/m ²mode coat this unstretching film after, with dry 90 seconds of the hot-air drying stoves of 120 DEG C, obtain the non-oriented polyester film of thickness 50 μm.

Elongation at break, fracture strength, uneven thickness rate are evaluated to the film obtained in embodiment 1 ~ 6, comparative example 1 ~ 3.Show the result in table 3.

[table 3]

The demoulding biaxially oriented polyester film obtained in embodiment 1 ~ 6, because fracture strength is low, elongation at break is high, even if so carry out the shaping fracture also not having film, is applicable shaping film.

The film of the demoulding biaxially stretched polyester obtained in embodiment 2 and the A layer of polyester film base material do not compare containing the film of the embodiment 4 of antioxidant, by adding antioxidant, improve fracture strength, elongation at break.

The film of comparative example 1 due in the copolymerization PETG of A layer forming base material the ratio of diethylene glycol composition few, so elongation at break is low, in comparative example 2, its ratio is many, due to thermal decomposition, bubble enters in film, so elongation at break is low, any shaping in, all can observe the position of fracture in a part for film.

The film of comparative example 3 is not owing to having the B layer of amorphous polyester resin layer as base material, so fracture strength is high, shaping middle film does not follow mould, exists shaping bad.

Embodiment 7 ~ 14, comparative example 4 ~ 6

By acid-modified polyolefin resin water-borne dispersions, the aqueous solution of isoxazoline compound and polyvinyl alcohol water solution mix in the mode becoming the solid constituent ratio shown in table 2, in addition to become the mode dilute with water of the solid constituent containing ratio shown in table 2, obtain each liquid.Use the liquid obtained, make the thickness of release layer become the value shown in table 4, in addition, obtain demoulding biaxially oriented polyester film similarly to Example 1.Because the liquid (E-1) and (E-11) coating to polyester film base material that do not contain polyvinyl alcohol are poor, so use the liquid being added with relative to liquid the acetylenediol as surfactant being 0.1 quality %.

Embodiment 15

In embodiment 1, omit the operation of coating liquid (E-3), do not formed the biaxially oriented polyester film base material of release layer.By liquid (E-3) with Meyer coiling rod (マイヤーバー) to become 4.5g/m ²mode coat the biaxially oriented polyester film base material obtained after, with dry 90 seconds of the hot-air drying stoves of 120 DEG C, obtain the demoulding biaxially oriented polyester film that thickness is 50 μm.

To embodiment 1,7 ~ 15, the film that obtains in comparative example 4 ~ 6 evaluates release property.Show the result in table 4.

[table 4]

The demoulding biaxially oriented polyester film obtained in embodiment 1,7 ~ 13 due to the peel strength of the index as release property and residual bonding rate excellent, so can easily stripping film after shaping.Crackle is not observed in addition at the release layer of the film peeled off.

The demoulding biaxially oriented polyester film obtained in embodiment 14,15 compared with defining the embodiment 1 of the release layer of same composition on identical polyester film base material, due to the peel strength of the index as release property and residual bonding rate slightly poor, so feel stop during shaping rear stripping film a little.Crackle is not observed at the release layer of the film peeled off.

The film of comparative example 4 due to the ratio of the sour altered contents forming the acid-modified polyolefin resin of release layer high, the film of comparative example 5,6 is not owing to containing crosslinking agent in release layer in addition, so with have same thickness release layer film compared with, all that peel strength is high, residual bonding rate is low in addition, release property is poor, and also depositing after shaping cannot the part of stripping film.Crackle is observed in addition at the release layer of the film peeled off.

Claims

1. a demoulding biaxially oriented polyester film, is characterized in that, is the biaxially oriented polyester film having release layer at least one mask of polyester film base material,

The uneven thickness rate of biaxially oriented polyester film is less than 5%.

2. demoulding biaxially oriented polyester film according to claim 1, it is characterized in that, the ratio that polyester film base material contains diethylene glycol composition is the copolymerization PETG layer of 4 ~ 12mol% and A layer and amorphous polyester resin layer and at least each 1 layer of B layer.

3. demoulding biaxially oriented polyester film according to claim 1, is characterized in that, release layer is further containing polyvinyl alcohol, and its content is 5 ~ 200 mass parts relative to acid-modified polyolefin resin 100 mass parts.

4. demoulding biaxially oriented polyester film according to claim 2, is characterized in that, A layer contains antioxidant 0.1 ~ 1 quality %.

5. demoulding biaxially oriented polyester film according to claim 2, is characterized in that, the copolymerization PETG forming A layer utilizes germanium catalyst to be polymerized.

6. the demoulding biaxially oriented polyester film according to any one of Claims 1 to 5, is characterized in that, biaxial stretch-formed face multiplying power is 9.0 ~ 12.3 times.