CN104395077B

CN104395077B - Demoulding biaxially oriented polyester film

Info

Publication number: CN104395077B
Application number: CN201380034394.6A
Authority: CN
Inventors: 南條成; 南條一成
Original assignee: Unitika Ltd
Current assignee: Unitika Ltd
Priority date: 2012-07-02
Filing date: 2013-07-01
Publication date: 2017-06-09
Anticipated expiration: 2033-07-01
Also published as: WO2014007187A1; HK1207035A1; KR101816619B1; TW201406525A; JP6165141B2; CN104395077A; JPWO2014007187A1; KR20150035549A; TWI541124B

Abstract

A kind of demoulding biaxially oriented polyester film, it is characterized in that, it is that there is the biaxially oriented polyester film of release layer at least one side of polyester film base material, the ratio that release layer contains sour altered contents is the mass parts of acid-modified polyolefin resin 100 and the mass parts of crosslinking agent 1~50 of 1~10 mass %, biaxially oriented polyester film elongation at break at 120 DEG C is 350~500%, fracture strength is 10~30MPa, and the uneven thickness rate of biaxially oriented polyester film is less than 5%.

Description

Demoulding biaxially oriented polyester film

Technical field

The present invention relates to demoulding biaxially oriented polyester film, more specifically it is related to have as the process paper peeled off after shaping The excellent demoulding biaxially oriented polyester film of release property.

Background technology

Polyester film with polyethylene terephthalate as representative is due to excellent mechanical property, heat resistance, resistance to Chemical corrosivity, so being widely used in industrial field and industrial circle.Wherein, the film that can be used as release materials is used as work Skill material, protection materials, in recent years demand be significantly expanded, particularly widely used in electronic motor field.

As the purposes of release materials, the adhesion bonding plane for sticky materials such as adhesive sheet, adhesive tapes can be enumerated Protection materials or process materials, the work for manufacturing printing distributing board, flexible printing patch panel, multi-layer printed circuit board etc. Skill material, as the polarizer of liquid crystal display part, the protection materials of polarizer, also, release materials also in structure Used in the shaping of body.

The shaping of the structure enumerated as the purposes of above-mentioned release materials, for example, can enumerate the film that will implement to print and insert Enter mould and in injection moulding while that is decorated is in-molded, the forming method with low cost due to that can carry out beauty Decoration, so being widely used in the shaping of housing of inside components, electronic equipment in automobile etc. etc..

In-molded to be roughly divided into two ways, a kind of is the mode of the stripping film after injection moulding, and another kind is in note Penetrate that shaping caudacoria and products formed are integrally formed and film stays in the mode of formed body.In the case of the mode of the latter, film is due to needing The 3D shape of complexity is followed, so using molding processibility acrylic film very high.

On the other hand, in the former mode, due to stretching film heat resistance, dimensional stability, printing, the thickness essence of polyester Degree is high and cheap, so widely using.However, the molding processibility of the stretched film of polyester, release property are sometimes insufficient.Therefore, In patent document 1, disclose and contain the scope that stress when stretching agent, extending 400% under 120 DEG C of atmosphere is 2~20MPa Non-stretched polyester film.

In order that with polyester film as release materials, typically, with polyester film as base material, by the demoulding containing releasing agent Layer is laminated and is assigned release property to film.And, the method as being laminated to release layer, it is proposed that many on film surface The method being coated.By the stacking that carries out of coating from the filming of release layer it is such from the viewpoint of be effective method.

For example, using the smears of solvent system, Patent Document 2 discloses polydimethylsiloxanes of the stacking containing vinyl The method of alkane, in addition Patent Document 3 discloses the method for stacking fluorine compounds.

In addition, can also enumerate the smears using water system, stacking wax class (patent document 4), low-molecular-weight it is siliconated Compound, fluorine system surfactant as release layer method, but there is these releasing agents transfer when peeling off in the release materials that obtain To being reduced by adhesion by such problems such as the function of adhesion such as adherences.

Therefore, the method that stacking organic siliconresin is disclosed in patent document 5,6, in addition Patent Document 7 discloses layer The method of folded fluorine resin, the method that patent document 8,9 discloses the vistanex for being laminated special composition in addition.

Prior art literature

Patent document

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

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

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

Patent document 4:Japanese Patent Publication 05-062897 publications

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

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

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

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

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

The content of the invention

Polyester film described in above-mentioned patent document 1 is due to being unstretching film, so not having sufficient thickness and precision.

Release layer described in patent document 2 is in order to be laminated, being solidified the treatment, it is necessary at high temperature.In addition, patent Not only price is high for resin described in document 3,7, and is difficult to the poison gas that burns and have in discarded burning disposal after Body.It is respectively provided with addition and problem as substantial amounts of organic solvent is used for equably coated release agent.

Using the smears of water system patent document 4 described in olefin-based waterborne liquid be substantially stacking low-molecular-weight Olefin-based wax, and contain surfactant, it is thus possible to which pollution is by adhesion.Described in patent document 5,6 The adaptation of release layer and base material is not enough, and release property etc. is also insufficient.

It is actual not to the evaluation of release sheet material in patent document 8.And because smears contains surfactant, institute That 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 be formed Release sheet material needs treatment at high temperature.

The present invention in order to solve the above problems, in order to obtain sufficient thickness and precision, it is desirable to though provide one kind drawn Can also implement after stretching with the demoulding biaxially oriented polyester film for being suitable as release materials of the shaping of large deformation.

The present inventor etc. have made intensive studies to solve above-mentioned problem, as a result find by with specific Elongation at break, the biaxially oriented polyester film of fracture strength at least one side set the vistanex containing specific composition and The release layer of the crosslinking agent of specified quantitative, can solve the problem that above-mentioned problem, so as to complete the present invention.

That is, purport of the invention is as follows.

(1) a kind of demoulding biaxially oriented polyester film, it is characterised in that be polyester film base material at least one side have it is de- The biaxially oriented polyester film of mold layer,

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

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 according to (1), it is characterised in that polyester film base material contains diethyl two The ratio of alcohol composition is copolymerization polyethylene terephthalate layer (A layers) and amorphous polyester resin layer (B of 4~12mol% Layer) it is at least each 1 layer.

(3) demoulding biaxially oriented polyester film according to (1), it is characterised in that release layer further contains poly- second Enol, its content is 5~200 mass parts relative to the mass parts of acid-modified polyolefin resin 100.

(4) demoulding biaxially oriented polyester film according to (2), it is characterised in that A layers contains antioxidant 0.1~1 Quality %.

(5) demoulding biaxially oriented polyester film according to (2), it is characterised in that the copolymerization for constituting A layers is poly- to benzene two Formic acid glycol ester is polymerized using germanium catalyst.

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

Demoulding biaxially oriented polyester film of the invention is good due to thickness and precision, and with specific elongation at break and Fracture strength, thus be used in it is in-molded also possess good mouldability and release property, can carry out implementing beauty The shaping of decoration.In addition, demoulding biaxially oriented polyester film of the invention due to necessarily containing wax class, low-molecular-weight it is organic The releasing agents such as silicon compound, surfactant, so will not be polluted by adhesion when peeling off, further, since not containing comprising fluorine Deng the releasing agent of halogens, so load when discarded to environment is also few.

Specific embodiment

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

For demoulding biaxially oriented polyester film of the invention, need to be as described above in 120 DEG C of elongation at breaks 350~500%, preferably 370~500%, more preferably 400~500%.It is real in the case that elongation at break is less than 350% Film is not followed when applying in-molded, is ruptured sometimes, the attractive in appearance of products formed is damaged sometimes.It is preferred that elongation at break is high, but with The film that mode of the elongation at break more than 500% is manufactured cannot get thickness and precision sometimes.

Need to be as described above 10 in 120 DEG C of fracture strengths for demoulding biaxially oriented polyester film of the invention ~30MPa, preferably 10~25MPa, more preferably 10~20MPa.When fracture strength is less than 10MPa, when implementing in-molded Film is broken sometimes, and the attractive in appearance of products formed is damaged sometimes.In the case that fracture strength is more than 30MPa, implement the tree injected during shaping Fat can not easily become shape defect over to each corner of mould, the products formed for obtaining.

The uneven thickness rate of demoulding biaxially oriented polyester film of the invention need to be less than 5%, preferably less than 4%.Such as More than 5%, then when implementing in-molded, film deforms uneven (deformation spot) fruit uneven thickness rate, is printed on the outward appearance on film Layout can also be deformed, and the attractive in appearance of products formed obtained by being transferred to it is damaged sometimes.The measure of uneven thickness rate Method is described below.

In order that uneven thickness rate is less than 5%, polyester film need to be biaxial stretch-formed film.Twin shaft is carried out as to polyester film The method of stretching, can select gradually biaxial stretching process, tentering formula simultaneously biaxial drawing method, expansion type simultaneously biaxial drawing method etc. Known method.

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

In addition, in biaxial stretch-formed, longitudinal direction (MD) is preferably 0.8~1.2 with the ratio of the laterally stretching ratio of (TD).If de- From the scope, then elongation at break at 120 DEG C, the anisotropy of fracture strength become big, when implementing in-molded, due to film hair The shape that changes is uneven, and the appearance design pattern of printing also deforms, so the products formed for obtaining 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, but as long as Uneven thickness rate is set to turn into less than 5%, from that can improve from the viewpoint of 120 DEG C of elongation at break, preferred draft temperature It is as far as possible high.If draft temperature exceedes (Tg+30 DEG C), it is difficult to make uneven thickness rate be less than 5%.

Dry-hot shrinkage of the demoulding biaxially oriented polyester film of the invention when processing 15 minutes for 160 DEG C is preferably- 0.5~1.0%, more preferably -0.3~0.5%.It is preferred that the dry-hot shrinkage of film is in longitudinal direction (MD), horizontal (TD) State scope.If departing from above range, when implementing in-molded, because film deforms inequality, the appearance design of printing Deform, so the products formed for obtaining is attractive in appearance impaired.

Demoulding biaxially oriented polyester film of the invention has base material and release layer.Base material need to be made up of polyester resin Film, for the polyester film base material, in order that its elongation at break at 120 DEG C is 350~500%, preferably comprises diethylene glycol The ratio of composition is at least 1 layer of copolymerization polyethylene terephthalate layer (A layers) of 4~12mol%, in order that fracture strength It is 10~30MPa, preferably comprises at least 1 layer of amorphous polyester resin layer (B layers).

Constitute in A layers of copolymerization polyethylene terephthalate, the ratio of diethylene glycol composition is relative to whole binary Alcohol composition is 4~12mol%, preferably 6~10mol%.If the ratio of diethylene glycol composition is less than 4mol%, sometimes To biaxially oriented polyester film become difficult more than 350% in 120 DEG C of elongation at break.On the other hand, if diethylene glycol The ratio of composition is more than 12mol%, then the heat endurance of the polyester film base material for obtaining sometimes is low, because of thermal decomposition gas during masking Foaming.

The copolymerization polyethylene terephthalate for constituting A layers is polymerized using known polymerization catalyst, but is preferably made It is polymerized with germanium catalyst.Because the crystallizing polyester being polymerized using germanium catalyst is low, it is possible to improving obtain double Elongation at break of the axle oriented polyester film at 120 DEG C.

Copolymerization polyethylene terephthalate is by obtained by diethylene glycol composition copolymerization, in without prejudice to effect of the invention In the range of fruit, can be by other monomer component copolymerization.

For example, as sour composition, can enumerate M-phthalic acid, phthalic acid, 2,6- naphthalene dicarboxylic acids, M-phthalic acid- 5- sodium sulfonates, oxalic acid, butanedioic acid, adipic acid, decanedioic acid, azelaic acid, dodecanedioic acid, dimeric dibasic acid, maleic anhydride, maleic acid, The dicarboxylic acids such as fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexane dicarboxylic acid, 4-HBA, 6-caprolactone, lactic acid Deng.

In addition, as alcohol composition, 1,3-PD, BDO, neopentyl glycol, 1,6- hexylene glycols, hexamethylene can be enumerated The oxirane of alkane dimethanol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ethylene glycol, bisphenol-A and bisphenol S adds Into thing etc..

Furthermore, it is possible to use trimellitic acid, trimesic acid, Pyromellitic Acid, trimethylolpropane, glycerine, season penta on a small quantity Trifunctional compound such as tetrol etc..

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

For A layers, in order to improve heat endurance, the mass % of antioxidant 0.1~1 is preferably comprised.Due to using anti-oxidant Agent suppresses the generation of bubble, so the elongation at break of result film is uprised, it is possible to increase the upper limit of the ratio of diethylene glycol composition.

As antioxidant, hindered phenol series antioxidant is preferably used.For example, N can be enumerated, N '-hexamethylene double (3,5- Di-t-butyl -4- hydroxyls-hydrocinnamamide), 3,5- di-tert-butyl-4-hydroxyl benzyls phosphonate ester-diethylester, 1,3,5- trimethyls - 2,4,6- tri- (3,5- di-t-butyl -4- Hydroxy-benzvls) benzene, the [3- (3,5- di-t-butyl -4- hydroxy benzenes of pentaerythrite base-four Base) propionic ester], four (2,4- di-tert-butyl-phenyls) -4,4 '-sub- biphenyl-two-phosphinate, triethylene glycol-bis- -3- (tertiary fourths of 3- Base -4- hydroxy-5-methyls base-phenyl) propionic ester etc., particularly preferably selected from N, N '-hexamethylene pair (3,5- di-t-butyl -4- hydroxyls - Hydrocinnamamide), 3,5- di-t-butyl -4- Hydroxy-benzvls phosphonate ester-diethylester, (the 3,5- bis- of 1,3,5- trimethyls -2,4,6- three Tertiary butyl-4-hydroxy-benzyl) in benzene and pentaerythrite base-four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester] At least a kind compound.

The amorphous polyester resin for constituting B layers refers to substantially not show crystalline polyester resin.Refer to from glass To the arbitrary temperature province of fusing point, when its resin is placed into enough long-times, crystallinity is less than 5% to glass transition temperature Resin.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, for example, it is preferable to polyalkylene terephthalates such as polyethylene terephthalates Poly- 2,6- naphthalenedicarboxylic acids alkylene glycol ester resin such as terephthalate resin or poly- 2,6- (ethylene naphthalate)s etc. carries out acid Modified and/or amorphism copolyester obtained by glycol modification.

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

In addition, as the glycol modification composition used in amorphous polyester resin, 1,3-PD, Isosorbide-5-Nitrae-fourth two can be enumerated It is alcohol, neopentyl glycol, 1,4 cyclohexane dimethanol, 1,3- cyclohexanedimethanols, 1,2- cyclohexanedimethanols, 1,6-HD, poly- The dihydroxylic alcohols such as the ethylene oxide adduct of ethylene glycol, polypropylene glycol, polytetramethylene ethylene glycol, bisphenol-A and bisphenol S, three hydroxyl first Polyfunctional compounds such as base propane, glycerine, pentaerythrite etc..These glycol modification compositions can be used alone, it is also possible to mix 2 Plant used above.

For amorphous polyester resin, consider from viewpoints such as heat resistance, mechanical characteristic, the transparencys, preferably will be poly- to benzene two Formic acid glycol ester with 1,4-CHDM it is modified obtained by amorphism copolyester, 1,4-CHDM composition Ratio is preferably 10~70mol% relative to whole glycol components.

B layers of the glass transition temperature of amorphous polyester resin is constituted preferably than " constituting A layers of the poly- terephthaldehyde of copolymerization + 10 DEG C of the glass transition temperature of sour glycol ester " is low.If the glass transition temperature of amorphous polyester resin is higher than its, Then the stacked film containing A layers and B layers is carried out biaxial stretch-formed to become difficult.The glass transition temperature of amorphous polyester resin can It is adjusted with by adjusting the ratio of copolymer composition, as copolymer composition, preferably uses decanedioic acid.

B layers contains amorphous polyester resin, is not damaging in the range of necessary characteristic, can contain other macromolecules Composition.Consider from molecular theory, other macromolecule components can mix with amorphous polyester resin, it is also possible to immiscible.

For the thickness of polyester film base material, from easily by fracture strength control the scope of regulation angle, preferably It is 30~200 μm, more preferably 40~150 μm.

Polyester film base material contain above-mentioned A layers and B layers it is at least each 1 layer.

B layers thickness (B layers be multilayer when, the thickness of total) be preferably 50 relative to the ratio of the thickness of polyester film base material ~95%, more preferably 65~85%.If B layers of thickness proportion is more than 95%, contain copolymerization poly terephthalic acid second two The action effect reduction of A layers of alcohol ester, obtained biaxially oriented polyester film cannot get heat resistance, mechanical characteristic, fracture and stretches sometimes Rate long and thickness and precision.On the other hand, if B layers of thickness proportion is less than 50%, obtained biaxially oriented polyester film is obtained Less than the fracture strength of above range.

Constituted as the specific layer of polyester film base material, with A layers/B layers, A layers/B layers/A layers as representative, B layers/A can be enumerated Layer/B layers, A layers/B layers/A layers/B layers/A layers etc..Layer is configured to the B layers of composition on non-top layer, i.e., with A layers of being configured to as top layer Prevent (B layer) of amorphous polyester resin layer from adhering mould, thus preferably, particularly preferably by A layers/B layers/A layers formed constitute.

In addition, for polyester film base material, as the layer beyond A layers, B layers, can be laminated for assigning adhesiveness between layers Bond layer etc..

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

As long as release layer polyester film base material at least one side formed, surface expose A layer with B layers both gather When ester film base material forms 1 layer of release layer, preferably release layer is formed on B layers of surface.If being formed on A layers of surface has the demoulding Property release layer, then B layer of surface connects and configures with mould when due to shaping, so during B layers of softening, B layers of surface possibility Merged with mould.

The thickness of release layer is not particularly limited, from coated release layer formation liquid when make film, economy From the viewpoint of property, preferably 0.01~1.0 μm, 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 to be containing olefinic component as principal component.Olefinic component is not particularly limited, preferably second The carbon numbers such as alkene, propylene, isobutene, 2- butylene, 1- butylene, 1- amylenes, 1- hexenes are 2~6 alkene, can be them Mixture, wherein, more preferably the carbon number such as ethene, propylene, isobutene, 1- butylene is 2~4 alkene, further preferred second Alkene, propylene, most preferably ethene.

In acid-modified polyolefin resin, the ratio of sour altered contents need to be 1~10 mass %, more preferably 2~10 matter Amount %, more preferably 2~9 mass %.

When the ratio of sour altered contents is less than 1 mass %, because the ratio of the polar group contained by release layer tails off, so Sometimes cannot get the sufficient adaptation between release layer and polyester film base material, may pollute by adhesion.Also, described later In the preparation of the liquid of release layer formation, have and be difficult to for acid-modified polyolefin resin stably to carry out aqueous dispersion Trend.On the other hand, when the ratio of sour altered contents is more than 10 mass %, because the ratio of the polar group contained by release layer becomes It is many, so release layer becomes abundant with the adaptation of polyester film base material, but because release layer is also same with by the adaptation of adhesion Shi Tigao, so having and the trend reduced by the release property of adhesion.

As the sour altered contents for constituting acid-modified polyolefin resin, unsaturated carboxylic acid composition can be enumerated.As unsaturation Carboxylic acid composition, except acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid etc. Outside, can also enumerate half ester, half amide of unsaturated dicarboxylic etc..Wherein, it is excellent from from the aspect of the dispersion stabilization of resin Select acrylic acid, methacrylic acid, maleic acid, maleic anhydride, particularly preferred acrylic acid, methacrylic acid, maleic anhydride.These acid Altered contents can be contained two or more in acid-modified polyolefin resin.

In addition, for acid-modified polyolefin resin, being examined the reasons why its cementability with polyester film base material is further improved Consider, preferably comprise ethylenic unsaturation composition of the side chain containing oxygen atom.

Ethylenic unsaturation composition of the side chain containing oxygen atom is identical with sour altered contents, and intramolecular has polar group.Cause This by making in acid-modified polyolefin resin the ethylenic unsaturation composition containing oxygen atom containing side chain so that release layer and polyester The adaptation of film base material is improved.On the other hand, if ethylenic unsaturation component amount of the side chain containing oxygen atom is excessive, lose and From the property of the resin of alkene, release layer may be reduced with by the release property of adhesion.It is contained in acid-modified polyolefin resin The ratio of ethylenic unsaturation composition of the side chain containing oxygen atom is preferably 1~40 mass %, more preferably 2~35 mass %, enters One step is preferably 3~30 mass %, particularly preferably 6~18 mass %.

The ethylenic unsaturation composition containing oxygen atom as side chain, can enumerate (methyl) acrylic acid and carbon number be 1~ The carboxylate of 30 alcohol, wherein from from the viewpoint of being readily available, preferably (methyl) acrylic acid and carbon number are 1~20 alcohol Carboxylate.As the concrete example of such compound, (methyl) methyl acrylate, (methyl) ethyl acrylate, (first can be enumerated Base) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid Last of the ten Heavenly stems ester, (methyl) lauryl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid Stearyl etc..Their mixture can be used.Wherein, from from the viewpoint of the cementability with base material film, more preferably (first Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, Hexyl 2-propenoate, 2-ethyl hexyl acrylate, further It is preferred that ethyl acrylate, butyl acrylate, particularly preferred ethyl acrylate." (methyl) acrylic acid~" refer to " acrylic acid~or Person's methacrylic acid~".

In acid-modified polyolefin resin, other monomers can copolymerization on a small quantity.As other monomers, for example, can enumerate Dienes, (methyl) acrylonitrile, halogen vinyl, vinylidene halide class, carbon monoxide, sulfur dioxide etc..

As long as constituting each composition copolymerization in acid-modified polyolefin resin of acid-modified polyolefin resin, its mode does not have There is restriction.As the mode of copolymerization, for example, 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, more preferably 90~130 DEG C.In addition, acid is modified poly- The Vicat softening point of olefin resin is preferably 50~130 DEG C, more preferably more preferably 53~110 DEG C, 55~90 DEG C.

If the fusing point of acid-modified polyolefin resin, Vicat softening point each exceed above range, in polyester film base material When surface forms resin bed, it is sometimes desirable to high-temperature process.On the other hand, if the fusing point of acid-modified polyolefin resin, dimension card are soft Change point and be each less than above range, then the release layer being formed on polyester film base material easily melts, and by the adaptation of adhesion Improve, release property reduction.

The melt flow rate (MFR) of acid-modified polyolefin resin is preferably 1~1000g/10 points under 190 DEG C, 2160g load Clock, more preferably 1~500g/10 minute, more preferably 1~100g/10 minute.If acid-modified polyolefin resin is molten Body flow rate is less than 1g/10 minutes, then the manufacture of the excellent water-borne dispersions of dispersion stabilization described later becomes difficult.It is another Aspect, if melt flow rate (MFR) was more than 1000g/10 minutes, resin bed is reduced with the adaptation of polyester film base material sometimes.

As the acid-modified polyolefin resin that can be used in the present invention, DUPONT-MITSUI can be enumerated NEWCREL series (trade name), the Japan as acid-modified polyolefin resin of POLYCHEMICALS company systems REXPEARL series (trade name) as sour modified polyvinyl resin of Polyethylene company systems.As specific commodity Name, has " AN42115C ", " N1050H ", " N1110H ", " A210K " of REXPEARL series of NEWCREL series etc..

In addition, the acid as the ethylenic unsaturation composition containing side chain containing oxygen atom that can be used in the present invention is modified Vistanex, can enumerate the BONDINE series (commodity as maleic anhydride modified vistanex of Arkema company systems Name).As specific trade name, there are " LX-4110 ", " HX-8210 ", " HX-8290 ", " TX-8030 ", " AX-8390 " etc..

Release layer also needs to contain crosslinking agent in addition to containing acid-modified polyolefin resin.

By containing crosslinking agent, the various performances such as cohesiveness, the water resistance of release layer can be further improved.Crosslinking agent Addition need to be 1~50 mass parts relative to the mass parts of acid-modified polyolefin resin 100, and more preferably 2~40 mass parts enter one Step is preferably 2~30 mass parts.

As crosslinking agent, it is possible to use there are multiple officials with carboxyl reaction with self-crosslinking crosslinking agent, intramolecular Compound that can be rolled into a ball etc., wherein preferred isocyanate compound, melamine compound, urea compounds, epoxide, carbon Diimine compounds, containCompound of oxazoline base etc., it is particularly efficient be carbodiimide compound,Oxazoline chemical combination Thing.These crosslinking agents can be applied in combination.

As long as the carbodiimide for having more than 1 in carbodiimide compound molecule is just not particularly limited.Carbon two is sub- 2 carboxyls of the amines in the sour modifying moieties of 1 carbodiimide part and acid-modified polyolefin resin form ester, realize Crosslinking.

As the concrete example of carbodiimide compound, for example, can enumerate to phenylene-bis- (2,6- xylyl carbon two is sub- Amine), tetramethylene-bis- (tert-butylcarbodiimide), hexamethylene -1,4- double (methylene-tert-butylcarbodiimide) etc. there is carbon The compound of di-imidogen, as the poly- carbodiimide of the polymer with carbodiimide.Can using a kind in them or Person two or more.Wherein, from maneuverable angle, preferably poly- carbodiimide.

As the commercially available product of poly- carbodiimide, the CARBODILITE series of Nisshinbo company system can be enumerated, it is more specific and Speech, can enumerate " SV-02 ", " V-02 ", " V-02-L2 ", " V-04 " of water-soluble type；" E-01 ", " E-02 " of emulsion types； " V-01 ", " V-03 " of organic solution type, " V-07 ", " V-09 "；" V-05 " of solventless type.

As long as having more than 2 in isoxazoline compound moleculeOxazoline base is just not particularly limited.Oxazoline Compound is at 2Oxazoline part forms carboxylic acid amide esters with 1 carboxyl in the sour modifying moieties of acid-modified polyolefin resin respectively, Realize crosslinking.

AsThe concrete example of isoxazoline compound, for example, 2,2 '-bis- (2- can be enumeratedOxazoline), 2,2 '-ethylidene-bis- (4,4 '-dimethyl -2-Oxazoline), 2,2 '-to phenylene-bis- (2-Oxazoline), double (2-Oxazoline butylcyclohexane) thioether Etc. havingThe compound of oxazoline base, containsThe polymer of oxazoline base.Can using a kind in them or two or more. Wherein, from maneuverable angle, preferably compriseThe polymer of oxazoline base.

As containingThe commercially available product of the polymer of oxazoline base, can enumerate the EPOCROS of NIPPON SHOKUBAI company systems Series, more specifically, can enumerate " WS-500 ", " WS-700 " of water-soluble type；" K-1010E " of emulsion types, " K- 1020E ", " K-1030E ", " K-2010E ", " K-2020E ", " K-2030E " etc..

In the present invention, release layer preferably comprises polyvinyl alcohol.Polyvinyl alcohol is modified poly- by being scattered in acid in release layer It is appropriate to reduce fissility that acid-modified polyolefin resin brought and play a role in olefin resin, while playing itself institute's band The adaptation come.Further, since polyvinyl alcohol with crosslinking agent together with release layer surface formed microspike, so The easy slip of release layer, the carrying of the film for demoulding for obtaining, windability raising can be significantly improved.

The content of polyvinyl alcohol is more excellent relative to the mass parts of acid-modified polyolefin resin 100, preferably 5~200 mass parts Elect 10~100 mass parts, more preferably 20~50 mass parts as.Content such as pectin/polyvinyl alcohol is more than 5 mass parts, then The influence that the heat treatment temperature (drying temperature) when release layer is formed is caused to fissility can be further reduced, on the other hand, Below 200 mass parts, then the stability of release layer formation liquid can be well kept, additionally be able to be difficult to Generation crawling.

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

The average degree of polymerization of polyvinyl alcohol is not particularly limited, for example, can be 300~5000, from raising release layer shape Into from the viewpoint of the stability with liquid, preferably 300~2000.

It is as described below, there is water solubility in order to use liquid, preferably polyvinyl alcohol in the formation of release layer.

As commercially available polyvinyl alcohol, if commodity in use name is illustrated, JAPANVAM＆POVAL companies can be enumerated The specific trade name " JC-05 " of " J-POVAL ", " VC-10 ", " ASC-05X ", " UMR-10HH "；KURARAY companies The specific trade name " PVA-103 " of " KURARAY POVAL ", " PVA-105 ", the specific trade name " AQ4104 " of " EXCEVAL ", “HR3010”；Specific trade name " PC-1000 ", " PC-2000 " of " DENKA POVAL " of Denki Kagaku Kogyo kabushiki etc..

In the present invention, release layer containing inorganic particulate and/or organic filler as roughened material, but can not necessarily must Must contain.Generally, in order to film assign slipping, add in most cases for example calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, Magnesia, silica, sodium metasilicate, aluminium hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, antimony trioxide, charcoal The inorganic particulates such as black, molybdenum bisuphide, acrylic acid series cross-linked polymer, polystyrene cross-linked polymer, organic siliconresin, fluorine tree Organic fillers such as fat, benzoguanamine resin, phenolic resin, nylon resin, Tissuemat E etc..

But, in inorganic particulate, leave condensed in aqueous dispersions by particle the generation of the oversize grain for causing, sedimentation, And particle from demoulding layer surface come off the problems such as.Inorganic particulate is preferably relative to the mass parts of acid-modified polyolefin resin 100 Below 0.5 mass parts, below more preferably 0.1 mass parts, do not contain particularly preferably.

On the other hand, in organic filler, due to organo-silicon compound, fluorine compounds, wax class, surfactant addition The slipping of film is significantly improved, but there are the following problems：In polyester film base material with the interface of release layer and in release layer table Face low molecular weight compositions are oozed out, and polyester film base material is reduced with the adaptation of release layer, or being contaminated by adhesion when peeling off. Therefore, organic filler is preferably below 0.5 mass parts relative to the mass parts of acid-modified polyolefin resin 100, more preferably 0.1 matter Below amount part, do not contain particularly preferably.

Above-mentioned wax class is the vegetable wax that number average molecular is less than 10000, 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, breast Wooden fruit oil, beeswax, shellac wax, lanolin wax, spermaceti, lignite wax, ceresin, paraffin, microwax, synthetic polyethylene waxes, synthesis Polypropylene wax, synthesizing ethylene-vinyl acetate copolymer waxes etc..

In addition, as above-mentioned surfactant, can enumerate cationic surfactant, anionic surfactant, Nonionic (non-ionic) surfactant, amphoteric surfactant, fluorine system surfactant, reactive surfactant Deng.Typically in addition to the material used in emulsion polymerization, also comprising emulsifying agent class.

For example, as anionic surfactant, can enumerate the sulfuric acid of higher alcohol, senior alkyl sulfonic acid and its Salt, alkyl benzene sulphonate and its salt, polyoxyethylene alkyl sulfate salt, polyoxyethylene alkyl phenyl ether sulfuric acid, vinyl sulphur Base succinate etc..

As nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, poly- second two can be enumerated Alcohol fatty acid ester, ethylene oxide-propylene oxide block copolymer, Polyoxyethylene fatty acid amides fatty acid ester, epoxy ethane-epoxy propane copolymerization Sorbitan 01 derivatives such as the compound with polyoxyethylene structure such as thing, polyoxyethylene sorbitan fatty acid ester etc..

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 can be enumerated ペニ Le Off ェノー Le Port リエチレ Application オキサイ De pay plus thing) and they sulfuric acid, allyl alkyl phenol gather Oxygen Addition on ethylene thing (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 plus thing) and their sulfuric acid Ester salt, 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 plus thing) and the compound with reactive double bond such as their sulfuric acid.

In the present invention, release layer industrially can be by that will be situated between containing acid-modified polyolefin resin, crosslinking agent and liquid The liquid of matter is coated on after polyester film base material and is dried such method and is simply forming.

Constitute the liquid medium preferably aqueous medium of above-mentioned liquid.

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

Amphipathic organic solvent refers to that water dissolubility in organic solvent is the organic molten of more than 5 mass % at 20 DEG C Agent (at 20 DEG C water dissolubility in organic solvent be for example recorded in " solvent handbook " (Kodansha Scientific, Nineteen ninety the 10th edition) etc. document).As the concrete example of amphipathic organic solvent, methyl alcohol, ethanol, normal propyl alcohol, isopropanol can be enumerated Deng alcohols, tetrahydrofuran, 1,4- bis-The ketones such as the ethers such as alkane, acetone, MEK, methyl acetate, n-propyl acetate, acetic acid The esters such as isopropyl ester, methyl propionate, ethyl propionate, dimethyl carbonate, other, can also enumerate the diethylamine containing ammonia, triethylamine, The organic amine compounds such as diethanol amine, triethanolamine, N, N- dimethylethanolamines, N, N- diethyl ethylene diamines, N- diethanol amine, Lactams such as 2-Pyrrolidone, METHYLPYRROLIDONE etc..

For liquid, not damaging in the range of its performance, can also add antioxidant, ultra-violet absorber, Lubricant, colouring agent etc..

Liquid can be obtained by mixing by by acid-modified polyolefin resin, crosslinking agent and liquid medium, the mixing When, it is possible to use the liquid of previously prepared acid-modified polyolefin resin, it is also possible to use acid-modified polyolefin resin Water-borne dispersions.The method that acid-modified polyolefin resin carries out aqueous dispersion is not particularly limited, for example, the world can be enumerated Method described in open No. WO02/055598.In addition, as the aqueous of the water-borne dispersions for constituting acid-modified polyolefin resin Medium, can enumerate the aqueous medium illustrated in above-mentioned liquid.

For the dispersion particle diameter of the acid-modified polyolefin resin of aqueous medium, stability when mixing with other compositions From the viewpoint of mixed storage stability, number average bead diameter is preferably less than 1 μm, more preferably less than 0.8 μm.It is such Dispersion particle diameter can be realized using the preparation method described in No. WO02/055598.Should illustrate, the number of acid-modified polyolefin resin is equal Particle diameter is using dynamic light scattering determination.

The solid constituent containing ratio of the water-borne dispersions of acid-modified polyolefin resin is not particularly limited, for appropriate holding The viscosity of water-borne dispersions, preferably 1~60 mass %, more preferably 5~30 mass %.

The solid constituent of the liquid that the water-borne dispersions of acid-modified polyolefin resin are obtained by mixing with crosslinking agent contains Rate can be properly selected according to stacking condition, target thickness or performance etc., be not particularly limited.But, for appropriate holding The viscosity of liquid, and uniform release layer is formed, the solid constituent containing ratio of liquid is preferably 2~30 matter Amount %, more preferably 3~20 mass %.

Method as being coated on liquid on polyester film base material, can enumerate known method, such as intaglio plate roller coat Cloth method, reverse roll rubbing method, bar rubbing method, die lip rubbing method, air knife coating method, curtain flowing rubbing method, spraying process, dip-coating Method, spread coating etc..

Release layer can be by biaxial stretch-formed polyester film base material coated release layer formation liquid and doing Dry method is formed.As coating liquid after liquid drying means, can enumerate blow 3~60 seconds 40~ The method of 180 DEG C of hot blast.

In the present invention, preferably by the polyester film base material or list of the unstretched state in the stretching process of polyester film base material After the polyester film base material of axle stretching is coated with above-mentioned liquid, the so-called online painting for stretched, being dried and formed release layer Cloth method (イ Application ラインコート methods) is manufactured.Release layer is formed using instant rubbing method, the heat treatment after film stretching can be utilized Temperature promote release layer crosslinking.

Embodiment

Next, being specifically described to the present invention using embodiment.

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

The 1.A layers of copolymerization polyethylene terephthalate of composition

(1)DEG10

To be the diethylene glycol and work of 9.5mol% as the ethylene glycol of glycol component and relative to whole dihydroxylic alcohols It is the terephthalic acid (TPA) input esterification groove of sour composition, is reacted 3 hours at 275 DEG C, obtains carboxylate.Next, will be used as anti- Pentaerythrite base-four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester] (BASF AG's system of oxidant Irganox1010) polyester after relative to polymerization is added in the way of turning into 0.6 mass %, under germanium catalyst, 1.3hPa Under decompression, at 300 DEG C melt polymerization is carried out, obtain relative viscosity 1.38,238 DEG C of fusing point, 70 DEG C of glass transition temperature and be total to Poly- polyethylene terephthalate (DEG10).Diethylene glycol composition is relative to the ratio of whole glycol components 9.5mol%.

(2)DEG14、DEG12、DEG8、DEG4、DEG2

In above-mentioned (1), by diethylene glycol relative to the input ratio of whole glycol components be changed to respectively 13.5mol%, 11.5mol%, 7.5mol%, 3.5mol%, 1.5mol%, in addition, carry out the operation same with (1), obtain copolymerization and gather Ethylene glycol terephthalate (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 be respectively 67 DEG C, 68 DEG C, 70 DEG C, 74 DEG C, 76 DEG C, diethylene glycol composition relative to the ratio of whole glycol components be respectively 14.2mol%, 12.1mol%, 8.1mol%, 3.7mol%, 2.2mol%.

(3)DEG8-2

In above-mentioned (2), without Irganox1010, in addition, carried out in the same manner as DEG8, obtain relative viscosity 1.38th, the copolymerization polyethylene terephthalate (DEG8-2) of 240 DEG C of fusing point, 70 DEG C of glass transition temperature.Diethylene glycol Composition is 8.1mol% relative to the ratio of whole glycol components.

The 2.B layers of amorphous polyester resin of composition (PETG)

To be the hexamethylene diformazan of 34.5mol% as the ethylene glycol of glycol component and relative to whole glycol components Alcohol and the terephthalic acid (TPA) input esterification groove as sour composition, react 3 hours at 275 DEG C, obtain carboxylate.Next, Polyester by Irganox1010 (BASF AG's system) after relative to polymerization is added in the way of turning into 0.6 mass %, in germanium catalysis Under agent, under the decompression of 1.3hPa, at 300 DEG C melt polymerization is carried out, obtain relative viscosity 1.38,75 DEG C of glass transition temperature Amorphous polyester resin (PETG).Cyclohexanedimethanol composition is 30mol% relative to the ratio of whole glycol components.

3. acid-modified polyolefin resin water-borne dispersions

(1)O-1

Using with heater and possessing the mixer of the pressure-resistant 1 liter capacity glass container that can be sealed, by 60.0g's " BONDINE LX-4110 " (Arkema company systems, maleic anhydride modified vistanex), the isopropanol (IPA) of 90.0g, In the triethylamine (TEA) of 3.0g and the distilled water input glass container of 147.0g.Then, the rotary speed for making stirring vane is 300rpm, 140~145 DEG C are maintained at by temperature in system, are stirred 30 minutes.Thereafter, in immersion water-bath, rotary speed is kept Room temperature (about 25 DEG C) is cooled in the state of 300rpm while stirring.By the distilled water of 180g and the N of 3.0g, N- dimethyl ethanol Amine (DMEA) puts into two mouthfuls of round-bottomed flasks of 0.5L, sets mechanical agitator and Li Bixi type coolers, and added with oil-bath Hot flask, evaporates aqueous medium.After evaporating the water and IPA of about 180g, heating terminates, and is cooled to room temperature.After cooling, 300 mesh are used Stainless steel filter (linear diameter 0.035mm, plain weave) liquid parts in flask are carried out with pressure filtration (air pressure 0.2MPa), milky acid-modified polyolefin resin water-borne dispersions (O-1) are obtained.The organic solvent of the aqueous medium Content is 1.0 mass %.

(2)O-2

Use " BONDINE HX-8210 " (Arkema company systems, maleic anhydride modified vistanex) modified as acid Vistanex, carries out operation same during with manufacture water-borne dispersions (O-1), obtains acid-modified polyolefin resin aqueous dispersion Body (O-2).

(3)O-3

Use " BONDINE AX-8390 " (Arkema company systems, maleic anhydride modified vistanex) modified as acid Vistanex, carries out operation same during with manufacture water-borne dispersions (O-1), obtains acid-modified polyolefin resin aqueous dispersion Body (O-3).

(4)O-4

Using with heater and possessing the mixer of the pressure-resistant 1 liter capacity glass container that can be sealed, by 30.0g's " REXPEARLEAA A210K " (Japan Polyethylene company systems, acrylic acid modified polyvinyl resin), 105.0g are just In propyl alcohol (NPA), the distilled water input glass container of the TEA and 157.2g of 7.8g, the rotary speed for making stirring vane is 300rpm.Then temperature in system is maintained at into 170 DEG C to stir 30 minutes.Keep being cooled in the state of rotary speed 300rpm Room temperature (about 25 DEG C).By in 2 mouthfuls of round-bottomed flasks of the DMEA inputs 0.5L of the distilled water of 180g and 3.0g, mechanical agitator is set With Li Bixi type coolers, and with oil-bath heat flask, evaporate aqueous medium.After evaporating the water and NPA of about 180g, heating Terminate, be cooled to room temperature.After cooling, with the stainless steel filter of 300 purposes (linear diameter 0.035mm, plain weave) in flask Liquid parts carry out pressure filtration (air presses 0.2MPa), obtain milky acid-modified polyolefin resin water-borne dispersions (O- 4).The content of the organic solvent of the aqueous medium is 1.0 mass %.

(5)O-5

Using with heater and possessing the mixer of the pressure-resistant 1 liter capacity glass container that can be sealed, by 60.0g's " PRIMACOR 5980I " (Dow Chemical company systems, acrylic acid modified polyolefins resin), the TEA and 223.2g of 16.8g Distilled water input glass container in.Then, make the rotary speed of stirring vane for 300rpm, temperature in system is maintained at 140~145 DEG C, stir 30 minutes.Thereafter, in immersion water-bath, keep being cooled down while stirring in the state of rotary speed 300rpm To room temperature (about 25 DEG C).Also, filtered (air with the stainless steel filter of 300 purposes (linear diameter 0.035mm, plain weave) Pressure 0.2MPa), obtain the water-borne dispersions (O-5) of micro- gonorrhoea.Now, almost without cull on filter.

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

[table 1]

4. assay method

(1) composition of acid-modified polyolefin resin

(Varian company systems GEMINI2000/300,300MHz) is analyzed by 1H-NMR to try to achieve.By o-dichlorohenzene (d4) As solvent, it is measured at 120 DEG C.

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

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

(3) fusing point of acid-modified polyolefin resin

Using resin 10mg as sample, determine device (Perkinelmer company system DSC7) using means of differential scanning calorimetry and exist It is measured under conditions of 10 DEG C/min of programming rate, fusing point is obtained by the heating curve for obtaining.

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

The method recorded with JIS K7206 is measured.

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

Appropriate water-borne dispersions are weighed, the quality that it is heated to residue (solid constituent) at 150 DEG C reaches perseverance Amount, obtains solid constituent containing ratio.

(6) organic solvent content of water-borne dispersions

Using Shimadzu Seisakusho Ltd. company system gas-chromatography GC-8A, by water-borne dispersions or dilute with water water-borne dispersions Obtained by Direct material input device, obtain the content of organic solvent.Detectable limit is 0.01 mass %.

The detailed conditions of gas-chromatography are as follows.

Detector：FID, carrier gas：Nitrogen, column packing (GL Sciences company systems)：PEG-HT (5%)-Uniport HP (60/80 mesh), column dimension：Diameter 3mm × 3m, sample puts 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

Company system Microtrac Particle Size Analyzers UPA150 (MODELNo.9340, dynamic light scattering method) are filled using day machine, Obtain number average bead diameter.The refractive index of the resin that particle diameter is used in calculating is 1.50.

(8) uneven thickness rate

To the demoulding biaxially oriented polyester film that obtains in transverse direction (TD) with 5mm measuring space thickness, obtain flat is used Average (Tave), maximum (Tmax), minimum value (Tmin), and calculate uneven thickness rate using following formula.

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

(9) elongation at break, fracture strength

Elongation at break and fracture strength use the cupping machine (company of Shimadzu Seisakusho Ltd. that clamp portion is covered with heating chamber System) determine.Sample the commenting as longitudinal direction (MD) of MD100mm × TD10mm is taken from the demoulding biaxially oriented polyester film for obtaining Valency sample, takes the sample of TD100mm × MD10mm as the evaluation sample of transverse direction (TD), is held on interval and is set to 50mm's Fixture is fixed.Then, using the heating chamber of the holder part for being arranged at cupping machine, sample is maintained at 120 DEG C Atmosphere.Sample was stretched with the speed of 200mm/ minutes, with the force cell measuring load for being installed on testing machine.

The load during fracture of load-elongation curve (lotus stretches bent Line) is read, is accumulated except the load with the sample in cross section before stretching Lotus, calculates fracture strength (MPa).

In addition, the grip separation (L1) during by initial grip separation (L0) and fracture uses following formula, calculate fracture and stretch Rate (%) long.

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

To longitudinal direction (MD) and laterally each sample of (TD) is measured with testing number n=5, stress when obtaining fracture and is stretched The average value of whole measurement results of rate long.

(10) mouldability

The demoulding biaxially oriented polyester film that will be obtained is not forming the side that the face of release layer connects with the Cavity surface of mould After formula is arranged in the chamber of the lower cavity die of differential pressure forming mould, attract to be fixed on mould inner wall by mould, then to lower cavity die Top project acrylic resin, by parts-moulding.Make the shape of part as a diameter of 50mm, the diameter of opening surface of bottom surface For 60mm, depth 30mm it is cup-shaped.Film and part are taken out from mould, lower film is peeled off from part.The release layer of the film peeled off is observed, The mouldability of demoulding biaxially oriented polyester film is evaluated by whetheing there is the fracture of film, having flawless.

(11) peel strength

Width 50mm, length 150mm are crimped in the release layer side rubber rollers of the demoulding biaxially oriented polyester film for obtaining Polyester adhesive tape (day east electrician's company system No.31B/ acrylic acid series sticker) as sample.By sample with metallic plate/rubber The mode of offset plate/sample/rubber slab/metallic plate is clamped, and is placed 20 hours under 2kPa load, 70 DEG C of atmosphere, is cooled down thereafter Return to normal temperature within more than 30 minutes and obtain peel strength measurement sample.Cupping machine is used in 25 DEG C of thermostatic chamber (Intesco company systems precision universal testing machine 2020 type) determines adhesive tape and the demoulding of peel strength measurement sample The peel strength of film.Make peel angle for 180 degree, peeling rate is 300mm/ minutes.

(12) bonding rate is remained

The polyester adhesion glue that will be got off from demoulding biaxially oriented polyester film sur-face peeling using above-mentioned peeling strength test Band is attached to the sided corona treatment of biaxially stretched polyester resin film (You Niji can company system " EmbletPET-12 ", 12 μm of thickness) Face, in 2kPa load, at room temperature place 20 hours.Thereafter, cupping machine (Intesco companies are used in 25 DEG C of thermostatic chamber The accurate type of universal testing machine 2020 of system) determine the peel strength of polyester adhesive tape and film.Make peel angle for 180 degree, Peeling rate is 300mm/ minutes.The peel strength obtained by the measure is designated as F1.

On the other hand, at biaxially stretched polyester resin film (You Niji can company system " EmbletPET-12 ", 12 μm of thickness) Sided corona treatment face attach polyester adhesive tape (day east electrician's company system No.31B/ acrylic acid of width 50mm, length 150mm Be sticker), in 2kPa load, at room temperature place 20 hours.Thereafter, cupping machine is used in 25 DEG C of thermostatic chamber (Intesco company systems precision universal testing machine 2020 type) determines the peel strength of polyester adhesive tape and film.Make stripping Angle is 180 degree, and peeling rate is 300mm/ minutes.The peel strength obtained by the measure is designated as F2.

Using peel strength F1, F2 for obtaining, obtained remaining bonding rate according to following formula.

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

When the release layer that the sticker surface of adhesive tape is demolded film pollutes, the reduction of adherence again of adhesive tape is damaged The harmful performance as adhesive tape.Therefore, the higher the better for residual bonding rate.

Embodiment 1

Using the DEG10 as the resin for constituting A layer, by its at 270 DEG C of temperature using extruder melting, use in addition As the PETG of the resin for constituting B layer, by it also at 270 DEG C of temperature using the melting of other extruders, each molten mass is set to exist Compound engagement device is extruded behind interflow by T-shaped mould, is obtained A layers/B layers/A layers this 3 layers and is constituted not with the quick cooling of cooling drum Stretching stacked film.Now, the spray volume of each extruder is adjusted in the way of thickness is constituted than for 1/4/1.

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

Non-stretched stacked film is stretched to 3.0 times along longitudinal direction first with roller stretching method at 80 DEG C, by liquid (E-3) With the gravure roll of 120 mesh with as 5g/m²Mode be coated on the longitudinal stretching film after, be passed to 50 DEG C of heated-air drying Stove 20 seconds.

Next, the longitudinal stretching film that liquid is applied and has been dried transversely is existed using tenter stretching method After 100 DEG C are stretched to 3.3 times, while being heat-treated the temperature of 3% slack side at 225 DEG C is laterally carried out.Further by film After cooling, using up- coiler wound into rolls, the demoulding biaxially oriented polyester film that thickness is 50 μm is obtained.

[table 2]

Embodiment 2~6, comparative example 1~2

The composition of polyester film base material is pressed into change shown in table 3, in addition, is carried out similarly to Example 1 and is obtained the demoulding Use biaxially oriented polyester film.

Comparative example 3

Using the DEG8 as the resin for constituting A layers, it is melted at 270 DEG C of temperature using extruder, by this Molten mass is extruded from T-shaped mould, is quickly cooled down with cooling drum and obtains non-stretched monofilm.Liquid (E-3) is used and is stepped Wire rod (マイヤーバー) is with as 4.5g/m²Mode coat the unstretching film after, with 120 DEG C of heated-air drying Stove is dried 90 seconds, obtains the non-stretched polyester film of 50 μm of thickness.

Film to being obtained in embodiment 1~6, comparative example 1~3 evaluates elongation at break, fracture strength, uneven thickness rate. Show the result in table 3.

[table 3]

The demoulding biaxially oriented polyester film obtained in embodiment 1~6 is because fracture strength is low, elongation at break is high, institute Even if being the film for being adapted to shaping to be molded the also fracture without film.

The film of the demoulding biaxially stretched polyester obtained in embodiment 2 is free of antioxidant with A layers of polyester film base material The film of embodiment 4 compares, and by adding antioxidant, improves fracture strength, elongation at break.

The film of comparative example 1 due in A layers of base material of copolymerization polyethylene terephthalate is constituted diethylene glycol into The ratio divided is few, so elongation at break is low, in comparative example 2, its ratio is more, and due to thermal decomposition, bubble enters in film, so Elongation at break is low, in any shaping, the position of fracture can be observed in a part for film.

The film of comparative example 3 due to without amorphous polyester resin layer as B layers of base material, so fracture strength is high, into Film does not follow mould in type, there is shaping bad.

Embodiment 7~14, comparative example 4~6

By acid-modified polyolefin resin water-borne dispersions,The aqueous solution and polyvinyl alcohol water solution of isoxazoline compound Mix in the way of as the solid constituent ratio shown in table 2, in addition in the way of as the solid constituent containing ratio shown in table 2 Dilute with water, obtains each liquid.Using the liquid for obtaining, make the thickness of release layer as the value shown in table 4, except this Outside, demoulding biaxially oriented polyester film is obtained similarly to Example 1.Due to the liquid (E-1) without polyvinyl alcohol (E-11) is poor to the coating of polyester film base material, thus using be added with relative to liquid be 0.1 mass % as The liquid of the acetylenediol of surfactant.

Embodiment 15

In embodiment 1, the operation of coating liquid (E-3) is omitted, do not formed the biaxial stretch-formed poly- of release layer Ester film base material.By liquid (E-3) with Meyer wire rod (マイヤーバー) with as 4.5g/m²Mode coat After the biaxially oriented polyester film base material for arriving, dried 90 seconds with 120 DEG C of hot-air drying stoves, obtain the demoulding that thickness is 50 μm and use double Axle oriented polyester film.

Film to being obtained in embodiment 1,7~15, 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 is strong due to the stripping of the index as release property Degree and residual bonding rate are excellent, so can be easily peeled off film after shaping.The release layer in the film peeled off is not observed in addition To crackle.

The demoulding biaxially oriented polyester film obtained in embodiment 14,15 with formd on identical polyester film base material it is identical The embodiment 1 of the release layer of composition is compared, because the peel strength and residual bonding rate of the index as release property are slightly worse, so Stop is somewhat felt after shaping during stripping film.Crackle is not observed in the release layer of the film peeled off.

The film of comparative example 4 is high due to constituting the ratio of the sour altered contents of the acid-modified polyolefin resin of release layer, in addition The film of comparative example 5,6 due in release layer be free of crosslinking agent, so compared with the film of the release layer with same thickness, being Peel strength is high, in addition remain bonding rate it is low, release property is poor, also deposit after shaping cannot stripping film part.Peeling off in addition The release layer of film observe crackle.

Claims

1. a kind of molded structure demoulding biaxially oriented polyester film, it is characterised in that be at least one side in polyester film base material Biaxially oriented polyester film with release layer,

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

The thickness of polyester film base material is 30~200 μm,

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

2. molded structure demoulding biaxially oriented polyester film according to claim 1, it is characterised in that polyester film base material Ratio containing diethylene glycol composition is that i.e. A layers of the copolymerization polyethylene terephthalate layer and amorphism of 4~12mol% gather Ester resin bed is B layers at least each 1 layer.

3. molded structure demoulding biaxially oriented polyester film according to claim 1, it is characterised in that release layer enters Step contains polyvinyl alcohol, and its content is 5~200 mass parts relative to the mass parts of acid-modified polyolefin resin 100.

4. molded structure demoulding biaxially oriented polyester film according to claim 2, it is characterised in that A layers containing anti- The mass % of oxidant 0.1~1.

5. molded structure demoulding biaxially oriented polyester film according to claim 2, it is characterised in that constitute A layers Copolymerization polyethylene terephthalate is polymerized using germanium catalyst.

6. the molded structure demoulding biaxially oriented polyester film according to any one of Claims 1 to 5, its feature exists In biaxial stretch-formed face multiplying power is 9.0~12.3 times.