CN101842236B - Releasing polyester film - Google Patents
Releasing polyester film Download PDFInfo
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- CN101842236B CN101842236B CN200880114167.3A CN200880114167A CN101842236B CN 101842236 B CN101842236 B CN 101842236B CN 200880114167 A CN200880114167 A CN 200880114167A CN 101842236 B CN101842236 B CN 101842236B
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- Prior art keywords
- film
- mylar
- polyester
- polyester resin
- wiring board
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/68—Release sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
- H05K3/4635—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating flexible circuit boards using additional insulating adhesive materials between the boards
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Disclosed is a releasing polyester film having a three-layer structure composed of a polyester resin layer A, a polyester resin layer B and another polyester resin layer A. The releasing polyester film is biaxially stretched. The polyester resin layers A serving as the surface layers contains 1.5-2.8% by mass of inactive particles having an average particle diameter of 3.0-4.3 [mu]m. The polyester resin layer B serving as the intermediate layer contains no or not more than 0.5% by mass of inactive particles. The average particle diameter of the inactive particles is not less than the thickness of the polyester resin layers A. The thickness of the polyester resin layers A is not less than 0.5 [mu]m but not more than 2.8 [mu]m, and the thickness of the entire polyester film is not less than 20 [mu]m but not more than 100 [mu]m.
Description
Technical field
The present invention relates to releasing polyester film, particularly be suitable as the releasing polyester film of the film carrier that uses in the lamination operation in the manufacturing process of printed wiring board.
Background technology
Printed wiring board with multi-layer conductive circuit, for example, the conductor circuit by will be formed with a plurality of through holes and make epoxy resin etc. be impregnated in the prepreg of glass cloth, for insulate, bonding and conductor protection and laminated multi-layer, thereby form.
In the manufacturing process of the printed wiring board of such laminar structure, the general use makes layered product integrated by a succession of operation that comprises heating, vacuum extrusion process and hyperbaric heating extrusion process.At this moment, layered product and being carried by the film carrier with release property by the substrate that this layered product obtains.The film carrier of release property uses for the layered product of the multilayer that consists of printed wiring board from the up and down clamping, after heating, vacuum extrusion process and hyperbaric heating extrusion process, from being peeled off and batched by the integrated printed wiring board that obtains of layered product.
The stripper plate driving fit of layered product and pressurizing unit in extrusion process when film carrier prevents the manufacturing of printed wiring board.But, the through hole that in layered product, softening epoxy resin etc. forms in by conducting channel in the heating extrusion process and contacting with film carrier, when therefore film carrier is poor for the release property of the layered product that consists of printed wiring board, cause the deterioration of significant operability, yield reduces.Therefore, the film carrier that uses in the lamination operation for printed wiring board requires the release property with the stripper plate of the material of printed wiring board, pressurizing unit, also requires to help simultaneously the even mouldability of layered product.Therefore, film carrier generally uses heat resistance, polyester film that dimensional stability is high.But present situation is the release property of requirement height.
From such a viewpoint, in JP2002-252458A, proposed by containing the large amorphous silica of particle diameter, the center line roughness on film surface is that 0.1~1.0 μ m and percent thermal shrinkage are the polyester film below 3%.But, as the embodiment that puts down in writing in JP2002-252458A, if coordinate the above large amorphous silica of particle diameter of 4.5 μ m, the degree of surface roughness raises, if make like this and contain the inorganic particulate that particle diameter surpasses 4.5 μ m in film, when film was made, the inorganic particulate secondary aggregation easily formed oversize grain.Therefore, for the manufacturing of film, the rate of rise of the filter of the melt extruder that resin melting is extruded significantly raises, the remarkable variation of operability.If use the absolute filtration diameter to surpass the thick filter of 30 μ m, although eliminated the worry of the rate of rise, because the secondary aggregation thing is sneaked in film, therefore produce the apparent problem of film.
In JP2005-111798A, for the raising of the release property of film carrier, proposed to arrange the polyester film of the release layer that is formed by silicone resin etc. on the center line roughness is the film of 0.1~1.0 μ m.But, in this case, after the manufacturing process of polyester film, need to form the other operation of release layer.Therefore, not only cost raises, and the releasable film of peeling off and batching from printed wiring board through the extrusion process of printed wiring board is except polyester film, also has the release layer that is formed by silicone resin etc., so can not supply with recirculation.In addition, easily produce residual solvent in the manufacturing procedure of silicone resin etc., therefore have the problem of environment aspect.
In JP2006-312263A, the film carrier that is improved as laminar structure and fissility, having proposed to make the average diameter of cooperation particle on top layer of the side is 3~10 μ m, making the use level of this particle is 3~30 % by weight, makes the surface roughness on this top layer count the polyester film of 0.30~1.00 μ m with arithmetic average roughness.But, if take a large amount of cooperation particle diameters of 3~30 % by weight as the macroparticle more than 3 μ m, the surface roughness of film increases, coordinate the particle secondary aggregation when film is made and form oversize grain, even perhaps secondary aggregation is not still primary particle, the rate of rise of the filter of melt extruder still can significantly raise, the remarkable variation of operability.With above-mentioned example similarly, in this case, if use the absolute filtration diameter to surpass the coarse filter of 60 μ m, although eliminated the worry of the rate of rise, because secondary aggregation thing, primary particle are sneaked in film, therefore produce the apparent problem of film.
Summary of the invention
The present invention completes in view of above-mentioned actual conditions, and purpose is to provide the film carrier in the manufacturing process that is suitable as printed wiring board, the polyester film of release property excellence.Here the manufacturing process of said printed wiring board; can enumerate for example for conductor circuit is insulated and protection; and the insulating substrate laminated multi-layer that this conductor circuit and the prepreg that makes epoxy etc. be impregnated in glass cloth are made; after the surface laminated film carrier of layered product therefrom, implement heating, vacuum extruding and hyperbaric heating and push and make the integrated operation of layered product in series-operation.
The inventor furthers investigate in order to solve such problem, found that the biaxial stretch-formed layered polyester film of specific formation shows the release property of height, thereby completes the present invention.
Namely, of the present inventionly to be intended to a kind of releasing polyester film, it is characterized in that, 3 layers by polyester resin layer A/ polyester resin layer B/ polyester resin layer A consist of, be implemented biaxial stretch-formed, the average grain diameter that the polyester resin layer A on formation top layer contains 1.5~2.8 quality % is the inactive particle of 3.0~4.3 μ m, and the polyester resin layer B that consists of the intermediate layer does not contain inactive particle or contains the following inactive particle of 0.5 quality %, and satisfies following formula (1)~formula (3).
D
A≥T
A (1)
2.8≥T
A≥0.5 (2)
100≥T≥20 (3)
Wherein, T
ABe the thickness (μ m) of polyester resin layer A, D
ABe the average grain diameter (μ m) of the inactive particle that contains in polyester resin layer A, T is total bed thickness (μ m) of polyester film.
Releasing polyester film of the present invention has been implemented biaxial stretch-formed, therefore can become the releasing polyester film of mechanical property, excellent in dimensional stability.The average grain diameter that consists of the inactive particle that contains in the polyester resin layer A on top layer is the scope of 3.0~4.3 μ m, and its content is the scope of 1.5~2.8 quality %, therefore can give the required fissility of resin bed A.Consist of the polyester resin layer B in intermediate layer, as the high support of ratio shared in the layer thickness of film integral body, do not contain inactive particle or contain the following inactive particle of 0.5 quality %, therefore can make inactive particle shared use level in the whole layers of film rest on Min..The so operational problem of wearing and tearing of cutter when therefore not having the generation cut off when stretching, finishing film end, and can obtain the film good like this mechanical property that is difficult to ftracture.The average grain diameter of the inactive particle that contains in polyester resin layer A is more than the thickness of polyester resin layer A, therefore can give the required fissility of resin bed A.Therefore total bed thickness of polyester film is 20 μ m~100 μ m, can give polyester film required intensity, and the carrier in can enough various automatic systems etc. stretches with brute force.
Therefore, according to releasing polyester film of the present invention, during as the film carrier of printed wiring board layered product, can keep to heavens the release property with the printed wiring board layered product, can be from the easily demoulding of layered product after heating, vacuum extruding, hyperbaric heating extruding.Therefore, releasing polyester film of the present invention can be kept the productivity ratio of printed wiring board manufacturing process to heavens, and its industrial value is very high.
Description of drawings
Fig. 1 is the sectional view for the device of the time of bleeding of measuring film.
The specific embodiment
Below the present invention is described in detail.
As the polyester resin layer A that consists of releasing polyester film of the present invention and the mylar of polyester resin layer B, so long as polyester based resins such as PETG, polybutylene terephthalate (PBT), PTTs, there is no particular restriction.Because the PETG price is low, draftability is excellent, therefore is fit to use.PETG usually adopts following methods and obtains: adopt the ester-interchange method by dimethyl terephthalate (DMT) and ethylene glycol, after perhaps obtaining oligomer by the direct esterification of terephthalic acid (TPA) and ethylene glycol, carry out melt polymerization or further carry out solid phase.
Also can other compositions of copolymerization in mylar.As other copolymer compositions, as the dicarboxylic acids composition, can enumerate the dicarboxylic acids such as M-phthalic acid, phthalic acid, NDA, 5-(sodium is for sulfo group) M-phthalic acid, oxalic acid, butanedioic acid, adipic acid, decanedioic acid, azelaic acid, dodecylic acid, dimeric dibasic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexane cyclohexanedimethanodibasic; 4-HBA; 6-caprolactone; Lactic acid etc.In addition, diol component as other copolymer compositions, can enumerate diethylene glycol (DEG), propane diols, 1, ammediol, 1,4-butanediol, neopentyl glycol, 1, the ethylene oxide adduct of 6-hexylene glycol, cyclohexanedimethanol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol-A, bisphenol S etc.
The intrinsic viscosity that consists of the mylar of releasing polyester film of the present invention is not particularly limited, and has enough mechanical properties in order to make film, more than being preferably 0.5dl/g.
Releasing polyester film of the present invention is made of 3 layers of polyester resin layer A/ polyester resin layer B/ polyester resin layer A.Consisting of the resin bed A on top layer, is the layer that has coordinated appropriate inactive particle in order to embody release property.Layer B as the intermediate layer coordinated the layer of inactive particle with relatively low concentration, as supporting layer performance function.
Polyester resin layer A contains the inactive particle that average grain diameter is 3.0~4.3 μ m, and its content is 1.5~2.8 quality %.Average grain diameter is during less than 3.0 μ m, and the time lengthening of bleeding described later can't obtain good fissility.In addition, in the situation of average grain diameter over the oversize grain of 4.3 μ m, the filter that melt extrudes melt extruder in operation during the manufacturing of polyester film is (when making polyester film, the size of absolute filtration diameter is generally 15~40 μ m) the rate of rise significantly improve, so the replacement frequency of filter improves.In addition, in the situation of oversize grain, but secondary aggregation thing, the primary particle of inactive particle in the Visual Confirmation film, product property tends to variation.In addition, might come off by inactive particle in the extrusion process of printed wiring board, the damage printed wiring board produces fatal defective.Particularly in hot pressing process, the softening through hole of insulating substrate by forming in conductor circuit, when having used adhesive, adhesive flows out, and therefore accompanies with it, and oversize grain easily comes off from film carrier.The content of inactive particle is during less than 1.5 quality %, and the time lengthening of bleeding described later can't obtain good fissility.On the contrary, when its content surpasses 2.8 quality %, when the manufacturing of polyester film melt extrude operation in the rate of rise of filter of melt extruder significantly improve, therefore the filter replacement frequency improves, and the occurrence frequency of the cut-out of film when stretching also improves, in addition, the wearing and tearing of the cutter during with the finishing of film end also accelerate, and produce the significantly problem of deterioration of above-mentioned operability.In addition, in the extrusion process of printed wiring board, inactive particle comes off.
In releasing polyester film of the present invention, need a large amount of larger inactive particles of size ratio that coordinate, the rate of rise that therefore melt extrudes the operation middle filtrator becomes large problem.Wherein, polyester resin layer B brings into play function as supporting layer, accounts for the more than half of total bed thickness, therefore the jumbo amount of melt extruding become essential.Therefore, this polyester resin layer B is made as the few layer of use level of inactive particle.Specifically, not contain inactive particle fully or only contain below 0.5 quality % be necessary to polyester resin layer B.If the content of inactive particle surpasses 0.5 quality %, the filter rate of rise is accelerated, and has problems in production.In addition, inactive particle comes off in the extrusion process of printed wiring board.
As making the method that contains inactive particle in polyester resin layer B, can enumerate independent use contains the inactive particle of ormal weight by polymerization, mixing the method for masterbatch, perhaps dilute above-mentioned masterbatch with the mylar that does not contain inactive particle and contain the method for the inactive particle of ormal weight.In addition, as described later, the film end of excision after also polyester film can being stretched is mixed and recycles with original raw material.If do like this, preferred from the viewpoint that industrial waste is cut down.
The average grain diameter of the inactive particle that contains in polyester resin layer B is not particularly limited, and is preferably 1~5 μ m.
Releasing polyester film of the present invention is suitable as film carrier and uses in various automatic systems, high mechanical property that therefore need to be take tensile properties as representative.Therefore, must be implemented biaxial stretch-formed.
Releasing polyester film of the present invention must satisfy the relation of following formula (1)~formula (3).
D
A≥T
A (1)
2.8≥T
A≥0.5 (2)
100≥T≥20 (3)
Wherein, T
ABe the thickness (μ m) of polyester resin layer A, D
ABe the average grain diameter (μ m) of the inactive particle that contains in polyester resin layer A, T is total bed thickness (μ m) of polyester film.
D
A<T
AThe time, the time lengthening of bleeding described later can't obtain good fissility.
The thickness T of polyester resin layer A
ABe necessary for 0.5~2.8 μ m, more preferably 1.0~2.5 μ m.During less than 0.5 μ m, the thickness of resin bed is excessively thin, so the inactive particle that contains in the polyester resin layer A on top layer comes off in the extrusion process of printed wiring board, the damage printed wiring board, and the possibility that produces fatal defective is high.As mentioned above, particularly in hot pressing process, the softening through hole of insulating substrate by forming in conductor circuit, adhesive flows out when having used adhesive, therefore accompanies with it, and particle comes off from film carrier.When surpassing 2.8 μ m, coordinated the extrusion capacity of the polyester resin layer A of inactive particle to increase, so the filter rate of rise of melt extruder is accelerated and not preferred.
As mentioned above, total bed thickness (T) of polyester film is that 20~100 μ m are necessary, is preferably 25~50 μ m.During less than 20 μ m, can't obtain required intensity.In this case, for example, through the extrusion process of printed wiring board, peel off polyester film and when batching, because the rigidity of polyester film is not enough, so produce fold on this film from printed wiring board, get involved in coiling tension and the possibility of film fracture is high.When weakening coiling tension in order to tackle this point and batching, fold is propagated to the hyperbaric heating press section sometimes, and its result affect product property, the fraction defective rising.On the contrary, when total bed thickness (T) of polyester film surpassed 100 μ m, not only quality was superfluous, cost is high, and the time lengthening of bleeding.
As the inactive particle that coordinates in releasing polyester film of the present invention, can enumerate following inactive particle.Namely, can enumerate the inorganic particulates such as silica, titanium oxide, calcium carbonate, barium sulfate, aluminium oxide, zeolite, kaolin, clay, talcum, mica, the organic fillers such as acrylic resin, polystyrene resin, phenolic resins, melamine resin, benzoguanamine resin, plexiglass, organic siliconresin.Wherein, the particle diameter of silica (silica) distributes and the masking excellence, and price is low, and is therefore preferred.In addition, can and use the inactive particle more than 2 kinds.
Releasing polyester film of the present invention, imagination is used as the film carrier of the manufacturing process of printed wiring board, and the time of bleeding of preferably adopting assay method described later is below 1.5 seconds.The time of bleeding is to mean below 1.5 seconds that fissility is good.On the contrary, the time of bleeding surpasses 1.5 seconds, means that fissility is bad.Namely, when peeling off polyester film through the extrusion process of printed wiring board from printed wiring board, mean and resisted and can't easily peel off, in addition, also mean when peeling off polyester film and batch from printed wiring board to produce fold, get involved in coiling tension and the tendency of film fracture is high.In addition, if the time of bleeding surpass 1.5 seconds, even when weakening coiling tension and batching, fold is propagated to the hyperbaric heating press section sometimes, affect product property, the tendency rising that fraction defective rises.
Releasing polyester film of the present invention is implemented known blasting treatment, embossing processing by effects on surface, can give concavo-convex to this film surface.Perhaps, can use silicone resin, epoxy resin etc., adopt known method to film surface enforcement coating processing.
Secondly, the example for the manufacture method of releasing polyester film of the present invention describes.
Supply with respectively each extruder with having coordinated 2 kinds, the mylar of the inactive particle of ormal weight, make it melting at the temperature of fusing point~(fusing point+40 ℃) at each mylar, filter by absolute filtration diameter 20~30 μ m that will form with the net sintering compression forming that stainless steel fibre forms respectively, make it to collaborate in the branch manifold die head or in feed block, extrude the lamination sheet of 3 layers into polyester resin layer A/ polyester resin layer B/ polyester resin layer A by T-shaped die head.Then, employing can add the known methods such as the tape casting, air knife method of static makes the lamination plates driving fit of extruding to the cooler drum below adjustment to 30 ℃, carry out chilling and solidify to reach temperature below glass transition temperature, the lamination that obtains desired thickness is stretched sheet not.Secondly, to the lamination that obtains not stretched sheet longitudinally and laterally carry out biaxial stretch-formedly, can obtain the fissility polyester film of mechanical property, excellent in dimensional stability.
As biaxial stretch-formed method, can use biaxial stretch-formed method when adopting the stenter formula biaxial plane is simultaneously longitudinally with cross directional stretch simultaneously, longitudinally stretch the horizontal stretching-machine of rear use stenter formula along the successively biaxial stretch-formed method of cross directional stretch etc. with the roll-type stretching-machine.But successively in the situation of biaxial stretch-formed method, even be stretched to the film of the area multiplying power identical with biaxial stretch-formed method of while, the time of bleeding also extends extraordinarily, therefore preferred biaxial stretch-formed method simultaneously.
Stretching ratio is with the area dynameter of polyester film, and is preferred more than 3 times, and more preferably 4~25 times, the scope of 6~20 times more preferably.The area multiplying power obtains low film difficulty of the time of bleeding during less than 3 times.
The scope of the glass transition temperature of draft temperature preferred polyester resin~(glass transition temperature+60 ℃).Film after stretching, making the relaxation rate of vertical and horizontal is 0~10%, after the heat treatment several seconds at the 150 ℃~temperature of (fusing point of polyester-5 ℃), cool to room temperature batches with the speed that 20~200m/ divides in stenter.Can access the film of desirable thickness thus.
Heat treatment after above-mentioned stretching is to reduce and essential operation for the percent thermal shrinkage that makes film.As heat treatment method, can use the method for spraying hot blast, shine the method for ultrared method, irradiating microwaves etc.Wherein, owing to heating accurately equably, preferably spray the method for hot blast.
In the manufacturing of biaxially-stretched film, the film end that to control with fixture in stenter after stretch processing cuts off, and can this cutting portion not carried out waste treatment and puts into and will be used for resin bed A or/and the extruder of the mylar melting of resin bed B recycles.
Releasing polyester film of the present invention makes by being used for consisting of a plurality of conductor layers of printed wiring board and the integrated lamination of layered product (build-up) engineering method that insulating barrier consists of, can be as the film carrier of release property excellence.As a plurality of conductor layers that make printed wiring board and insulating barrier lamination and integrated lamination engineering method, the method of lamination is carried out in the prepreg heating pressurization that can enumerate the conductor that will be made of Copper Foil and make epoxy resin etc. be impregnated in glass cloth, to carry out the method for lamination with the Copper Foil of the resins such as epoxy, polyimides heating pressurization, be applied to copper facing on the insulating resin body that forms on film in the resin liquid with epoxy, polyimides etc. and prepreg heating pressurization carry out the method etc. of lamination.Releasing polyester film of the present invention, the film carrier that can be used as for any method uses.
Embodiment
By the following examples to the detailed description of the invention.But, the present invention is not limited to these embodiment.Have, in following embodiment and comparative example, the physics value of polyester film is as described below to be measured again.
(1) each layer thickness
Adopt electron microscope (SEM) to carry out the observation in film cross section, measure the thickness of each layer.
(2) particle diameter of inorganic particulate and organic filler
Adopt the laser diffraction and scattering formula particle size determination machine SALD-2000 of society of Shimadzu Seisakusho Ltd. system to measure.
(3) bleed the time (fissility of film)
Use device shown in Figure 1 to measure.That is, at the central portion of table 1, circular glass plate 2 is installed.Along the periphery of glass plate 2, form air groove 8 and airport 9 with the state that is interconnected on table 1.In addition, use the flexible pipe 3 with cock 4 that airport 9 is connected with vavuum pump 5.Use the fixedly test portion film 6 of the size on the surface of stacked coated glass sheets 2 of adhesive tape 7 on table 1.
During mensuration, drive vavuum pump 5, open cock 4 with vacuum exhaust in system.At this moment, test portion film 6 is sealed at the surface of glass plate 2, and after interference fringe appearred in its periphery, it was to glass plate 2 integral extension, measure until its final mobile time (second) that stops, with it as the time of bleeding.
(4) the filter rate of rise
In vertical vertical-type minor axis screw rod (L/D=15) of the screw diameter 14mm with gear pump of the melt extruder that uses, the filter (the Japanese smart line NASLON processed of society) of the absolute filtration diameter 20 μ m that the fixing net sintering compression forming that stainless steel fibre is formed forms on the porous plate that filters bore 10mm φ.Then, the extruded velocity with 1.0kg/hr under 280 ℃ melt extrudes polyester, measures the extrusion pressure after 1 hour, obtains the rate of rise (MPa/hr).
When the rate of rise surpassed 3.0MPa/hr, the filter rate of rise was too fast, was therefore becoming problem in production continuously.
(5) model measurement 1 of printed wiring board
Use is with 5/cm
2Form the Copper Foil (400mm * 400mm) and make epoxy resin be impregnated in the prepreg (400mm * 400mm), prepare the laminate that is formed by consisting of of Copper Foil/prepreg/Copper Foil/prepreg/Copper Foil of glass cloth of the through hole of diameter 0.1mm.(450mm * 450mm) this laminate of clamping is fixed, and then (420mm * 420mm) clamping imports the oil pressure extruder with aluminium sheet with a pair of polyester film from the two sides.Secondly, the temperature that makes oil gear is 105 ℃, carries out 10 minutes extrusion process under the pressure of 2.5MPa.Then, from the oil pressure extruder, test portion is taken out, cooling after, aluminium sheet is taken out, and then polyester film is peeled off.
At this moment, peel strength can easily be peeled off during less than 0.1N/cm, is evaluated as zero.Be that 0.1~0.3N/cm is evaluated as △ with peel strength.Peel strength surpasses 0.3N/cm, is resisted when from laminate, polyester film being peeled off and can not easily peel off, therefore be evaluated as *.
(6) the printed wiring board model measurement 2
Different test portion when using the printed wiring board model measurement 1 from above-mentioned (5) carries out the extrusion process of 10 minutes in the same manner with the printed wiring board model measurement 1 of (5).Then, the limit is with the end of 10N/cm oriented polyester film, and the limit discharges the oil pressure extruding.At this moment, if in the situation that film does not have fracture can discharge be evaluated as zero, if the film fracture, be evaluated as *.
(7) particle that comes off
Microscopic examination is carried out on surface to the laminate that obtains in printed wiring board model measurement 1, and the number of the inorganic particulate that the laminate surface of every 1cm * 1cm is adhered to carries out 10 instrumentations.Be that situation below 1 is designated as zero with confirming to have the counting of (being that inorganic particulate comes off from film) of adhering to of inorganic particulate, with confirm to have situation more than 2 be designated as *.
(8) film production status
Carry out the continuous manufacturing of the biaxial stretch-formed layered polyester film in a week, carry out the extraction of the problem points of this moment.
Manufacture method for the mylar that uses in embodiment, comparative example describes.
(manufacturing of mylar 1)
With terephthalic acid (TPA) 100 mass parts and the ethylene glycol 52 mass parts esterification groove of packing into, depress in adding of 0.3MPaG and carry out esterification under 260 ℃.Then, the polyester oligomer that obtains is supplied in the polycondensation reaction groove, carry out polycondensation reaction in 120 minutes under 280 ℃, obtain inherent viscosity and be 0.62 mylar 1.The filter rate of rise of the mylar 1 that obtains is 0MPa/hr, does not boost fully.
(manufacturing of mylar 2-1)
With terephthalic acid (TPA) 100 mass parts and the ethylene glycol 52 mass parts esterification groove of packing into, depress in adding of 0.3MPaG and carry out esterification under 260 ℃.Then, the polyester oligomer that obtains is supplied in the polycondensation reaction groove.Then, add in the polyester oligomer of polycondensation reaction groove the average grain diameter 3.9 μ m that the filter with mesh 30 μ m filters silica (SYLYCIA 550 processed of FUJI SILYSIA company) ethylene glycol dispersion liquid (concentration 5.5 quality %) so that in the generation polyester containing ratio of silica be 2.0 quality %.Then, carry out polycondensation reaction in 120 minutes under 280 ℃, obtain inherent viscosity and be 0.60 mylar 2.The filter rate of rise of the mylar 2 that obtains is 1.5MPa/hr.
(manufacturing of mylar 2-2)
Same formula when adopting the manufacturing with mylar 2-1, obtain containing 2.5 quality % average grain diameter 3.9 μ m silica, inherent viscosity is 0.60 mylar 2-2.The rate of rise of the mylar 2-2 that obtains is 1.8MPa/hr.
(manufacturing of mylar 2-3)
Same formula when adopting the manufacturing with mylar 2-1, obtain containing 1.7 quality % average grain diameter 3.9 μ m silica, inherent viscosity is 0.60 mylar 2-3.The rate of rise of the mylar 2-3 that obtains is 1.2MPa/hr.
(manufacturing of mylar 2-4)
Same formula when adopting the manufacturing with mylar 2-1, obtain containing 3.0 quality % average grain diameter 3.9 μ m silica, inherent viscosity is 0.60 mylar 2-4.The rate of rise of the mylar 2-4 that obtains is 3.2MPa/hr.
(manufacturing of mylar 2-5)
Same formula when adopting the manufacturing with mylar 2-1, obtain containing 0.8 quality % average grain diameter 3.9 μ m silica, inherent viscosity is 0.60 mylar 2-5.The rate of rise of the mylar 2-5 that obtains is 0.6MPa/hr.
(manufacturing of mylar 2-6)
Same formula when adopting the manufacturing with mylar 2-1, obtain containing 0.3 quality % average grain diameter 3.9 μ m silica, inherent viscosity is 0.60 mylar 2-6.The rate of rise of the mylar 2-6 that obtains is 0.2MPa/hr.
(manufacturing of mylar 2-7)
Same formula when adopting the manufacturing with mylar 2-1, obtain containing 0.7 quality % average grain diameter 3.9 μ m silica, inherent viscosity is 0.60 mylar 2-7.The rate of rise of the mylar 2-7 that obtains is 0.5MPa/hr.
(manufacturing of mylar 3)
Used the silica (the FUJI SILYSIA SYLYCIA420 processed of company) of average grain diameter 3.1 μ m.In addition, same formula when adopting the manufacturing with mylar 2-1, obtain containing 2.0 quality % silica, inherent viscosity is 0.60 mylar 3.The rate of rise of the mylar 3 that obtains is 1.1MPa/hr.
(manufacturing of mylar 4)
Used the silica (the FUJI SILYSIA SYLYCIA440 processed of company) of average grain diameter 6.2 μ m.In addition, same formula when adopting the manufacturing with mylar 2-1, obtain containing 2.0 quality % silica, inherent viscosity is 0.60 mylar 4.The rate of rise of the mylar 4 that obtains is 3.8MPa/hr.
(manufacturing of mylar 5)
Used the silica (the FUJI SILYSIA SYLYCIA740 processed of company) of average grain diameter 5.0 μ m.In addition, same formula when adopting the manufacturing with mylar 2-1, obtain containing 2.0 quality % silica, inherent viscosity is 0.60 mylar 5.The rate of rise of the mylar 5 that obtains is 3.4MPa/hr.
(manufacturing of mylar 6)
Used the silica (the FUJI SILYSIA SYLYCIA310P processed of company) of average grain diameter 2.7 μ m.In addition, same formula when adopting the manufacturing with mylar 2-1, obtain containing 2.0 quality % silica, inherent viscosity is 0.60 mylar 6.The rate of rise of the mylar 6 that obtains is 1.0MPa/hr.
(manufacturing of mylar 7)
Replace silica to use the zeolite (the marshy land chemistry JC-40 processed of society) of average grain diameter 4.0 μ m.In addition, adopt the formula same with polyester 2-1, obtain containing 2.0 quality % zeolite, inherent viscosity is 0.60 mylar 7.The rate of rise of the mylar 7 that obtains is 1.2MPa/hr.
(manufacturing of mylar 8)
Used the silica (the marshy land chemistry MizukasilP-754C processed of society) of average grain diameter 4.7 μ m.In addition, adopt the formula same with polyester 2-1, obtain containing 2.0 quality % average grain diameter 4.7 μ m silica, inherent viscosity is 0.60 mylar 8.The rate of rise of the mylar 8 that obtains is 3.3MPa/hr.
Below be elaborated for embodiment, comparative example.
Embodiment 1
Will to make moisture rate be that the above-mentioned mylar 2-1 of 20ppm drops into extruder A (screw diameter 150mm) with the dehumidified air (dew point :-41 ℃) of 150 ℃ is dry, by the filter of absolute filtration diameter 20 μ m, melt extrude under 280 ℃.On the other hand, to make with dry 5 hours of the dehumidified air (dew point :-41 ℃) of 150 ℃ moisture rate is that the above-mentioned mylar 1 of 20ppm drops into extruder B (screw diameter 220mm), filter by the absolute filtration diameter 20 μ ms identical with extruder A melt extrudes under 280 ℃.2 kinds of resins with melting in the branch manifold die head overlap, and mylar 2-1 as resin bed A, as resin bed B, is become the three-decker of A/B/A with mylar 1, extrude as sheet take total extrusion capacity 900kg/hr from T-shaped die head.Then, the tape casting that employing can add static makes its driving fit and cooling on the cooler drum of 250 ℃ of surface temperatures, obtains the not stretched sheet of A/B/A=20/210/20 (μ m).
Use biaxial stretch-formed machine of stenter formula while under 92 ℃ of draft temperatures, implement simultaneously biaxial stretch-formed to the not stretched sheet that obtains under the condition of vertical 3 times, horizontal 3.3 times.Then, implement heat treatment in 5 seconds at 240 ℃ of temperature, and then after making horizontal relaxation rate be 5% under the state of 240 ℃ of temperature, carry out cooling under 80 ℃.Then, for the clamping vestige that the two ends of the width of film are controlled with fixture is removed, adopt the OLFA MBW50K processed of company (the thick 0.25mm of sword) cutting machine that it is cut off (cutting portion is 15 quality % of film integral body), then batch with coiling machine, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).
The characteristic of the film that obtains is shown in table 1.
Embodiment 2
Use mylar 3 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 3
Making not, the thickness of stretched sheet is A/B/A=27/190/27 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 24.4 μ m.The film that obtains is A/B/A=2.7/19.0/2.7 (μ m).The characteristic of this film is shown in table 1.
Embodiment 4
Use mylar 2-2 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 5
Use mylar 2-3 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 6
Making not, the thickness of stretched sheet is A/B/A=20/360/20 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 40.0 μ m.The film that obtains is A/B/A=2.0/36.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 7
Use mylar 7 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 8
Use mylar 3 in resin bed A, making not, the thickness of stretched sheet is A/B/A=27/210/27 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 26.4 μ m.The film that obtains is A/B/A=2.7/21.0/2.7 (μ m).The characteristic of this film is shown in table 1.
Embodiment 9
Making not, the thickness of stretched sheet is A/B/A=7/230/7 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 24.4 μ m.The film that obtains is A/B/A=0.7/23.0/0.7 (μ m).The characteristic of this film is shown in table 1.
Embodiment 10
Making not, the thickness of stretched sheet is A/B/A=20/170/20 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 21.0 μ m.The film that obtains is A/B/A=2.0/17.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 11
Making not, the thickness of stretched sheet is A/B/A=20/900/20 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 94.0 μ m.The film that obtains is A/B/A=2.0/90.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 12
Use mylar 2-6 in resin bed B.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 13
Make the both ends of the width of the film that in embodiment 1, cut-out is removed pulverize the pellet that the tablet that forms is increased to diameter 10mm, grows 20~50mm left and right, make regenerative granular material (dioxide-containing silica 0.38 quality %, silica particle diameter 3.9 μ m).It is dropped into extruder B, and in extrusion capacity 145kg/hr, adjusting and making regenerative granular material is 115kg/hr.In addition, adopt formula similarly to Example 1, the silica concentration that obtains in resin bed B is the trilamellar membrane of the thick 25.0 μ m of 0.3 quality %.
The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Embodiment 14
The not stretched sheet of the A/B/A=20/210/20 (μ m) that will obtain according to formula similarly to Example 1, after using 3.0 times of the roll-type stretching-machine longitudinal stretchings of 95 ℃, under 120 ℃ with 3.3 times of stenter formula transverse drawing mill cross directional stretch.Then, implement heat treatment in 5 seconds at 240 ℃ of temperature, and then after making horizontal relaxation rate be 5% under the state of 240 ℃, carry out cooling batching under 80 ℃, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.
Comparative example 1
Used mylar 4 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.
The result of doing like this is, although obtain film, the average grain diameter of silica is excessive, so the filter rate of rise of extruder A becomes too high, and problem is arranged in production.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.Find coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
Comparative example 2
Used mylar 5 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.
The result of doing like this is, although obtain film, the average grain diameter of silica is excessive, so the filter rate of rise of extruder A becomes too high, and problem is arranged in production.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.Find coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
Comparative example 3
Used mylar 8 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.
The result of doing like this is, although obtain film, the average grain diameter of silica is excessive, so the filter rate of rise of extruder A becomes too high, and problem is arranged in production.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.Find coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
Comparative example 4
Used mylar 6 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.Because the average grain diameter of the particle that contains in resin bed A is too small, so the speed of evacuation is slow, therefore, during from the laminate stripping film, does not easily peel off in the manufacturing process of printed wiring board.
Comparative example 5
Making not, the thickness of stretched sheet is A/B/A=3/240/3 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 24.6 μ m.The film that obtains is A/B/A=0.3/24.0/0.3 (μ m).The characteristic of this film is shown in table 1.A is thin due to resin bed, so finds coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
Comparative example 6
Making not, the thickness of stretched sheet is A/B/A=50/150/50 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.
The result of doing like this is that although obtain film, the filter rate of rise of extruder A becomes too high, and problem is arranged in production.The film that obtains is A/B/A=5.0/15.0/5.0 (μ m).The characteristic of this film is shown in table 1.The average grain diameter of the particle that contains in this resin bed of the Thickness Ratio of resin bed A A is thick, and the time of therefore bleeding is long.Therefore, during from the laminate stripping film, easily do not peel off in the manufacturing process of printed wiring board.
Comparative example 7
Making not, the thickness of stretched sheet is A/B/A=30/200/30 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 26.0 μ m.
The result of doing like this is that although obtain film, the filter rate of rise of extruder A becomes too high, and problem is arranged in production.The film that obtains is A/B/A=3.0/20.0/3.0 (μ m).The characteristic of this film is shown in table 1.
Comparative example 8
Making not, the thickness of stretched sheet is A/B/A=20/120/20 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 16.0 μ m.The film that obtains is A/B/A=2.0/12.0/2.0 (μ m).The characteristic of this film is shown in table 1.Because total bed thickness of film is excessively thin, during the manufacturing after-drawing film of printed wiring board, produced the film fracture.Therefore, in the series-operation the during manufacturing of printed wiring board, worry the generation of film fracture, fold when releasable film is batched, lack practicality.
Comparative example 9
Used mylar 2-4 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.But in resin bed A, the content of silica is too much, although therefore obtained film, the filter rate of rise of extruder A becomes too high, and therefore producing has problem.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.Found coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
Comparative example 10
Used mylar 2-5 in resin bed A.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.In resin bed A, the content of silica is very few, and the time of therefore bleeding is long.Therefore, in the manufacturing process of printed wiring board from laminate easily stripping film be difficult.
Comparative example 11
Used mylar 6 in resin bed A, making not, the thickness of stretched sheet is A/B/A=28/210/28 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 26.6 μ m.The film that obtains is A/B/A=2.8/21.0/2.8 (μ m).The characteristic of this film is shown in table 1.The average grain diameter of the particle that contains in this resin bed of the Thickness Ratio of resin bed A A is thick, and the time of therefore bleeding is long.Therefore, easily do not peel off during from the laminate stripping film in the manufacturing process of printed wiring board.
Comparative example 12
Making not, the thickness of stretched sheet is A/B/A=20/1000/20 (μ m).In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 104.0 μ m.The film that obtains is A/B/A=2.0/100.0/2.0 (μ m).The characteristic of this film is shown in table 1.B is thick due to resin bed, and the time of therefore bleeding is long.Therefore, easily do not peel off during from the laminate stripping film in the manufacturing process of printed wiring board.
Comparative example 13
Used mylar 2-8 in resin bed B.In addition, adopt formula similarly to Example 1, obtain the trilamellar membrane of thick 25.0 μ m.But in resin bed B, the content of silica is too much, although therefore obtained film, the filter rate of rise of extruder B becomes too high.Therefore, in production, problem is arranged.The film that obtains is A/B/A=2.0/21.0/2.0 (μ m).The characteristic of this film is shown in table 1.The content of the silica in resin bed B is too much, so has found coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
[table 1]
As shown in Table 1, the film of embodiment 1~14 is excellent releasing polyester film.
To this, following problem is arranged in each comparative example.
Comparative example 1~3 because the average grain diameter of silica in resin bed A has surpassed the scope of stipulating in the present invention, so has been found coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
The average grain diameter of the silica in the resin bed A of comparative example 4 is less than the scope of stipulating in the present invention, and the time of therefore bleeding is long.Therefore, in the manufacturing process of printed wiring board, the release property of film is poor, therefore from printed wiring board stripping film difficulty, the fracture that has also produced film.
The thin thickness of the resin bed A of comparative example 5 beyond the scope of formula (2), has been found coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
The thickness of comparative example 6 and 7 resin bed A is thick, outside the scope of formula (2).Therefore, coordinated the filter rate of rise of extruder A of the resin bed A of inactive particle to accelerate, on producing, problem has been arranged.
The total bed thickness of the film of comparative example 8 is thin, beyond the scope of formula (3), and therefore film fracture in the manufacturing process of printed wiring board.
Therefore in comparative example 9, in resin bed A, the content of silica has surpassed the scope of stipulating in the present invention, is used for having coordinated the filter rate of rise of extruder A of the resin bed A of inactive particle to accelerate, and problem is arranged in production.In addition, found coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
In comparative example 10, the scope of regulation in the discontented unabridged version invention of the content of silica in resin bed A, the time of therefore bleeding is long.Therefore, in the manufacturing process of printed wiring board, the release property of film is poor, therefore from printed wiring board stripping film difficulty, the fracture that has also produced film.
In comparative example 6 and 11, the average grain diameter of the particle that contains in this resin bed of the Thickness Ratio of resin bed A A is large, outside the scope of (1).Therefore, the time of bleeding is long, in the manufacturing process of printed wiring board, can't easily peel off during from the laminate stripping film.
The total bed thickness of the film of comparative example 12 is thick, and beyond the scope of formula (3), the time of therefore bleeding is long.Therefore, in the manufacturing process of printed wiring board, the release property of film is poor, therefore from printed wiring board stripping film difficulty.
Therefore in the resin bed B of comparative example 13, the content of silica has surpassed the scope of stipulating in the present invention, has coordinated the filter rate of rise of extruder B of the resin bed B of inactive particle to accelerate, and problem is arranged in production.In addition, found coming off of silicon dioxide granule in the manufacturing process of printed wiring board.
Claims (3)
1. releasing polyester film, it is characterized in that, 3 layers by polyester resin layer A/ polyester resin layer B/ polyester resin layer A consist of, be implemented biaxial stretch-formed, the average grain diameter that the polyester resin layer A on formation top layer contains 1.5~2.8 quality % is the inactive particle of 3.0~4.3 μ m, the polyester resin layer B that consists of the intermediate layer does not contain inactive particle or contains the following inactive particle of 0.5 quality %, and satisfies following formula (1)~formula (3)
D
A≥T
A (1)
2.8≥T
A≥0.5 (2)
100≥T≥20 (3)
Wherein, T
ABe the thickness of polyester resin layer A, unit is μ m; D
ABe the average grain diameter of the inactive particle that contains in polyester resin layer A, unit is μ m; T is total bed thickness of polyester film, and unit is μ m.
2. releasing polyester film according to claim 1, is characterized in that, is implemented biaxial stretch-formed forming simultaneously.
3. the film carrier used of the manufacturing process of printed wiring board, is characterized in that, is made of the described releasing polyester film of claim 1 or 2.
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JP2007283974 | 2007-10-31 | ||
JP2007-283974 | 2007-10-31 | ||
PCT/JP2008/003127 WO2009057315A1 (en) | 2007-10-31 | 2008-10-31 | Releasing polyester film |
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KR (1) | KR101496874B1 (en) |
CN (1) | CN101842236B (en) |
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JP5361589B2 (en) * | 2009-07-21 | 2013-12-04 | ユニチカ株式会社 | Release sheet |
CN104395077B (en) * | 2012-07-02 | 2017-06-09 | 尤尼吉可株式会社 | Demoulding biaxially oriented polyester film |
JP6067492B2 (en) * | 2013-06-21 | 2017-01-25 | 富士フイルム株式会社 | Laminated film, back sheet for solar cell module, and solar cell module |
JP6159207B2 (en) * | 2013-09-20 | 2017-07-05 | 三井化学東セロ株式会社 | Multi-layer release film |
TW202237368A (en) * | 2016-05-20 | 2022-10-01 | 日商日立化成股份有限公司 | Releasing film |
KR102387993B1 (en) * | 2021-01-06 | 2022-04-19 | (주)엘프스 | adhesive member, adhesive sheet comprising the same and manufacturing method thereof |
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2008
- 2008-10-31 KR KR20107006705A patent/KR101496874B1/en active IP Right Grant
- 2008-10-31 TW TW097141937A patent/TWI501871B/en active
- 2008-10-31 JP JP2009538949A patent/JP5409378B2/en active Active
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JPWO2009057315A1 (en) | 2011-03-10 |
WO2009057315A1 (en) | 2009-05-07 |
TW200930574A (en) | 2009-07-16 |
JP5409378B2 (en) | 2014-02-05 |
CN101842236A (en) | 2010-09-22 |
TWI501871B (en) | 2015-10-01 |
KR20100087082A (en) | 2010-08-03 |
KR101496874B1 (en) | 2015-02-27 |
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