CN101531080A - Mold releasing laminated film - Google Patents
Mold releasing laminated film Download PDFInfo
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- CN101531080A CN101531080A CNA2009101328031A CN200910132803A CN101531080A CN 101531080 A CN101531080 A CN 101531080A CN A2009101328031 A CNA2009101328031 A CN A2009101328031A CN 200910132803 A CN200910132803 A CN 200910132803A CN 101531080 A CN101531080 A CN 101531080A
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Abstract
The invention provides a mold releasing laminated film, including a layer composed of a modified polyolefin resin does not easily generate interlayer peeling, has excellent workability and cost performance, while having surface characteristics of fluorine resin, and further, can easily follow a step-like shape of a multilayer board at the time of press formation. A mold releasing laminated film is provided with such layer and a layer composed of an adhesive fluorine resin laminated at least on one surface of such layer.
Description
The application is that denomination of invention is dividing an application of " mold releasing laminated film ", and its applying date is on May 27th, 2005, and application number is 200580017179.0.
Technical field
The present invention relates to the mold releasing laminated film that a kind of surface has the layer that is made of fluororesin, relate to the mold releasing laminated film of the compression moulding that is suitable for very much multilager base plate particularly.
Background technology
So-called mold release film is meant the film that is used for following purposes: the various jointing materials of coating, coating etc. and make it to solidify on this film, and on this film, form thus and film, then this is filmed and peel off and can use.
All the time, as these mold release film, use fluororesin film, poly-(4-methylpentene-1) film that teflon (registration mark) (PTFE) waits and the film that on biaxial stretch-formed PETG (PET) top layer, has been coated with the silicon based material etc.Particularly, known its cohesive of film of fluororesin of using on the top layer is extremely low, the release property excellence.For example patent documentation 1 has proposed to use the scheme of fluorine resin film as mold release film.In addition, to have proposed the top layer be the scheme that fluorine resin and the film of skin lamination on thermoplastic resin use as mold release film to patent documentation 2.
In addition, when making printed circuit board (PCB), ceramic electronic components, thermosetting resin goods, decorative panel etc., mold release film also sandwiches in operation sometimes and uses between the metallic plate or between the resin, bonds between the metallic plate or between the resin avoiding.
For example, the following method of the general employing of the manufacturing of printed circuit board (PCB): the pre-preg sheet (prepreg that infiltration in the glass fabric is had epoxy resin; Prepreg) suitable overlapping several pieces, metal forming such as mounting Copper Foil again, thus by the press process machine heat, pressurization is integrated, and when this pressure processing, make that mold release film is clipped between the increased pressure board and printed circuit board (PCB) of press process machine, this substrate each other, thereby prevent mutual adhesion.
Particularly, in recent years along with the densification of printed circuit board (PCB), the formation that install on the surface is also changing, and in order to carry surface mounting assembly such as chip, uses mostly to have stair-stepping concavo-convex multilager base plate.The occasion of the multilager base plate of such shape laminated into type, be difficult to being exerted pressure equably with common forming method by article shaped, therefore adopt in the following method: in stair-stepping part and this shape are as one man imbedded silicon rubber etc., exert pressure while heat.In addition, in order to exert pressure equably, also proposed to utilize vacuum multistage laminater to come the scheme of moulding.
In addition, be inserted into when preventing compression moulding multilager base plate interlayer the resin fusion of pre-preg sheet and partly flow out to cavity, patent documentation 3 discloses a kind of lamination compacting multilayer film, this film is made of three-decker, two layers are formed by heat-resistant resins such as fluororesin up and down, and sandwich layer is formed by thermoplastic resins such as polyethylene.This multilayer film becomes the fusion pressurized state in the intermediate layer when pressurization, can prevent the outflow of pre-preg sheet.
[patent documentation 1] spy opens flat 8-186141 communique
[patent documentation 2] spy opens the 2002-208782 communique
[patent documentation 3] spy opens flat 10-296765 communique
Summary of the invention
The problem that invention will solve
, in patent documentation 1 and patent documentation 2, because the price height of fluororesin film, therefore want as mold release film and practicability existing problems aspect cost.In addition, if use thin fluororesin film in order to eliminate the cost problem, following problem takes place then: the forfeiture of the deflection of film, operability is poor, and hot sticky attached or the like with corrosion resistant plate taken place when making printed circuit board (PCB).
In addition, to resemble the patent documentation 2 on the top layer be in the layered product of fluororesin because the cohesive of fluororesin is low, therefore with the bonding force of the thermoplastic resin of non-fluorine system etc. a little less than, have the problem that splitting easily takes place.
In addition, patent documentation 3 disclosed multilayer films, must be up and down two layers fluorine resin layer and bonding as the polyvinyl resin layer of sandwich layer.With fluororesin layer and the bonding occasion of polyvinyl resin layer, adopt the method for dry lamination usually.Take the occasion of the method for dry lamination, bonding in order not have bubble etc., what make applying two-layerly has the above thickness of regulation and becomes necessary.This will cause the high fluorine resin of a large amount of use costs, become the problem of reason that the cost of multilayer film raw material improves and so on.
In addition, make each layer respectively, and be the operation of wasting time and energy, become the reason that manufacturing cost improves the dry lamination self that their are fitted.In addition, have the above thickness of regulation, also exist multilayer film can not follow the problem of the stair-stepping shape and so on of multilager base plate well during compression moulding in order to make each layer.
Therefore, problem of the present invention is to provide a kind of mold releasing laminated film, and this mold releasing laminated film has the surface characteristic of fluororesin, is difficult for taking place splitting simultaneously, operability, economy are also excellent, and can easily follow the stair-stepping shape of multilager base plate when further compression moulding.
The measure of dealing with problems
Below the present invention will be described.Moreover, in order to understand the present invention easily, with bracket mode remarks the reference marks of accompanying drawing, but the form that the present invention is not illustrated therefrom limits.
The present invention's first main points relate to a kind of mold releasing laminated film (100A), and it comprises layer (10) that is made of modified polyolefin resin and the layer (20) that is made of adhesive fluorine of pressing on the upper strata of one side at least of this layer.
In first main points of the present invention, preferably constitute by modified polyolefin resin the layer (10) the two sides lamination by adhesive fluorine constitute the layer (20a, 20b).
In first main points of the present invention, preferably by adhesive fluorine constitute the layer (20) thickness be 1～15 μ m, by modified polyolefin resin constitute the layer (10) thickness be 10～100 μ m.
Second main points of the present invention relate to a kind of mold releasing laminated film (100C), constitute by vistanex the layer (30) at least the one side on sequentially lamination by modified polyolefin resin constitute the layer (10) and by adhesive fluorine constitute the layer (20).
In second main points of the present invention, preferably constitute by vistanex the layer (30) the two sides on sequentially lamination by modified polyolefin resin constitute the layer (10a, 10b) and by adhesive fluorine constitute the layer (20a, 20b).
In second main points of the present invention, preferably by adhesive fluorine constitute the layer (20) thickness be 1～15 μ m, by modified polyolefin resin constitute the layer (10) thickness be 0.5～100 μ m, by vistanex constitute the layer (30) thickness be 10～100 μ m.
The 3rd main points of the present invention relate to a kind of mold releasing laminated film (100E), constitute by modified polyolefin resin the layer (10) at least the one side on sequentially lamination by adhesive fluorine constitute the layer (20) and by fluororesin constitute the layer (40).
In the 3rd main points of the present invention, preferably constitute by modified polyolefin resin the layer (10) the two sides on sequentially lamination by adhesive fluorine constitute the layer (20a, 20b) and by fluororesin constitute the layer (40a, 40b).
In the 3rd main points of the present invention, preferably by fluororesin constitute the layer (40) thickness be 1～15 μ m, by adhesive fluorine constitute the layer (20) thickness be 0.5～15 μ m, by modified polyolefin resin constitute the layer (10) thickness be 10～100 μ m.
The 4th main points of the present invention relate to a kind of mold releasing laminated film (100G), constitute by vistanex the layer (30) at least the one side on sequentially lamination by modified polyolefin resin constitute the layer (10), by adhesive fluorine constitute the layer (20) and by fluororesin constitute the layer (40).
In the 4th main points of the present invention, preferably constitute by vistanex the layer (30) the two sides on sequentially lamination by modified polyolefin resin constitute the layer (10a, 10b), by adhesive fluorine constitute the layer (20a, 20b) and by fluororesin constitute the layer (40a, 40b).
In the 4th main points of the present invention, preferably by fluororesin constitute the layer (40) thickness be 1～15 μ m, by adhesive fluorine constitute the layer (20) thickness be 0.5～15 μ m, by modified polyolefin resin constitute the layer (10) thickness be 0.5～100 μ m, by vistanex constitute the layer (30) thickness be 10～100 μ m.
In the present invention first～the 4th main points, the modified polyolefin resin that is preferably formed the layer (10) that is made of modified polyolefin resin is a modified polyvinyl resin.
In third and fourth main points of the present invention, the fluororesin that is preferably formed the layer (40) that is made of fluororesin is an ethylene-tetrafluoroethylene copolymer.
Five points of the present invention relates to a kind of mold releasing laminated film, the layer that is made of fluororesin that it has the layer that is made of heat-resistant resin and presses on the upper strata of one side at least of this layer.
In five points of the present invention, preferably constitute by heat-resistant resin the layer the two sides on lamination by fluororesin constitute the layer.
In five points of the present invention, preferably by fluororesin constitute the layer thickness be 1～15 μ m, by heat-resistant resin constitute the layer thickness be 10～150 μ m.
In five points of the present invention, the fluororesin that forms the layer that is made of fluororesin is ethylene-tetrafluoroethylene copolymer, low melting point ethylene-tetrafluoroethylene copolymer or their mixture preferably.
In five points of the present invention, the heat-resistant resin that forms the above-mentioned layer that is made of heat-resistant resin is any in Merlon, ethylene-vinyl alcohol copolymer, the polyamide preferably.
The 6th main points of the present invention relate to a kind of mold releasing laminated film (100J), it is the laminated film that will when heating laminated compression moulding, be configured in by the layered product that the overlapping multi-piece substrate of adhesive forms between increased pressure board and this layered product, be have sandwich layer (50a) and on the two sides of this sandwich layer lamination by adhesive fluorine constitute the layer (20a, 20b) laminated film, sandwich layer (50a) is formed by the resin with the low fusing point of specific adhesion fluororesin.
In the 6th main points of the present invention, the layer that sandwich layer (50a) preferably is made of modified polyolefin resin.
In the 6th main points of the present invention, preferably further have intermediate layer (60a, 60b) between layer (20a, 20b) and the sandwich layer (50a) that is made of adhesive fluorine, described intermediate layer is by more than one the thermoplastic resin formation that is selected from modified polyolefin resin, ethylene-vinyl alcohol copolymer (EVOH) and the polyamide.
In the 6th main points of the present invention, modified polyolefin resin is modified poly ethylene preferably.
In the 6th main points of the present invention, by adhesive fluorine constitute the layer (20a, 20b) preferred 5～20 μ m of thickness.
In the 6th main points of the present invention, preferably the outer side at the layer (20a, 20b) that is made of adhesive fluorine has the layer (70a, 70b) that is made of fluororesin, and described fluororesin comprises more than one the resin that is selected from the group of being made up of polytetrafluoroethylene (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polychlorotrifluoroethylene (CTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride and sour modification ETFE (EFEP).
In the 6th main points of the present invention, the thickness of film integral body is 100～1200 μ m preferably.
Mold releasing laminated film (100) in first～the 6th main points of the present invention preferably forms by coextrusion.
The invention effect
According to the present invention, a kind of mold releasing laminated film can be provided, and it has the release property of the excellence of fluororesin, is difficult for taking place splitting simultaneously, operability, economy are also excellent, and can also easily follow the stair-stepping shape of multilager base plate when further compression moulding.
Description of drawings
Fig. 1 (a)～(d) is layer ideograph that constitutes that the mold releasing laminated film of first embodiment is shown.
Fig. 2 (a)～(d) is layer ideograph that constitutes that the mold releasing laminated film of first embodiment is shown.
Fig. 3 (a)～(c) is layer ideograph that constitutes that the mold releasing laminated film of the 3rd embodiment is shown.
Fig. 4 (a)～(b) is the key diagram that the effect of mold releasing laminated film in the compression moulding process is shown.
Fig. 5 is the figure that the compression molding device that uses in an embodiment is shown.
Symbol description
100A～100L mold releasing laminated film
10 by modified polyolefin resin constitute the layer
20 by adhesive fluorine constitute the layer
30 by vistanex constitute the layer
40 by fluororesin constitute the layer
50 sandwich layers
60 intermediate layers
70 by fluororesin constitute the layer
200,300 lamination compression molding devices
The specific embodiment
＜the first embodiment 〉
The layer that Fig. 1 illustrates mold releasing laminated film of the present invention constitutes.Shown in Fig. 1 (a), mold releasing laminated film 100A of the present invention, the layer 20 that constitutes by adhesive fluorine that has the layer 10 that constitutes by modified polyolefin resin and press on the upper strata of one side at least of this layer.
" adhesive fluorine " among so-called the present invention, be meant following fluororesin: with fusing point is 150 ℃～250 ℃, as a kind of レ Network ス パ-Le R A3150 (Japanese polyethylene corporate system) of modified polyolefin resin and fluororesin 4 * 10
5～5 * 10
5Under the sample pressure of Pa, 240 ℃ of pressurizations 10 minutes, the laminate of making, cut-out becomes width 2.5cm, length 25cm and the sample obtained, employing is according to the method for JIS Z0237 standard, and 180 degree peel strengths when carrying out the mensuration of 180 degree peel strengths under 23 ℃ of peeling rate 5mm/min, temperature are more than the 4N/cm.
In addition, the IR spectrum of " adhesive fluorine " among the present invention is at 1780cm
-1～1880cm
-1Between have absworption peak.Preferably the IR spectrum of " adhesive fluorine " is at 1790cm
-1～1800cm
-1Between and 1845cm
-1～1855cm
-1Between have and result from the absworption peak of acid anhydrides such as maleic anhydride base, perhaps, at 1800cm
-1～1815cm
-1Between have and result from the absworption peak of end carbon perester radical, perhaps at 1790cm
-1～1800cm
-1Between, 1845cm
-1～1855cm
-1Between and 1800cm
-1～1815cm
-1Between have and result from the absworption peak of mixture of acid anhydrides such as maleic anhydride base and end carbon perester radical.
The IR spectrum of further preferred " adhesive fluorine " is at 1790cm
-1～1800cm
-1Between and 1845cm
-1～1855cm
-1Between have and result from the absworption peak of acid anhydrides such as maleic anhydride base, perhaps at 1800cm
-1～1815cm
-1Between have and result from the absworption peak of end carbon perester radical.
In addition, the 1790cm of acid anhydrides such as maleic anhydride base
-1～1800cm
-1Between the absworption peak height, with respect to resulting from the CH of main chain
2The 2881cm of base
-1Near the ratio of absworption peak height, be 0.5～1.5, be preferably 0.7～1.2, more preferably 0.8～1.0.
In addition, result from the 1800cm of end carbon perester radical
-1～1815cm
-1Between the absworption peak height, with respect to resulting from the CH of main chain
2The 2881cm of base
-1Near the ratio of absworption peak height, be 1.0～2.0, preferred 1.2～1.8, more preferably 1.5～1.7.
As fluororesin with such bonding strength, for example be homopolymers, copolymer with tetrafluoroethylene units, can enumerate endways or side chain has the resin of functional groups such as carbonate group, halogenated carboxylic acid base, hydroxyl, carboxyl, epoxy radicals.If present above-mentioned fusing point and bonding strength, then also can mix various kinds of resin.As the fluororesin that in commercially available product, has bonding strength as described above, for example can enumerate ネ オ Off ロ Application EFEP (ダ イ キ Application industrial group system), Off Le オ Application LM-ETFEAH2000 (Asahi Glass corporate system).
" modified polyolefin resin " among so-called the present invention is meant the resin that the employing arbitrary method makes the acid of inorganic acid, unsaturated carboxylic acid or derivatives thereof etc. obtain with becoming the vistanex graft reaction of matrix.As the polyolefin that becomes matrix, for example use polyethylene and polypropylene etc.As the unsaturated carboxylic acid class, for example use phorone (ボ ロ Application) acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and their acid anhydrides, ester, acid amides, acid imide, slaine etc.As modified polyolefin resin, the copolymer of optimal ethylene and GMA.As the such ethene and the copolymer of GMA, for example can enumerate レ Network ス パ-Le RA3150 (Japanese polyethylene corporate system), ボ Application De Off ア-ス ト E (sumitomo chemical company system).
Mold releasing laminated film 100A of the present invention, the several layers 90 of further lamination on this layer 10 that constitutes by modified polyolefin resin as required.Wherein, shown in Fig. 1 (b), layer 20a, the 20b that is made of adhesive fluorine at layer 10 the two sides lamination that is made of modified polyolefin resin constitutes 100B, and release property can both be brought into play in the two sides, and economy is also excellent, is preferred from this point.
Resemble the occasion that constitutes mold releasing laminated film 100A, the 100B shown in Fig. 1 (a), Fig. 1 (b), preferably layer 20,20a, the 20b that is made of adhesive fluorine is 1～15 μ m, the layer 10 that is made of modified polyolefin resin is 10～100 μ m.By constituting in this wise, even the layer 20,20a, the 20b that are made of adhesive fluorine are thinner, also can make the layer 10 that constitutes by modified polyolefin resin have the thickness and the rigidity of appropriateness, so can be made into mold releasing laminated film 100A, the 100B of operability excellence with deflection.In addition, because the adhesive fluorine of high price is only used necessary minimum, so economy is also excellent.
Shown in Fig. 1 (c), mold releasing laminated film 100 of the present invention can be made on the face of layer 30 at least one side that is made of vistanex layer 10 that lamination sequentially is made of modified polyolefin resin and the laminated film 100C of the layer 20 that is made of adhesive fluorine.
As the layer 30 employed vistanex that constitute by vistanex, can enumerate polyethylene, polypropylene etc., but wherein, the resiliency during from pressurization, the viewpoint of sealing, preferably polyethylene.When constituting in this wise, in laminated film 100A, 100B in order to make operability better, only utilize the layer 10 that constitutes by improved polyalkene to have thickness, but in laminated film 100C, utilize the more cheap layer 30 that constitutes by vistanex also can have thickness, the use amount of modified polyolefin resin can be reduced, thereby the more excellent mold releasing laminated film 100C of economy can be made.
In the mold releasing laminated film 100C that is provided with the layer 30 that constitutes by vistanex, also can the several layers 90 of further as required lamination.Wherein, shown in Fig. 1 (d), preferably be formed in layer 30 the two sides that constitute by the vistanex mold releasing laminated film 100D of layer 10a, the 10b that constitute by modified polyolefin resin of lamination and the layer 20a, the 20b that constitute by adhesive fluorine sequentially.By forming such formation, can access the two sides and all can bring into play the also excellent mold releasing laminated film of release property and economy.
Resemble the occasion that constitutes mold releasing laminated film 100C, the 100D shown in Fig. 1 (c), Fig. 1 (d), the layer 30 that preferably layer 20,20a, the 20b that is made of adhesive fluorine is 1～15 μ m, the layer 10,10a, the 10b that are made of modified polyolefin resin be 0.5～100 μ m, be made of vistanex is 10～100 μ m.By constituting in this wise,, also can make the layer 30 that constitutes by vistanex have the thickness of appropriateness, so can make mold releasing laminated film 100C, the 100D of operability excellence with deflection even the layer 20,20a, the 20b that are made of adhesive fluorine are thinner.In addition, because the adhesive fluorine of high price is only used necessary minimum, so economy is also excellent.
Fig. 2 illustrates another formation of mold releasing laminated film of the present invention.Shown in Fig. 2 (a), mold releasing laminated film 100 of the present invention can be made at the one side at least of the layer 10 that is made of the modified polyolefin resin sequentially layer 20 that is made of adhesive fluorine of lamination and layer 40 the mold releasing laminated film 100E that is made of fluororesin.
As employed fluororesin in the layer 40 that constitutes by fluororesin, for example can enumerate ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymer (THV) etc.Wherein, from the preferred ETFE in aspects such as release property, processability.ETFE can easily obtain as commercially available product, for example can enumerate ア Off ロ Application COP (Asahi Glass corporate system), Tefzel (デ ユ Port Application corporate system), ネ オ Off ロ Application ETFE (ダ イ キ Application industrial group system) etc.
In mold releasing laminated film 100E, because outermost layer has the layer 40 that is made of fluororesin, therefore be positioned at outermost occasion relatively with the layer 20 that constitutes by adhesive fluorine, especially in the release property excellence of the occasion that is used for the compression moulding under the high temperature (more than 200 ℃).Can think this be because, adhesive fluorine presents bond properties when reaching its fusing point when above, has the tendency of release property reduction, in contrast, common fluororesin cohesive at high temperature is little.
Shown in Fig. 2 (a), mold releasing laminated film 100E of the present invention can be as required on its layer 10 that constitutes by modified polyolefin resin several layers 90 of lamination again.Wherein, shown in Fig. 2 (b), preferably be formed in layer 10 the two sides that constitute by the modified polyolefin resin mold releasing laminated film 100F that constitutes of layer 20a, the 20b that constitute by adhesive fluorine of lamination and the layer 40a, the 40b that constitute by fluororesin sequentially.In this laminated film 100F, can make the two sides and all bring into play release property and the also excellent mold releasing laminated film of economy.
Resemble the occasion that constitutes mold releasing laminated film 100E shown in Fig. 2 (a), Fig. 2 (b) or the 100F, the layer 10 that preferably layer 40,40a, the 40b that is made of fluororesin is 1～15 μ m, the layer 20,20a, the 20b that are made of adhesive fluorine be 0.5～15 μ m, be made of modified polyolefin resin is 10～100 μ m.By constituting in this wise, even the layer 40,40a, the 40b that are made of fluororesin are thinner, also can make the layer 10 that constitutes by modified polyolefin resin have the thickness and the rigidity of appropriateness, so can make mold releasing laminated film 100E, the 100F of operability excellence with deflection.In addition, because the fluororesin of high price only uses necessary minimum, so economy is also excellent.
Shown in Fig. 2 (c), mold releasing laminated film 100 of the present invention can be made at the one side at least of the layer 30 that is made of the vistanex sequentially layer 10 that is made of modified polyolefin resin of lamination, the layer 20 that is made of adhesive fluorine and layer 40 the mold releasing laminated film 100G that is made of fluororesin.
When constituting in this wise, mold releasing laminated film 100E, 100F are in order to make operability good, only utilize the layer 10 that constitutes by modified polyolefin resin to have thickness, but mold releasing laminated film 100G utilizes the layer 30 that is made of more cheap vistanex also can have thickness, therefore the use amount of modified polyolefin resin can be reduced, the more excellent mold releasing laminated film 100G of economy can be made.
Same with above-mentioned mold releasing laminated film 100E, in mold releasing laminated film 100G, also can the several layers 90 of further as required lamination.Wherein, preferably resemble layer 10a, 10b that the two sides order lamination that is formed in the layer 30 that is made of vistanex the mold releasing laminated film 100H that Fig. 2 (d) illustrates is made of modified polyolefin resin, layer 20a, the 20b that constitutes by adhesive fluorine and the mold releasing laminated film 100H of the layer 40a, the 40b that constitute by fluororesin.By forming such formation, can make the two sides and can both bring into play release property and the also excellent mold releasing laminated film of economy.
Resemble the occasion that constitutes mold releasing laminated film 100G or the mold releasing laminated film 100H, the layer 30 that layer 10,10a, the 10b that preferably layer 40,40a, the 40b that is made of fluororesin is 1～15 μ m, the layer 20,20a, the 20b that are made of adhesive fluorine be 0.5～15 μ m, be made of modified polyolefin resin be 0.5～100 μ m, be made of vistanex is 10～100 μ m.By constituting in this wise,, but, therefore can make the mold releasing laminated film of operability excellence with deflection owing to make the layer 30 that constitutes by vistanex have appropriate thickness even the layer 40,40a, the 40b that are made of fluororesin are thinner.In addition, because the fluororesin of high price only uses necessary minimum, so economy is also excellent.
＜the second embodiment 〉
Mold releasing laminated film 100 of the present invention can form the such structure of layer that is made of fluororesin that has the layer that is made of heat-resistant resin and press on the upper strata of one side at least of this layer.The invention that second embodiment relates to, the especially mold releasing laminated film that under high temperature environment, also can very suitably use.
In addition, with the above-mentioned layer that constitutes by heat-resistant resin in the face of the opposite side of face of the layer that constitutes by fluororesin of lamination on, can be as required further several layers of lamination.Wherein, can both bring into play on the two sides on the point of release property and economy excellence and consider, preferably constitute the layer that the two sides lamination at the layer that is made of heat-resistant resin is made of fluororesin.
Here, by fluororesin constitute the layer thickness be preferably 1～15 μ m, by heat-resistant resin constitute the layer thickness be preferably 10～150 μ m.By constituting in this wise,, but, therefore can make the mold releasing laminated film of operability excellence with deflection owing to make the layer that constitutes by heat-resistant resin have appropriate thickness and rigidity even the layer that is made of fluororesin is thinner.In addition, because the fluororesin of high price only uses necessary minimum, so economy is also excellent.
Fluororesin in second embodiment, that form the layer that constitutes by fluororesin, preferably ethylene-tetrafluoroethylene copolymer, low melting point ethylene-tetrafluoroethylene copolymer or their mixture.
Here, so-called low melting point ethylene-tetrafluoroethylene copolymer is an adhesive fluorine of putting down in writing definition in the first embodiment.
As the heat-resistant resin that forms the layer that constitutes by heat-resistant resin, can enumerate Merlon, polycarbonate-based alloy, PEI, ethylene-vinyl alcohol copolymer, polyamide, polyamide-based alloy.Wherein, preferably use Merlon, ethylene-vinyl alcohol copolymer, polyamide.
By adopting these resins to form the layer that constitutes by heat-resistant resin, can make the release property laminated film of cheapness, excellent heat resistance.In addition, these resins can be by the co-extrusion moulding of coming out.Can solve the problem of sneaking at interlayer generation impurity the occasion that resembles lamination PET film thus.
Under high temperature (for example more than 180 ℃), the elastic modelling quantity of above-mentioned heat-resistant resin reduces, but by with supersonic welder to the sealing etc. that fuses of the end of mold releasing laminated film, Fig. 3 shown in the back (a) is such, the bonding layer that is made of fluororesin in the end can solve the problem of softening, the fusing of above-mentioned resin.
In addition, the mold releasing laminated film of the present embodiment even use cutlery to cut off film, also has the not temporary transient adaptation of the interlayer of extent of exfoliation.In addition, adhesive tape is installed on mold releasing laminated film, the occasion of extension section is set, hold this extension section and can easily peel off mold releasing laminated film, separate each layer.Like this, that mold releasing laminated film of the present invention has is peelable after use, separate each layer, the advantage that can discard respectively.
＜the three embodiment 〉
Fig. 3 (a) is the sectional view that the thickness direction that the layer of the mold releasing laminated film 100J of third embodiment of the invention constitutes is shown.Illustrated laminated film 100J possesses three-decker, disposes the layer 20a, the 20b that are made of adhesive fluorine in the both sides of sandwich layer 50a.In the present embodiment, the resin that constitutes sandwich layer 50a must be the low resin of fusing point specific adhesion fluororesin.By taking such formation, heating during by compression moulding has only the resin fusion that constitutes sandwich layer 50a to become possibility, can easily follow the stair-stepping shape of multilager base plate when compression moulding.End at laminated film 100J, shown in Fig. 3 (a) left side, the layer 20a, the 20b that are made of adhesive fluorine that preferably takes two layers be directly bonding, with the structure of sandwich layer 50a sealing, but, laminated film 100J approaches because comparing with its surface area fully, usually the size of laminated film 100J is bigger than mould contact surface in addition, and therefore above-mentioned hermetically-sealed construction is optional.
The kind that constitutes the resin of sandwich layer 50a is not particularly limited, but from layer 20a, the 20b that can easily carry out and constitute by adhesive fluorine bonding, have viewpoint in addition than the low-melting fusing point of available adhesive fluorine, preferably be selected from more than one the thermoplastic resin in modified polyolefin resin, ethylene-vinyl alcohol copolymer (EVOH) and the polyamide.
" modified polyolefin resin " in the present embodiment and " adhesive fluorine " respectively with first embodiment in identical.
The laminated film 100J of the present embodiment disposes two layers of layer 20a, 20b that is made of adhesive fluorine in the mode of clamping sandwich layer 50a in layer constitutes.Therefore, the layer that constitutes with sandwich layer 50a with by adhesive fluorine does not need adhesive between 20a, the 20b when bonding.Like this, when making the laminated film 100J of the present embodiment, need be via dry lamination operation in the past, layering of relief press mold 100J becomes possibility by one step of coextrusion.In addition, owing to can come out to make film by co-extrusion, therefore the layer attenuate that will be made of the adhesive fluorine as the high price of raw material is possible.
In the laminated film 100J of the present embodiment, the thickness of layer 20a, the 20b that is made of adhesive fluorine is not particularly limited, preferably in the scope of 5～20 μ m.When the thickness of the layer 20a, the 20b that are made of adhesive fluorine is crossed when thin, might be on intensity the generation problem.When the thickness of the layer 20a, the 20b that are made of adhesive fluorine when thicker than above-mentioned scope, the cost of raw material rises, and will lose by the come out advantage of making layer press mold 100J of co-extrusion.In addition, two layers of thickness by layer 20a, 20b that adhesive fluorine constitutes can be identical, also can be different.
On the other hand, by forming layer 20a, the 20b that constitutes by adhesive fluorine than unfertile land in above-mentioned scope, the flexibility of laminated film 100J during the resin fusion of sandwich layer 50a increases, therefore when lamination is suppressed, can easily follow the stair-stepping shape of multilager base plate, be inserted in the time of can preventing compression moulding multilager base plate interlayer the resin fusion of pre-preg sheet and partly flow out to cavity.
The gross thickness of the laminated film 100J of the present embodiment does not limit especially., get final product so long as seamlessly be filled into the thickness range of the interlayer of multilager base plate when being out of shape as far as possible by the heating of compression moulding after all, from such viewpoint, the thickness of preferred 100～1200 μ m.
Shown in Fig. 3 (b), the mold releasing laminated film 100 of the present embodiment can be made into the mold releasing laminated film 100K that further has intermediate layer 60a, 60b between layer 20a, 20b that is made of adhesive fluorine and sandwich layer 50b, wherein, described intermediate layer 60a, 60b are made of more than one the thermoplastic resin that is selected from improved polyalkene, ethylene-vinyl alcohol copolymer (EVOH) and the polyamide.In the present embodiment, constitute the resin of sandwich layer 50b, must be the resin that has than the low-melting fusing point of the resin that constitutes the layer 20a, the 20b that constitute by adhesive fluorine.By taking such formation, heating during by compression moulding has only the resin fusion that constitutes sandwich layer 50b to become possibility, can easily follow the stair-stepping shape of multilager base plate when compression moulding.End at laminated film 100K, shown in Fig. 3 (b) left side, preferably take intermediate layer 60a, 60b directly bonding, with the structure of sandwich layer 50 sealing, but, laminated film 100K approaches because comparing with its surface area fully, usually the size of laminated film 100K is bigger than mould contact surface in addition, and therefore above-mentioned hermetically-sealed construction is optional.
In the present embodiment, the resin that constitutes intermediate layer 60a, 60b preferably has good fusible resin with the resin that constitutes the layer 20a, the 20b that are made of adhesive fluorine, from such viewpoint, constitute intermediate layer 60a, 60b resin and preferably be selected from more than one thermoplastic resin in improved polyalkene, ethylene-vinyl alcohol copolymer (EVOH) and the polyamide.
In the laminated film 100K of the present embodiment, the kind that constitutes the resin of sandwich layer 50b is not particularly limited, but has good cohesive between the resin of preferred and formation intermediate layer 60a, 60b.Use the occasion of above-mentioned preferred thermoplastic resin as intermediate layer 60a, 60b, sandwich layer 50b and intermediate layer 60a, 60b's is bonding, and the occasion of specific adhesion sandwich layer 50b and the layer 20a, the 20b that are made of adhesive fluorine is easy.In addition, from having viewpoint, can preferably use polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene etc. than the low-melting fusing point of available adhesive fluorine.
The laminated film 100K of the present embodiment disposes two layers intermediate layer 60a, 60b in the mode of clamping sandwich layer 50b in layer constitutes, and disposes layer 20a, the 20b that is made of adhesive fluorine in the outside of this intermediate layer 60a, 60b.That is, sandwich layer 50b and constitute by adhesive fluorine the layer 20a, 20b between the configuration intermediate layer 60a, 60b, seek two-layer bonding.Therefore, two interlayers do not need adhesive.Like this, when making the laminated film 100K of the present embodiment, need be via dry lamination operation in the past, the laminated film 100K that forms 5 layers of structure by one step of coextrusion ground becomes possibility.In addition, owing to can come out to make film by co-extrusion, therefore layer 20a, the 20b attenuate that will be made of the adhesive fluorine as the high price of raw material is possible.
In addition, the laminated film 100K of the present embodiment, intermediate layer 60a, 60b are entrusted bonding task with the layer 20a, the 20b that are made of adhesive fluorine, and sandwich layer 50b can be only selects from having than the viewpoint of the low-melting fusing point of the resin that constitutes the layer 20a, the 20b that are made of adhesive fluorine.Therefore, can enlarge the resin choice scope that constitutes sandwich layer 50b.Like this, reduce the cost of raw material, give new function to laminated film 100K and become easy.
In the laminated film 100K of the present embodiment, the thickness of layer 20a, the 20b that is made of adhesive fluorine is not particularly limited, preferably in the scope of 5～20 μ m.Cross when thin when the thickness of the layer 20a, the 20b that constitute by adhesive fluorine, on intensity, problem might take place.When the thickness of the layer 20a, the 20b that are made of adhesive fluorine when thicker than above-mentioned scope, the cost of raw material rises, the advantage of the making layer press mold 100K forfeiture by coextrusion.In addition, two layers of thickness by layer 20a, 20b that adhesive fluorine constitutes can be identical, also can be different.
In the laminated film 100K of the present embodiment, the thickness of intermediate layer 60a, 60b is not particularly limited, preferably in the scope of 1～20 μ m.When the thickness of intermediate layer 60a, 60b comes out to make by co-extrusion than this scope unfertile land, on making, have difficulties.On the contrary, when the thickness of intermediate layer 60a, 60b was thicker than this scope, the cost of raw material rose, by the come out advantage forfeiture of making layer press mold 100K of co-extrusion.In addition, the thickness of two layers of intermediate layer 60a, 60b can be identical, also can be different.
Like this, form layer 20a, the 20b and intermediate layer 60a, the 60b that by adhesive fluorine constitute than unfertile land by resembling above-mentioned, the flexibility of laminated film 100K during the resin fusion of sandwich layer 50b increases, therefore can easily follow the stair-stepping shape of multilager base plate during the lamination compacting, be inserted in the time of can preventing compression moulding multilager base plate interlayer the resin fusion of pre-preg sheet and partly flow out to cavity.
The gross thickness of the laminated film 100K of the present embodiment does not limit especially.After all, so long as when being out of shape by the heating of compression moulding, the thickness range that seamlessly is filled into the interlayer of multilager base plate gets final product as far as possible, from such viewpoint, the thickness of preferred 100～1200 μ m.
Shown in Fig. 3 (c), in the mold releasing laminated film 100 of the present embodiment, can be made into the layer 20a that is constituting by adhesive fluorine, the outer side of 20b has the layer 70a that is made of fluororesin, the formation of 70b, described fluororesin comprises and is selected from polytetrafluoroethylene (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polychlorotrifluoroethylene (CTFE), ethylene-tetrafluoroethylene copolymer (ETFE), low melting point ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride, with more than one the resin among the sour modification ETFE (EFEP).At this, so-called low melting point ethylene-tetrafluoroethylene copolymer (ETFE) is to have low-melting resin among ETFE, for example can enumerate the Off Le オ Application LM720 of Asahi Glass corporate system.
By taking such formation, this laminated film 100L further improves to the non-transfer printing of multilager base plate side from laminated film 100L fissility, gas barrier and the impurity of mould and multilager base plate during compression moulding.
Layer 70a, 70b that setting is made of fluororesin are as outer field occasion, and the thickness of outer 70a, 70b can be identical, also can be different.Preferred 5～20 μ m of its thickness in addition.Cross when thin when outer field thickness, on intensity, problem might take place.When outer field in addition thickness was blocked up, the cost of raw material rose, by the come out advantage forfeiture of making layer press mold 100L of co-extrusion.
The manufacture method of＜mold releasing laminated film 100 〉
Laminating method as the mold releasing laminated film 100 that the first above-mentioned embodiment～the 3rd embodiment relates to, can enumerate heat fused compacting or coextrusion etc., but wherein, consider from productivity, cost aspect, preferably make method as the mold releasing laminated film 100 of target by the multi-layer co-extruded step ground that comes out.In addition, the method that also can adopt the combination coextrusion and make the intermembranous fusible laminated film of raising.
The purposes of＜mold releasing laminated film 100 〉
The mold releasing laminated film of the present invention 100 that the first above-mentioned embodiment～the 3rd embodiment relates to, as the various jointing materials of coating, coating etc. also solidify on this film in order to pass through, film and on this film, form, peel off this then and film and can use such demoulding film.In addition, mold releasing laminated film 100B, 100D, 100F, 100H, 100J, 100K, the 100L of form of layer that 10 two sides lamination is made of adhesive fluorine in the intermediate layer or the layer that is made of fluororesin is also as the demoulding usefulness film 100 that uses in the compression moulding of multilager base plate with layered product of following explanation.
Below about the lamination compression moulding of multilager base plate, enumerate and use the situation of the mold releasing laminated film 100 that the 3rd embodiment relates to illustrate as example.Mold releasing laminated film 100 of the present invention by the overlapping multi-piece substrate of adhesive phase and lamination the time, uses in order to suppress adhesive resin to flow out.Mold releasing laminated film 100 of the present invention is configured in as Fig. 4 (a) in the lamination compression molding device 200 and uses.
Lamination compression molding device 200 possesses the end that is installed in oil pressure cylinder 210a, 210b, pressurization hot plate 220a, the 220b that disposes opposed to each other up and down.Fig. 4 (a) be pattern the vertical cross-section diagram of state before the pressurization is shown, the pressurization of downside with hot plate 220b on a plurality of substrates 230,230 of mounting ....Each substrate 230,230 ... between be inserted with the pre-preg sheet.The pre-preg sheet resin that infiltrates in cores such as glass fibre forms.
As the resin that the pre-preg sheet is used, can enumerate epoxy resin, BT resin, phenolic resins, unsaturated polyester resin, vinyl ester resin, polyimide resin, polyphenylene oxide resin, fluororesin, pet resin, polybutylene terephthalate (PBT) resin, diallyl phthalate resin, or the like single resin or the thermosetting resin of their mixture or modifier etc.Wherein, from the viewpoint of heat-resisting reliability, preferably use epoxy resin and BT resin.In these resins, can contain the cellulosic packing material such as inorganic particle filled material, glass fibre, asbestos fibre, ceramic fibre of talcum, clay, silica, calcium carbonate etc. as required.The pre-preg sheet, is infiltrated up in the core in specified solvent then with resin dissolves, makes the pre-preg sheet.Core as the pre-preg sheet is generally glass fibre, but also can use aromatic polyamide fibre in addition.In addition, also can use glass, polyester, the aromatic polyamide of felted.And the amount of resin of pre-preg sheet is 30～80 quality % with respect to pre-preg sheet integral body usually.
Multilager base plate carries out under 160～280 ℃ temperature usually with the lamination compression moulding of layered product.At this moment, the sandwich layer 50a, the 50b that are made of thermoplastic resin become molten condition, and on the other hand, the layer 20a, the 20b that are made of adhesive fluorine that clip sandwich layer 50a, 50b become softening state.At this, " molten condition " of so-called sandwich layer 50a, 50b except liquid condition, also comprises: easily cause distortion by moulding pressure, can be soft enough to landfill in fact seamlessly by the state of the degree of the concaveconvex shape of article shaped part.In addition, " softening " of so-called layer 20a, the 20b that is made of adhesive fluorine means: when compression moulding, the interior pressure of the molten resin by sandwich layer 50a, 50b becomes to soften to and gives easily along by the state of the degree of the concavo-convex shape of article shaped.For this reason, when pressurizeing with hot plate 220a, 220b with pressurization up and down, the molten resin of sandwich layer 50a, 50b is closed in the layer space that 20a, 20b surrounded that is made of adhesive fluorine, become pressurized state, by adhesive fluorine constitute the layer 20a, 20b, the interior pressure of the molten resin by sandwich layer 50a, 50b is endowed along by the concavo-convex shape of article shaped (Fig. 4 (b)).Its result, the molten resin landfill of sandwich layer 50a, the 50b of the pressurized state in space that forms with hot plate 220a, 220b by stair-stepping cavity part and pressurization.Therefore the pressure of this molten resin and equal or big than it from the pressure of the adhesive that flows out between substrate can suppress conduct by the outflow of the pre-preg sheet resin between the multilager base plate of article shaped.The relation of the thickness of layer 20a, 20b that the pressure of above-mentioned molten resin constitutes according to the volume of cavity part with by adhesive fluorine waits to determine.That is, according to the body of the molten resin of sandwich layer 50a, 50b
, and the magnitude relationship of the volume of stair-stepping cavity part determine the pressure of molten resin.This pressure is high more, and the effect that suppresses the outflow of pre-preg sheet resin is big more.
[embodiment]
The making of＜mold releasing laminated film (1) 〉
(embodiment 1)
By the mode that becomes following formation, 280 ℃ from the combination die coextrusion, obtain film as target.
The 1st layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 10 μ m
The 2nd layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 80 μ m
The 3rd layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 10 μ m
(embodiment 2)
By the mode that becomes following formation, employing method similarly to Example 1, obtain film as target.
The 1st layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 10 μ m
The 2nd layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 10 μ m
The 3rd strata olefin resin (Japanese Port リ ケ system corporate system ノ バ テ Star Network HD HJ580) 60 μ m
The 4th layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 10 μ m
The 5th layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 10 μ m
(embodiment 3)
By the mode that becomes following formation, at 280 ℃ from the combination die coextrusion, 5 * 10
-3Pa (5kgf/cm
2) pressure under 240 ℃ of pressurized treatments 10 minutes, obtain film as target.
The 1st layer of adhesive fluorine (the system ネ オ 7 ロ Application EFEP EP-5000 of ダ イ キ Application industrial group) 5 μ m
The 2nd layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 5 μ m
The 3rd strata olefin resin (Japanese Port リ ケ system corporate system ノ バ テ Star Network HD HJ580) 60 μ m
The 4th layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 5 μ m
The 5th layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 5 μ m
(embodiment 4)
As adhesive fluorine, use the Off Le オ Application LM-ETFE AH2000 of Asahi Glass corporate system, in addition, carry out similarly to Example 1, obtained mold releasing laminated film.
(embodiment 5)
As adhesive fluorine, use the Off Le オ Application LM-ETFE AH2000 of Asahi Glass corporate system, in addition, carry out similarly to Example 2, obtained mold releasing laminated film.
(embodiment 6)
As adhesive fluorine, use the Off Le オ Application LM-ETFE AH2000 of Asahi Glass corporate system, in addition, carry out similarly to Example 3, obtained mold releasing laminated film.
(comparative example 1)
Make the 1st layer, the 3rd layer of embodiment 1 to be hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymer (ダ イ ニ オ Application corporate system THV220G), in addition, carry out similarly to Example 1, obtained mold releasing laminated film.
(comparative example 2)
Make the 1st layer, the 3rd layer of embodiment 1 to be tetrafluoraoethylene-hexafluoropropylene copolymer (ダ イ キ Application corporate system ネ オ Off ロ Application FEP), in addition, carry out similarly to Example 1, obtained mold releasing laminated film.
(comparative example 3)
Make the 1st layer, the 3rd layer of embodiment 1 to be vinylidene fluoride (Network レ Ha corporate system KF Port リ マ one T#850), in addition, carry out similarly to Example 1, obtained mold releasing laminated film.
(embodiment 7)
By the mode that becomes following formation, 280 ℃ from the combination die coextrusion, obtain film as target.
The 1st layer of fluororesin (Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) 5 μ m
The 2nd layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 10 μ m
The 3rd layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 40 μ m
The 4th layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 10 μ m
The 5th layer of fluororesin (Asahi Glass corporate system Off Le オ Application ETFEC-88AXP) 5 μ m
(embodiment 8)
By the mode that becomes following formation, at 280 ℃ from the combination die coextrusion, 5 * 10
-3Pa (5kgf/cm
2) pressure under, 240 ℃ of pressurized treatments 10 minutes, obtain film as target.
The 1st layer of fluororesin (Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) 5 μ m
The 2nd layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 5 μ m
The 3rd layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 80 μ m
The 4th layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 5 μ m
The 5th layer of fluororesin (Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) 5 μ m
(embodiment 9)
By the mode that becomes following formation, employing method similarly to Example 7, obtain film as target.
The 1st layer of fluororesin (Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) 5 μ m
The 2nd layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 10 μ m
The 3rd layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 10 μ m
The 4th strata olefin resin (Japanese Port リ ケ system corporate system ノ バ テ Star Network HD HJ580) 70 μ m
The 5th layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 10 μ m
The 6th layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 10 μ m
The 7th layer of fluororesin (Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) 5 μ m
(embodiment 10)
By the mode that becomes following formation, employing method similarly to Example 8, obtain film as target.
The 1st layer of fluororesin (Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) 5 μ m
The 2nd layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 5 μ m
The 3rd layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 5 μ m
The 4th strata olefin resin (Japanese Port リ ケ system corporate system ノ バ テ Star Network HD HJ580) 70 μ m
The 5th layer of modified polyolefin resin (Japanese polyethylene corporate system レ Network ス パ-Le RA3150) 5 μ m
The 6th layer of adhesive fluorine (the system ネ オ of ダ イ キ Application industrial group Off ロ Application EFEP EP-5000) 5 μ m
The 7th layer of fluororesin (Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) 5 μ m
(embodiment 11)
As adhesive fluorine, use the Off Le オ Application LM-ETFE AH2000 of Asahi Glass corporate system, in addition, carry out similarly to Example 7, obtained mold releasing laminated film.
(embodiment 12)
As adhesive fluorine, use the Off Le オ Application LM-ETFE AH2000 of Asahi Glass corporate system, in addition, carry out similarly to Example 8, obtained mold releasing laminated film.
(embodiment 13)
As adhesive fluorine, use the Off Le オ Application LM-ETFE AH2000 of Asahi Glass corporate system, in addition, carry out similarly to Example 9, obtained mold releasing laminated film.
(embodiment 14)
As adhesive fluorine, use the Off Le オ Application LM-ETFE AH2000 of Asahi Glass corporate system, in addition, carry out similarly to Example 10, obtained mold releasing laminated film.
(comparative example 4)
Make the 2nd layer, the 4th layer of embodiment 7 to be polyvinyl resin (Japanese Port リ ケ system corporate system ノ バ テ Star Network HD HJ580), in addition, carry out similarly to Example 7, obtained mold releasing laminated film.
(comparative example 5)
Make the 2nd layer, the 4th layer of embodiment 7 to be hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymer (ダ イ ニ オ Application corporate system THV220G), in addition, carry out similarly to Example 7, obtained mold releasing laminated film.
(comparative example 6)
Make the 2nd layer, the 4th layer of embodiment 7 to be tetrafluoraoethylene-hexafluoropropylene copolymer (ダ イ キ Application corporate system ネ オ Off ロ Application FEP), in addition, carry out similarly to Example 7, obtained mold releasing laminated film.
(comparative example 7)
The 2nd layer, the 4th layer that makes embodiment 7 is that (Network レ Ha corporate system KF Port リ マ-T#850), in addition, carry out has similarly to Example 7 obtained mold releasing laminated film to vinylidene fluoride.
(comparative example 8)
Directly having used thickness with the constant state of former state is ETFE (the Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) film of 50 μ m.
The lamination compression moulding (1) of＜substrate 〉
The film that use is made in the above embodiments 1～14 and comparative example 1～8 is as the mold release film in the printed circuit board forming process.Film become sequentially placing from lower floor on the press process machine that printed circuit board forming is used [padded coaming/stainless steel (SUS) decorative panel/mold release film/material laminated into type (and outside decorate with copper plate pressing plate, interior trim with the copper plate pressing plate, have the pre-preg sheet that infiltration has the glass cloth of epoxy resin)/mold release film/stainless steel (SUS) decorative panel/padded coaming], pressurizeing, to suppress be to be that 3.6MPa, pressed temperature are that 180 ℃, heat time heating time are to carry out under 77 minutes the condition at press pressure.
＜evaluation method (1) 〉
For film of in the above embodiments 1～14 and comparative example 1～8, making and the film that in lamination compression moulding, uses, adopt following assessment item to estimate.Evaluation result gathered be shown in table 1 and the table 2.
(extruding processability)
Zero: can stably obtain film by coextrusion (according to circumstances being coextrusion+compacting).
*: splitting during coextrusion, can not stably batch.
(interlaminar adhesion)
Zero: splitting does not take place.
*: splitting takes place when batching etc.
(sealing)
Whether visual investigation epoxy resin is extruded from through-holes of printed circuit boards.
Zero: resin is not extruded from through hole.
△: resin is extruded in the 0.5mm from through hole.
*: resin is extruded to more than the 0.5mm from through hole.
(surperficial release property)
After the press process, between visual valuation stainless steel (SUS) decorative panel and the material laminated into type whether release property is arranged.
Zero: release property is arranged, can peel off lightly.
*: no release property, can not use.
(operability)
Estimated the processing ease of the mold releasing laminated film when coating, when packing forcing press into.
Zero: film has deflection, easily places, and does not play fold.
*: film does not have deflection, is difficult to place, and easily plays fold.
Table 1
| Extrude processability | Interlaminar adhesion | Sealing | The surface release property | Operability | |
| Embodiment 1 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 2 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 3 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 4 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 5 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 6 | ○ | ○ | ○ | ○ | ○ |
| Comparative example 1 | ○ | × | - | - | - |
| Comparative example 2 | ○ | × | - | - | - |
| Comparative example 3 | ○ | × | - | - | - |
As shown in table 1, mold releasing laminated film of the present invention (embodiment 1～6), the interlaminar adhesion of film is good, and as mold release film, sealing, surperficial release property, operability are all excellent.On the other hand, the laminated film of comparative example 1～3, interlaminar adhesion is poor, and each layer peeled off, and can not carry out the evaluation as mold release film.
Table 2
| Extrude processability | Interlaminar adhesion | Sealing | The surface release property | Economy | Operability | |
| Embodiment 7 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 8 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 9 | ○ | ○ | ○ | ○ | ○ | ○ |
| |
○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 11 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 12 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 13 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 14 | ○ | ○ | ○ | ○ | ○ | ○ |
| Comparative example 4 | ○ | × | ○ | ○ | ○ | × |
| Comparative example 5 | ○ | △ | ○ | ○ | ○ | ○ |
| Comparative example 6 | × | × | ○ | ○ | ○ | × |
| Comparative example 7 | ○ | × | ○ | ○ | ○ | × |
| Comparative example 8 | - | - | △ | ○ | × | × |
As shown in Table 2, mold releasing laminated film of the present invention (embodiment 7～14), all excellent aspect all at interlaminar adhesion, release property etc.And the film of comparative example 4～7, though release property, sealing, economy excellence are then poor on other arbitrary project.In addition, former state is directly used the film (comparative example 8) of ETFE film unchangeably, though the release property excellence, economy, operability are poor.
＜mold releasing laminated film is made system (2) 〉
(embodiment 15)
By the mode that becomes following formation, 300 ℃ from the combination die coextrusion, obtain film as target.
The 1st layer of fluororesin (Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le corporate system テ Off ゼ Le 290) 5 μ m
The 2nd layer of heat-resistant resin (エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ Star Network corporate system ユ-ピ ロ Application S-2000) 100 μ m
The 3rd layer of fluororesin (Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le corporate system テ Off ゼ Le 290) 5 μ m
(embodiment 16)
As fluororesin, use the ネ オ Off ロ Application EFEP RP-5000 of ダ イ キ Application industrial group system, in addition, carry out similarly to Example 15, obtain mold release film.
(embodiment 17)
As heat-resistant resin, use the ウ Le テ system 1000 of Japanese GE プ ラ ス チ Star Network system, in addition, carry out similarly to Example 15, obtain mold release film.
(embodiment 18)
By the mode that becomes following formation, 300 ℃ from the combination die coextrusion, obtain film as target.
The 1st layer of fluororesin (Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le corporate system テ Off ゼ Le 290) 5 μ m
The 2nd layer of heat-resistant resin (エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ Star Network corporate system ユ-ピ ロ Application S-2000) 100 μ m
The 3rd layer of fluororesin (Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le corporate system テ Off ゼ Le 290) 5 μ m
(embodiment 19)
As fluororesin, use the ネ オ Off ロ Application EFEP RP-5000 of ダ イ キ Application industrial group system, in addition, carry out similarly to Example 18, obtain mold release film.
(embodiment 20)
As heat-resistant resin, use the ウ Le テ system 1000 of Japanese GE プ ラ ス チ Star Network corporate system, in addition, carry out similarly to Example 18, obtain mold release film.
(embodiment 21)
As heat-resistant resin, use the UBE NYLON610 15B of the emerging product corporate system of space portion, in addition, carry out similarly to Example 18, obtain mold release film.
(embodiment 22)
As heat-resistant resin, use the ソ ア ノ-Le A4412 of Japanese synthetic chemical industry corporate system, in addition, carry out similarly to Example 18, obtain mold release film.
(embodiment 23)
As fluororesin, use the THV220 of Sumitomo ス リ-エ system corporate system, in addition, carry out similarly to Example 15, obtain mold release film.
(embodiment 24)
As fluororesin, use the ネ オ Off ロ Application FEP of ダ イ キ Application industrial group system, in addition, carry out similarly to Example 15, obtain mold release film.
(comparative example 9)
The direct unchangeably used thickness of former state is ETFE (the Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) film of 50 μ m.
(embodiment 25)
As fluororesin, use the THV220 of Sumitomo ス リ-エ system corporate system, in addition, carry out similarly to Example 18, obtain mold release film.
(embodiment 26)
As fluororesin, use the ネ オ Off ロ Application FEP of ダ イ キ Application industrial group system, in addition, carry out similarly to Example 18, obtain mold release film.
(comparative example 10)
The direct unchangeably used thickness of former state is ETFE (the Asahi Glass corporate system Off Le オ Application ETFE C-88AXP) film of 50 μ m.
(reference example 1)
Use the film of embodiment 1.
The lamination compression moulding (2) of＜substrate 〉
By using the film of in the above embodiments 15～26, comparative example 9～10 and reference example 1, making, carry out performance evaluation as the mold release film in the printed circuit board forming process.Film be become sequentially placing from lower floor on the press process machine that printed circuit board forming is used [padded coaming/stainless steel (SUS) decorative panel/mold release film/material laminated into type (and outside decorate with copper plate pressing plate, interior trim with the copper plate pressing plate, have the pre-preg sheet that infiltration has the glass cloth of epoxy resin)/mold release film/stainless steel (SUS) decorative panel/padded coaming], it is to be that 3.6MPa, pressed temperature are that 180 ℃, heat time heating time are to carry out under 77 minutes the condition at pressure press pressure that pressurization is suppressed.
＜evaluation method (2) 〉
Adopt following assessment item to estimate film of in the above embodiments 15～26, comparative example 9～10 and reference example 1, making and the film that in lamination compression moulding, uses.Evaluation result gathered be shown in Table 1.
(extrusion processability)
Zero: can stably obtain film by coextrusion.
△: can carry out coextrusion, but can see when batching and peeling off.
*: splitting during coextrusion, can not stably batch.
(interlaminar adhesion)
Zero: cut off with cutlery, when cut-off parts usefulness is pointed crooked one time, splitting does not take place.
△: cut off with cutlery, cut-off parts during with crooked one time of finger, splitting is taken place.
*: when cutting off with cutlery, splitting takes place.
(sealing)
Whether visual investigation epoxy resin is extruded from through-holes of printed circuit boards.
Zero: resin is not extruded from through hole.
△: resin is extruded in the 0.5mm from through hole.
*: resin is extruded to more than the 0.5mm from through hole.
(elevated-temperature seal)
Heating-up temperature in the lamination compression moulding is become 200 ℃ from 180 ℃, in addition, with above-mentioned " sealing " the Hang Evaluation value of Jin similarly.
(surperficial release property)
After the press process, between visual valuation stainless steel (SUS) decorative panel and the material laminated into type whether release property is arranged.
Zero: release property is arranged, can peel off lightly.
△: release property is arranged, but have the part that is difficult to peel off.
*: no release property, can not use.
(operability)
Estimated the processing ease of the mold releasing laminated film when coating, when packing forcing press into.
Zero: film has deflection, easily places, and does not play fold.
△: a little less than the deflection of mould, when placing, easily play fold.
*: film does not have deflection, is difficult to place, and easily plays fold.
Table 3
| Extrude processability | Interlaminar adhesion | Sealing | Elevated-temperature seal | The surface release property | Operability | |
| Embodiment 15 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 16 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 17 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 18 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 19 | ○ | ○ | ○ | ○ | ○ | ○ |
| |
○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 21 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 22 | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 23 | ○ | ○ | ○ | ○ | △ | △ |
| Embodiment 24 | △ | △ | ○ | ○ | ○ | ○ |
| Comparative example 9 | - | - | △ | ○ | ○ | × |
| Embodiment 25 | ○ | ○ | ○ | ○ | △ | △ |
| Embodiment 26 | △ | △ | ○ | ○ | ○ | ○ |
| Comparative example 10 | - | - | △ | ○ | ○ | × |
| Reference example 1 | ○ | ○ | ○ | △ | ○ | ○ |
The lamination compression moulding (3) of the making of＜mold releasing laminated film and substrate 〉
(embodiment 27)
Use mold releasing laminated film 100 of the present invention to be manufactured on BGA (Ball Grid Array) with the substrate of the layered product that uses in the multilager base plate, having used in glass baseplate infiltration that the substrate of BT resin (trade name: HL830 (gas chemical company of Mitsubishi system)) is arranged.In addition, the pre-preg sheet has used to infiltrate in the glass core the pre-preg sheet of BT resin (trade name: HL830 (gas chemical company of Mitsubishi system)).Amount of resin is 75%.
The mold releasing laminated film 100 of Shi Yonging is the film of the form of the 100L shown in Fig. 3 (c) in the present embodiment.Laminated film 100 is by obtaining from the combination die coextrusion at 240 ℃.Each layer to laminated film 100 describes, by fluororesin constitute the layer 70a, 70b by ETFE (trade name: Off Le オ Application LM720; The Asahi Glass corporate system) thickness with 2.5 μ m forms. Layer 20a, 20b by adhesive fluorine constitutes are formed with the thickness of 2.5 μ m by the industrial ネ オ Off ロ Application EFEP EP-5000 that makes of ダ イ キ Application.In addition, sandwich layer 50a is by modified poly ethylene (trade name: レ Network ス パ-Le RA3150; Japan's polyethylene corporate system) thickness with 500 μ m forms.Moreover the fusing point of ETFE is that 230 ℃, the fusing point of adhesive fluorine are 200 ℃.
Lamination compression moulding is following to be carried out.As shown in Figure 5, between the mould 310a, the 310b that dispose opposed to each other up and down of compression molding device 300,3 plate substrate 330a, 330b, 330c, pre-preg sheet 340a, 340b and mold releasing laminated film 100 that configuration corrosion resistant plate 320a, 320b, padded coaming (not shown), substrate are used.That is, in mold releasing laminated film 100, dispose with the mode that the upper face side of base material 330a contacts with the following side contacts of corrosion resistant plate 320a, the layer (for example 70b) that constitutes by fluororesin by the layer (for example 70a) that constitutes by fluororesin.They are respectively equipped with pin-and-hole, are standing to be arranged between mould 310a, the 310b pin 350 that allocation really uses and to insert from this pin-and-hole, determine the position.
Corrosion resistant plate 320a, 320b have used the SUS630 stainless steel.Moulding pressure is defined as the 2 stages pressurization of 0.98MPa, 1.96MPa.Forming temperature is 200 ℃, in the moment reach 110 ℃ from the normal temperature temperature-rise period, pressure is switched to 1.96MPa from 0.98MPa.200 ℃ retention time is 5 minutes.Under such condition of molding, be pressed, after moulding is finished, take out layered product.With the layered product that electron microscope observation post obtains, the result does not find the outflow of pre-preg sheet.
(comparative example 11)
Do not use mold releasing laminated film just to carry out moulding, carried out the manufacturing of multilager base plate in addition similarly to Example 27 with layered product.Observe with electron microscope, the result can see the outflow of pre-preg sheet on the concaveconvex shape face of resulting layered product.
Claims (13)
1. mold releasing laminated film, the layer that constitutes by adhesive fluorine that it has the layer that is made of heat-resistant resin and presses on the upper strata of one side at least of this layer.
2. according to the described mold releasing laminated film of claim 1, wherein, the layer that lamination is made of adhesive fluorine on the two sides of the layer that is made of heat-resistant resin.
3. according to claim 1 or 2 described mold releasing laminated films, wherein, above-mentioned adhesive fluorine is at 1790cm
-1～1800cm
-1Between and 1845cm
-1～1855cm
-1Between or at 1800cm
-1～1815cm
-1Between have the IR absorption spectrum.
4. according to claim 1 or 2 described mold releasing laminated films, wherein, the thickness of the above-mentioned layer that is made of adhesive fluorine is 1～15 μ m, and the thickness of the above-mentioned layer that is made of heat-resistant resin is 10～150 μ m.
5. according to claim 1 or 2 described mold releasing laminated films, wherein, the adhesive fluorine that forms the above-mentioned layer that is made of adhesive fluorine is the low melting point ethylene-tetrafluoroethylene copolymer.
6. according to claim 1 or 2 described mold releasing laminated films, wherein, the heat-resistant resin that forms the above-mentioned layer that is made of heat-resistant resin is any in Merlon, ethylene-vinyl alcohol copolymer, the polyamide.
7. according to claim 1 or 2 described mold releasing laminated films, it forms by coextrusion.
8. mold releasing laminated film, its have the layer that constitutes by heat-resistant resin and with the layer that constitutes by fluororesin of the adjacent and lamination of one side at least of the above-mentioned layer that constitutes by heat-resistant resin, described heat-resistant resin is selected from Merlon, polycarbonate-based alloy, PEI, ethylene-vinyl alcohol copolymer, polyamide, polyamide-based alloy.
9. according to the described mold releasing laminated film of claim 8, it is the above-mentioned layer that is made of heat-resistant resin and the above-mentioned layer coextrusion that is made of fluororesin and moulding.
10. according to claim 8 or 9 described mold releasing laminated films, wherein, press on the upper strata, two sides of the above-mentioned layer that constitutes by heat-resistant resin and to state the layer that constitutes by fluororesin.
11. according to claim 8 or 9 described mold releasing laminated films, wherein, above-mentioned by fluororesin constitute the layer thickness be 1～15 μ m, above-mentioned by heat-resistant resin constitute the layer thickness be 10～150 μ m.
12. according to claim 8 or 9 described mold releasing laminated films, wherein, form above-mentioned by fluororesin constitute the layer fluororesin be ethylene-tetrafluoroethylene copolymer.
13. according to claim 8 or 9 described mold releasing laminated films, wherein, form above-mentioned by adhesive fluorine constitute the layer fluororesin be the low melting point ethylene-tetrafluoroethylene copolymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP158052/04 | 2004-05-27 | ||
| JP2004158052A JP2005014598A (en) | 2003-05-30 | 2004-05-27 | Release laminated film |
| JP170306/04 | 2004-06-08 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800171790A Division CN100526066C (en) | 2004-05-27 | 2005-05-27 | Mold releasing laminated film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101531080A true CN101531080A (en) | 2009-09-16 |
Family
ID=38072078
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800171790A Expired - Fee Related CN100526066C (en) | 2004-05-27 | 2005-05-27 | Mold releasing laminated film |
| CNA2009101328031A Pending CN101531080A (en) | 2004-05-27 | 2005-05-27 | Mold releasing laminated film |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800171790A Expired - Fee Related CN100526066C (en) | 2004-05-27 | 2005-05-27 | Mold releasing laminated film |
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| CN (2) | CN100526066C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107921732A (en) * | 2015-08-20 | 2018-04-17 | 旭硝子株式会社 | The manufacture method of laminated substrate and its formed body |
| CN108884554A (en) * | 2016-03-31 | 2018-11-23 | 株式会社东亚电化 | The film formation method of metal surface |
| CN112874097A (en) * | 2021-02-07 | 2021-06-01 | 刘烈新 | High-temperature efficient release type teflon and nylon multilayer composite material |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG11201607467XA (en) * | 2014-03-07 | 2016-10-28 | Asahi Glass Co Ltd | Process for producing package for mounting a semiconductor element and mold release film |
| CN107530918B (en) * | 2015-04-27 | 2020-08-04 | 株式会社寺冈制作所 | Adhesive tape for mold release |
| DE102015213507A1 (en) * | 2015-07-17 | 2017-01-19 | Tesa Se | Adhesive tape, which can be used in particular in a method for molding a body in a mold |
| CN105172292A (en) * | 2015-09-15 | 2015-12-23 | 蚌埠冠宜型材科技有限公司 | Film for casting |
| CN112936914A (en) * | 2019-12-11 | 2021-06-11 | 东丽先端材料研究开发（中国）有限公司 | Composite film and application thereof |
| WO2021166560A1 (en) * | 2020-02-19 | 2021-08-26 | 三井化学東セロ株式会社 | Release film and electronic device manufacturing method |
| CN112549714A (en) * | 2020-11-23 | 2021-03-26 | 北京东方雨虹防水技术股份有限公司 | Polytetrafluoroethylene composite isolation material, preparation method thereof and self-adhesive asphalt waterproof coiled material |
-
2005
- 2005-05-27 CN CNB2005800171790A patent/CN100526066C/en not_active Expired - Fee Related
- 2005-05-27 CN CNA2009101328031A patent/CN101531080A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107921732A (en) * | 2015-08-20 | 2018-04-17 | 旭硝子株式会社 | The manufacture method of laminated substrate and its formed body |
| CN107921732B (en) * | 2015-08-20 | 2019-08-13 | Ａｇｃ株式会社 | The manufacturing method of laminated substrate and its formed body |
| CN108884554A (en) * | 2016-03-31 | 2018-11-23 | 株式会社东亚电化 | The film formation method of metal surface |
| CN108884554B (en) * | 2016-03-31 | 2019-07-12 | 株式会社东亚电化 | The film formation method of metal surface |
| CN112874097A (en) * | 2021-02-07 | 2021-06-01 | 刘烈新 | High-temperature efficient release type teflon and nylon multilayer composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100526066C (en) | 2009-08-12 |
| CN1960866A (en) | 2007-05-09 |
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