CN1329185C - Laminated film and method for producing same - Google Patents

Abstract

A laminated film which is excellent in thermal dimensional stability, cushion properties and low dielectric characteristics is disclosed. The laminated film comprises at least two layers among which at least one layer is a biaxially oriented film composed of a thermoplastic resin composition and at least one other layer is a film having a network structure.

Description

Laminated film and manufacture method thereof

Technical field

The present invention relates to laminated film, for example, relate to the composite membrane that uses applicable to various industrial materials purposes such as circuit board, magnetic recording medium, engineering paper/release materials, Plate making printing material, optics/display material, moulding material, building, electrically insulating material.

Background technology

Film the various industrial materials of magnetic recording medium, circuit material, plate-making/printing material, engineering/release materials usefulness, printing material usefulness, moulding material usefulness, electrically insulating material etc. with, agricultural with, pack to use with, building materials etc. in the various fields that a large amount of needs are arranged and has obtained use.

Yet various uses is more expected the high performance of film in recent years.

In recent years, along with the technological progress of the electronic equipment of portable phone etc., the demand of flexible printed circuit board (FPC) is at rapid growth, in addition with the miniaturization of this equipment, the filming that FPC is carried out in lightweight accordingly.Therefore, also carry out the filming of copper of the copper-surfaced Kapton that FPC uses or the filming of Kapton at the same time, but after therefore the rigidity of film itself reduced, it is difficult that the processing when making FPC becomes.In order to simplify the operation that adds man-hour, after pasting process finishing in advance, employing can peel off the method that the little adhering film for reinforcing of removing makes it to have rigidity.As film for reinforcing, for example use polyester film sometimes.Make when making FPC in such a way, the operation that heats pressurized treatments or be cured or assemble the IC chip under the state of pasting film for reinforcing is arranged, but compare with the copper-surfaced Kapton, because the polyester film thermal coefficient of expansion is big, thermal dimensional stability is insufficient, so in making the FPC process, cause thermal deformation generation warpage, or produce the problem of flatness deterioration etc.

In addition, in electricity, field of electrical components, PPS films is owing to there is little etc. the advantage of good heat resistance, the change in size that causes of suction, thus becoming circuit usefulness shaping substrate material likely, but the big problem of thermal coefficient of expansion is arranged.Though disclose the solution of interpolation glass fibre or particulate inorganic filler (with reference to Patent Document 1 at this problem, 2), but these method differs and obtains satisfied effect surely, and also has difficult point aspect the flatness of film or surface smoothing even the cost.

In addition, flooring material of building etc. requires adiabatic resiliency sometimes.Know foam polyolefin material as material with adiabatic resiliency.But because this material is difficult to make thin film, therefore become the material that limits purposes such as unsatisfied material when being located at underfloor adiabatic padded coaming, then require the material of adiabatic resiliency as thin film.

In addition, the printing material film that printing seal base material or image form with material etc. also requires resiliency, and for example disclosing implements to stretch by thermoplastic resin beyond the mixed polyester or inorganic particulate to polyester is provided with the film (with reference to Patent Document 3,4,5) in space.But such film has the dimensional stability or the inadequate difficult point of flexibility of being heated.

In addition, electronic equipment is in recent years further increasing high speed signal processingization and digitized requirement that high function is used, and the employed film of this purposes is also required high performance.Especially, the thermoplastic resin membrane's that the insulation of printed substrate, cable lining insulation and engine transformer part etc. is used occasion, as the electrical characteristics that adapt with high-frequencyization, the low-kization and the low-dielectric loss angle tangentization of loss usefulness when requiring to suppress transmission with the high speed signal processingization.Particularly, the machine of the whirler of engine etc. is arranged, carry out for high efficiency and multifunction can accurate control conversion control, cause the increase of leakage current of the radio-frequency component of insulating element easily.

In order to give low-dielectric to insulation film, have and utilize dielectric constant to be low to moderate the method that 1 gas forms the emptying aperture of separated foam, for example, there is (1) to form the method (with reference to Patent Document 6) of bubble by making the blowing agent foaming, (2) form the method (with reference to Patent Document 7 and Patent Document 8) of little porous by mixing the resin stretched moulding of non-conforming, (3) adopting Si Pinuoda to decompose is separated the thermoplastic resin generation of the above resin composition of 2 kinds of compositions, by etching or thermal decomposition, alkali decomposition etc. is removed at least a kind or the resin that divides and is formed the method (with reference to Patent Document 9) of little porous.

Yet the thermoplastic resin membrane that above-mentioned (1) method makes is owing to becoming emptying aperture film pockety, so dielectric constant is because of measuring the different instabilities in position or destroying moulding processability or hear resistance sometimes because of utilizing blowing agent to form emptying aperture.And the thermoplastic resin membrane that the method for above-mentioned (2) makes, because the mixing of non-compatible resin so decentralised control is insufficient, makes emptying aperture generation distribution or destroys the moulding processability sometimes.In addition, the thermoplastic resin membrane that the method for above-mentioned (3) makes, must remove the resin of at least a kind of composition, because in fact complex procedures is difficult to use sometimes in order to form emptying aperture.

Patent Document 1: the spy opens flat 5-310957 communique

Patent Document 2: specially permit No. 2952923 communique

Patent Document 3: special fair 6-96281 communique

Patent Document 4: the spy opens flat 2-29438 communique

Patent Document 5: the spy opens flat 6-322153 communique

Patent Document 6: specially permit No. 3115215 communique

Patent Document 7: the spy opens flat 9-286867 communique

Patent Document 8: the spy opens flat 11-92577 communique

Patent Document 9: the spy opens the 2003-64214 communique

Therefore the object of the invention is to provide thermal dimensional stability, resiliency, the low good film of dielectric property.

In addition, Patent Document 10,11 discloses and has made liquid-crystalline polymer be dispersed in film in the polyester.Yet, not open network structure, be full of cracks or emptying aperture as described later.

No. 298313 communiques of Patent Document 10: Te Kaiping

Patent Document 11: the spy opens flat 11-5855 communique

Summary of the invention

The present invention is made up of following constituting.

(1) laminated film is characterized in that it being the laminated film that is made of at least 2 layers film, and at least 1 layer of this laminated film is the film of the biaxial tension of thermoplastic resin composition's system, and in addition at least 1 layer is that cancellated film is arranged.

(2) above-mentioned (1) described laminated film is characterized in that two outsides that cancellated thin layer arranged aforementioned, the layer of the resinous biaxial tension of composite thermoplastic.

(3) above-mentioned (1) or (2) described laminated film is characterized in that aforementionedly having cancellated thin layer to be made by the resin combination of non-ductility.

(4) any one described laminated film of above-mentioned (1)-(3) is characterized in that aforementionedly having cancellated thin layer to contain liquid-crystalline polymer.

(5) above-mentioned (4) described laminated film is characterized in that aforementionedly having cancellated thin layer also to contain non-liquid crystalline polyester.

(6) above-mentioned (5) described laminated film is characterized in that, non-liquid crystalline polyester is PETG, PEN or its modifier.

(7) any one described laminated film of above-mentioned (4)-(6) is characterized in that the content of cancellated thin layer is arranged is 20-90 weight % to liquid-crystalline polymer with respect to aforementioned.

(8) any one described laminated film of above-mentioned (4)-(7) is characterized in that, the liquid crystal polymer content whole with respect to laminated film is 3-30 weight %.

(9) any one described laminated film of above-mentioned (1)-(8) is characterized in that aforementioned the thickness of cancellated thin layer is arranged is the 1-90% of the whole thickness of laminated film.

(10) above-mentioned (9) described laminated film is characterized in that, aforementioned the thickness of cancellated thin layer is arranged is the 10-80% of laminated film full depth.

(11) any one described laminated film of above-mentioned (1)-(10), it is characterized in that, the thermoplastic resin composition of the thin layer of biaxial tension is contained at least a kind that is selected from polyester, polyphenylene sulfide, PEI, Merlon, polyether-ketone, polyether sulfone, polysulfones, PLA.

(12) any one described laminated film of above-mentioned (1)-(11) is characterized in that the vertical and horizontal Young's modulus of laminated film all is 2-7GPa.

(13) any one described laminated film of above-mentioned (1)-(12), what it is characterized in that laminated film all is 0-2% with horizontal percent thermal shrinkage under 150 ℃ of temperature vertically.

(14) any one described laminated film of above-mentioned (1)-(13) is characterized in that the vertical and horizontal thermal coefficient of expansion of laminated film all is 3-45ppm/ ℃.

(more than, claim " the 1st group laminated film of the present invention " with (1)-(14))

(15) laminated film, it is characterized in that it being the laminated film that constitutes by at least 2 layers film, at least 1 layer of this laminated film is the film of the biaxial tension of thermoplastic resin composition's system, and in addition at least 1 layer is the film of the resin combination system of non-ductility, and the proportion of laminated film is 0.2-1.2.

(16) above-mentioned (15) described laminated film is characterized in that at two outsides of the resin combination institute preparative layer of aforementioned non-ductility, the layer of the resinous biaxial tension of composite thermoplastic.

(17) above-mentioned (15) or (16) described laminated film is characterized in that the resin combination of aforementioned non-ductility contains liquid-crystalline polymer.

(18) above-mentioned (17) described laminated film is characterized in that the resin combination of aforementioned non-ductility has also closed non-liquid crystalline polyester.

(19) above-mentioned (18) described laminated film is characterized in that, non-liquid crystalline polyester is PETG, PEN or its modifier.

(20) any one described laminated film of above-mentioned (17)-(19) is characterized in that liquid-crystalline polymer is 20-90 weight % with respect to the content of the resin combination of aforementioned non-ductility.

(21) any one described laminated film of above-mentioned (17)-(20) is characterized in that the liquid crystal polymer content whole with respect to laminated film is 3-30 weight %.

(22) any one described laminated film of above-mentioned (15)-(21) is characterized in that the thickness of the resin combination institute preparative layer of aforementioned non-ductility is the 1-90% of all thickness of laminated film.

(23) above-mentioned (22) described laminated film is characterized in that the thickness of the resin combination institute preparative layer of aforementioned non-ductility is the 10-80% of laminated film full depth.

(24) any one described laminated film of above-mentioned (15)-(23), the thermoplastic resin composition who it is characterized in that the thin layer of biaxial tension is contained and is selected from least a of polyester, polyphenylene sulfide, PEI, Merlon, polyether-ketone, polyether sulfone, polysulfones, PLA.

(25) any one described laminated film of above-mentioned (15)-(24) is characterized in that the vertical and horizontal Young's modulus of laminated film all is 2-7GPa.

(26) any one described laminated film of above-mentioned (15)-(25), what it is characterized in that laminated film all is 0-2% with horizontal percent thermal shrinkage under 150 ℃ of temperature vertically.

(27) any one described laminated film of above-mentioned (15)-(26) is characterized in that the vertical and horizontal thermal coefficient of expansion of laminated film all is 3-45ppm/ ℃.

(more than, claim " the 2nd group laminated film of the present invention " (15)-(27).)

(28) manufacture method of laminated film, it is characterized in that, it is the manufacture method of the laminated film of resin combination coextrusion that will at least 2 layers, at least 1 layer of this laminated film is used the thermoplastic resin composition, at least 1 layer of resin combination that uses non-ductility in addition uses the layer of the resin combination of non-ductility to produce be full of cracks by biaxial tension.

(29) manufacture method of above-mentioned (28) described laminated film is characterized in that the layer in two outsides of the layer of the non-ductility resin combination of aforementioned use uses the thermoplastic resin composition.

(30) circuit material of any one described laminated film of use above-mentioned (1)-(27).

(31) release materials of any one described laminated film of use above-mentioned (1)-(27).

(32) electrically insulating material of any one described laminated film of use above-mentioned (1)-(27).

Adopt the present invention, can make thermal dimensional stability and resiliency, the low good film of dielectric property.

The simple declaration of accompanying drawing

Fig. 1 schematically shows the viewed typical network structure of the cancellated thin layer of having of laminated film of the present invention.

Fig. 2 is illustrated in observed cancellated microphotograph in the A layer of the laminated film that embodiment 1 makes.

The preferred plan that carries out an invention

Laminated film of the present invention is made of at least 2 layers film, and at least 1 layer of this laminated film is made of the thermoplastic resin composition.

As the polymer that constitutes this thermoplastic resin composition, so long as but the polymer of biaxial tension gets final product, for example, can enumerate polyester, polyarylate, polyphenylene sulfide, polyimides, PEI, polyamide, polyamidoimide, Noryl, Merlon, polypropylene, polyethylene, polyether-ketone, polyketone, polyether sulfone, polyethers, PLA etc., with these copolymer etc.In addition, also can be at least a blend that contains these polymer.The present invention considers from biaxial tension, the viewpoint that presents effect of the present invention, wherein preferred polyester, polyphenylene sulfide, PEI, Merlon, polyether-ketone, polyether sulfone, polysulfones, PLA, special preferred polyester or polyphenylene sulfide, especially preferred polyester.

Polyester can produce continuously other material the large-area film that can not make, utilization can be given the characteristics of its intensity, durability, the transparency, flexibility, surface characteristic applicable to various purposes.

As polyester, the sour composition and the dihydroxylic alcohols of optimization aromatic dicarboxylic acids, alicyclic dicarboxylic acid or aliphatic dicarboxylic acid etc. are the polyester of main composition composition.

As the aromatic dicarboxylic acid composition, for example, can use terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, benzophenone dicarboxylic acids, 4,4 '-diphenyldicarboxylic acid, 3,3 '-diphenyldicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acids, 4,4 '-the diphenyl sulphone (DPS) dicarboxylic acids etc., wherein, preferred terephthalic acid (TPA), phthalic acid, 2, the 6-naphthalene dicarboxylic acids.As alicyclic dicarboxylic acid's composition, for example, can use six hydrogen terephthalic acid (TPA)s, 1,3-adamantane dicarboxylic acids, cyclohexane dicarboxylic acid etc.As the aliphatic dicarboxylic acid composition, for example, can use adipic acid, butanedioic acid, azelaic acid, suberic acid, decanedioic acid, dodecanedioic acid etc.These sour composition can only use a kind, also can be more than 2 kind and usefulness, the carboxylic acid of '-hydroxyethoxy yl benzoic acid etc. etc. can also be carried out the part copolymerization.

In addition, as glycol component, for example, can use chlorohydroquinone, methyl hydroquinone, 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxydiphenylsulisomer, 4,4 '-the dihydroxy diphenyl sulfide, 4,4 '-dihydroxy benaophenonel, the aromatic diol of terephthalyl alcohol etc., ethylene glycol, 1, the 2-propane diols, 1, ammediol, neopentyl glycol, 1, the 3-butanediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, PAG, 2,2 '-two (4 '-β-hydroxy ethoxy phenyl) propane etc., wherein, preferably make spent glycol, 1, the 4-butanediol, 1, the 4-cyclohexanedimethanol, diethylene glycols etc. especially preferably make spent glycol.These diol component both can also can will use more than 2 kinds together only with a kind.

In addition, polyester, promptly can laruyl alcohol, the monofunctional compound of phenyl isocyanate etc. carries out copolymerization, also can trimellitic acid, Pyromellitic Acid, glycerine, pentaerythrite, 2,3 functional compounds of 4-dihydroxy-benzoic acid etc. etc. are in polymer branching within reason or crosslinked and be actually in the scope of wire and carry out copolymerization.In addition, beyond deacidification composition, the glycol component, also can the minor amounts of copolymerized P-hydroxybenzoic acid under the condition of not destroying effect of the present invention, m-hydroxybenzoic acid, 2, the aromatic hydroxy-carboxylic of 6-hydroxynaphthoic acid etc. and para-aminophenol, p-aminobenzoic acid etc.

As polyester, consider from the viewpoint of mechanical strength, production efficiency and operability etc. that more preferably use PETG, gather 2, that selects in 6-(ethylene naphthalate) and copolymer thereof or the modifier is at least a.So-called such PETG, poly-2, the 6-(ethylene naphthalate) is as sour composition, contains terephthalic acid (TPA) or 2, the polymer that at least 80 moles of % of 6-naphthalenedicarboxylic acid are above also can be with a spot of other dicarboxylic acids composition copolymerization.In addition, as glycol component, though for containing the polymer of 80 moles of above ethylene glycol of %, the glycol component that also can add other is as copolymer composition.

Consider from the viewpoint of system film, hear resistance, water-disintegrable, processing stability, dimensional stability etc., as the inherent viscosity of polyester, more than the preferred 0.50dl/g of lower limit, more preferably 0.55dl/g above, again more than the preferred 0.6dl/g.And below the preferred 2.0dl/g of higher limit, more preferably 1.4dl/g following, again below the preferred 1.0dl/g.

As polyphenylene sulfide (PPS), preferably contain 80 moles of above phenylene sulfide compositions of %, more preferably contain 90 moles more than the %.By containing 80 moles of above phenylene sulfide compositions of %, can make the contour PPS of crystallinity or thermal transition temperature, can obtain hear resistance, dimensional stability, mechanical property, dielectric property as the PPS feature etc.If can guarantee the phenylene sulfide composition of this content in addition, but then also can contain the unit of other thioether bonds with copolymerization.As such unit, for example, can enumerate 3 functional units, ether unit, sulfone unit, ketone unit, a position combining unit of trihalogenated benzene etc., the substituent aryl unit that alkyl etc. is arranged, xenyl unit, connection phenyl unit, Sanya, ethenylidene unit, carbonate unit etc., both can use wherein a kind, also can use more than 2 kinds.As the form of copolymerization, can be any of random or block type.

Except the feature of aforesaid PPS, expectation heat fused characteristic, moisture absorption dimensional stability etc. and adopt the occasion of PPS as the constituent of resin combination are preferably made and are contained the above composition of PPS composition 60 weight %.By the content that makes PPS is more than the 60 weight %, also can obtain the feature of PPS as resin combination.If can guarantee the PPS of this content, then also can add the polymer beyond the PPS, inorganic or organic filler, lubricant, colouring agent etc.

In addition, be the melt viscosity of the resin combination of main component as PPS, 300 ℃, shear rate 2000 seconds ^-1Condition under preferred 500-50000 pool, be more preferably the 1000-20000 pool.

The layer that the thermoplastic resin composition constitutes, importantly biaxial tension.Can obtain can be used for the intensity of various uses by biaxial tension.

The 1st group laminated film of the present invention, importantly other at least 1 layer is that cancellated film is arranged.By forming network structure or the structure in space being arranged, can obtain low-k or excellent in cushioning properties.In addition, because the rigidity as laminated film is reduced, so can obtain excellent morphological stability.In addition, thermal expansion is reduced, can obtain excellent thermal dimensional stability.

This network structure, the wire inscape that forms fibrillation shape, strip or beads shape form in thin layer is the form of the netted company of passing through.In addition, for example, also can be that longitudinally and/or laterally the plan of the company of passing through is netted in the space on the face parallel with film surface.In this network structure, the key element that constitutes mesh also can be crooked, and in addition, only otherwise influence effect of the present invention especially, its space is passed through also and can partly be interrupted.

In addition,, be preferably formed cancellated structure, or any of structure even passed through in the space to the thickness direction of film.

Forming the material of wire inscape in addition, both can be that the resin combination of non-ductility described later is whole, also can be the material that liquid-crystalline polymer contained in the resin combination of described later equally, non-ductility etc. presents the part of non-ductility.

Observe the minor axis of the wire inscape of aforesaid fibrillation shape, strip or beads shape etc. with the infiltration type electron micrograph, preferred 5nm-100 μ m, more preferably 50nm-10 μ m, 0.1 μ m-5 μ m preferably again.Thick line partly represents to form cancellated wire inscape among Fig. 1, and D represents the minor axis of this wire inscape.By making this minor axis is below the 100 μ m, can keep the system film, suppresses the fluctuating of film surface, keeps the flatness of film, keeps the processability of the film that can be used for various uses.In addition, though this minor axis can be thin, what obtain at present is more than the 5nm.

Have in this cancellated thin layer, both can contain the different wire inscape of diameter dimension, also can form the different many network structures of size, can also form fine network structure in the inside of wire inscape.These occasion can be controlled at above-mentioned preferable range to the diameter that forms bigger cancellated wire inscape.

As the voidage in the network structure, consider that from the viewpoint that presents various effects of the present invention face integration rate in the preferred aspect is 20-80%, more preferably 30-70%, preferred 30-60% again.

Moreover said in the laminated film of the present invention " other at least 1 layer " also is film, for example do not contain nonwoven.

As the above-mentioned network structure or the form in relevant space, to the 2nd group laminated film of the present invention, also all as preferred form.

As above-mentioned network structure or space, for example can obtain by this layer being adopted the resin combination of non-ductility.

That is, the 2nd group laminated film of the present invention, at least 1 layer of importantly other resin combination by non-ductility constitutes.

The resin combination of said non-ductility among so-called the present invention, " assay method " percentage elongation under 100 ℃ of temperature described later that is employing embodiment are the resin combination below 50%.That is, be the resin combination that the stress-strain diagram in the tension test rises rapidly.By make that layer that so non-ductility resin combination constitutes and thermoplastic resin composition constitute layer compound after carry out biaxial tension, can form network structure or space.

As at least a portion that constitutes non-ductility resin combination, present the resin of non-ductility, preferably contain the resin of liquid-crystalline polymer particularly.Perhaps, the 1st group laminated film of the present invention cancellated thin layer arranged, preferably contain liquid-crystalline polymer.

As liquid-crystalline polymer, for example, can adopt the copolyester that constitutes by the construction unit that is selected from aromatic series oxygen carbonyl unit, aromatic series dioxy unit, aromatic series dicarbapentaborane unit, alkylidene dioxygen unit etc.

As commercially available product, can suitably select to adopt " シ ベ ラ ス " (Dong Li Co., Ltd system), " ベ Network ト ラ " (poly-plastics Co., Ltd system), " ゼ Na ィ ト " (E.I.Du Pont Company's system), " ス ミ power ス one パ one " (Sumitomo Chemical Co., Ltd system), " ザ ィ ダ one " (Solvay's system), " u'eno LCP " (u'eno pharmaceutical Co. Ltd system), " ィ Application " (Easterman corporate system) etc.

As liquid-crystalline polymer, consider preferred liquid-crystalline polymer with the viewpoint of construction unit, can enumerate

Contain following (I), (II), (III) and (IV) construction unit copolyester,

Contain following (I), (III) and (IV) construction unit copolyester,

Contain following (I), (II) and (IV) construction unit copolyester,

Or the blend of these copolyesters.

O-R ₂-O (II)

And the R in the formula ₁Expression

And/or

R ₂Expression is selected from

More than one,

R ₃Expression is selected from

More than one.In addition, X represents hydrogen atom or chlorine atom in the formula.

In addition, by said structure unit (I), (II) occasion with the copolyester that (IV) constitutes, preferred especially R ₁Be

And, by said structure unit (I), (III) occasion with the copolyester that (IV) constitutes, preferred especially R ₁Be

Construction unit, R ₃Be

Construction unit.

In addition, by said structure unit (I), (II), (III) occasion with the copolyester that (IV) constitutes, preferred especially R ₁Be

R ₂Be

R ₃Be

In these the copolyester, construction unit (II) and construction unit (IV) form the repetitive in the polymer, and construction unit (III) also forms repetitive in the polymer with construction unit (IV).That is, in these the copolyester, construction unit (II) and/or molal quantity sum (III) in fact equate with the molal quantity of construction unit (IV).Here so-called " in fact ", mean any of the carboxyl end groups that can increase as required among the polyester terminal groups or hydroxyl end groups, during this occasion, strictly say, the molal quantity sum of the molal quantity of construction unit (IV) and construction unit (II), (III) is also unequal, but also comprises such occasion.

By said structure unit (I), (II), (III) occasion with the copolyester that (IV) constitutes, the molal quantity sum of said structure unit (I), (II) is with respect to the preferred 5-95 mole of the branch rate % of the molal quantity sum of (I), (II), (III), more preferably 30-90 mole %, preferred 50-80 mole % again.And molal quantity (III) is with respect to the preferred 5-95 mole of the branch rate % of the molal quantity sum of construction unit (I), (II), (III), more preferably 10-70 mole %, 20-50 mole % most preferably.In addition, the mol ratio of considering construction unit (I)/(II) from the viewpoint of flowability preferably 75/25-95/5, be more preferably 78/22-93/7.

By said structure unit (I), (III) occasion with the copolyester that (IV) constitutes, the molal quantity of said structure unit (I) is with respect to the preferred 5-95 mole of the branch rate % of the molal quantity sum of (I), (III), more preferably 50-80 mole %.

By said structure unit (I), (II) occasion with the copolyester that (IV) constitutes, preferably with by construction unit (I), (II), (III) is with the copolyester that (IV) constitutes and/or carry out blending by construction unit (I), (III) with the copolyester that (IV) constitutes and use.The occasion of this alloyed polymer, the molal quantity sum of construction unit (I), (II) is with respect to the preferred 5-95 mole of the branch rate % of the molal quantity sum of construction unit (I), (II), (III), more preferably 30-90%, preferred 50-80 mole % again.

In addition, as the copolyester of liquid-crystalline polymer, except that said structure unit (I)-(IV), also can copolymerization in the scope of not destroying effect of the present invention other composition.As such copolymer composition, can adopt 3,3 '-diphenyldicarboxylic acid, 2,2 '-aromatic dicarboxylic acid of diphenyldicarboxylic acid etc., or adipic acid, azelaic acid, decanedioic acid, the aliphatic dicarboxylic acid of dodecanedioic acid etc., the ester ring type dicarboxylic acids of six hydrogen terephthalic acid (TPA)s etc., or chlorohydroquinone, methyl hydroquinone, 4,4 '-dihydroxydiphenylsulisomer, 4,4 '-the dihydroxy diphenyl sulfide, 4,4 '-aromatic diol of dihydroxy benaophenonel etc., or 1, the 4-butanediol, 1, the 6-hexylene glycol, neopentyl glycol, 1, the 4-cyclohexane diol, 1, the aliphatic of 4-cyclohexanedimethanol etc., the ester ring type dihydroxylic alcohols, or m-hydroxybenzoic acid, 2, the aromatic hydroxy-carboxylic of 6-hydroxynaphthoic acid etc., or para-aminophenol, p-aminobenzoic acid etc.

As the flow starting temperature of liquid-crystalline polymer, consider preferred 200-360 ℃ from the viewpoint that forms network structure or space, from considering more preferably 230-320 ℃ with the blended viewpoint of non-liquid crystalline polyester described later.

As at least a portion of the resin combination that constitutes non-ductility, present the resin of non-ductility, except that liquid-crystalline polymer, also can enumerate polyolefin, Merlon, polystyrene, PEI, polyether-ketone, polyether sulfone, polysulfones, PLA etc.

Laminated film of the present invention, the resin combination of non-ductility preferably also contain the polymer beyond the polymer that presents non-ductility.Perhaps the 1st group laminated film of the present invention has cancellated thin layer, the preferred polymer polymer in addition that presents non-ductility that also contains.Present non-ductile polymers polymer in addition by making to contain in the non-ductility resin combination, appropriateness is followed thermoplastic resin composition's layer when carrying out biaxial tension as laminated film, but the high efficiency landform reticulates structure or space.

As presenting non-ductile polymers polymer in addition, consider from adherence between thin layer and the viewpoint that presents effect of the present invention, preferably with the thermoplastic resin composition's of the thin layer that constitutes the thin layer adjacency that cancellated thin layer inclusive NAND ductility resin combination constitutes polymer phase with polymer, as such thermoplastic resin composition, as described above because special preferred polyester, so that is to say as presenting non-ductile polymers polymer in addition, also preferred non-liquid crystalline polyester.Non-liquid crystalline polyester is as thermoplastic resin composition's polyester, also is the polyester that sour composition and glycol component by aromatic dicarboxylic acid, alicyclic dicarboxylic acid or aliphatic dicarboxylic acid etc. constitute as described above.

As the inherent viscosity of mixing the non-liquid crystalline polyester that uses with liquid-crystalline polymer, consider from the stability of film forming processing or with the blended viewpoint of liquid-crystalline polymer, preferred 0.55-3.0dl/g, be more preferably 0.60-2.0dl/g.

Liquid-crystalline polymer is with respect to having cancellated thin layer or with respect to the content of non-ductility resin combination, more than the preferred 20 weight % of lower limit, more preferably 30 weight % above, more preferred 35 weight % above, again more than the preferred 40 weight %.In addition, below the preferred 90 weight % of higher limit, more preferably below the 85 weight %, below the preferred again 80 weight %, below the preferred again 70 weight %.By the content that makes liquid crystal polymer is more than the 20 weight %, can obtain network structure or space, is below the 90 weight % by making content, can suppress to make the multiple of film breakage.

As the liquid-crystalline polymer content whole with respect to laminated film, preferred 3-30 weight %, more preferably 5-25 weight %, 7-23 weight % preferably again.By making the liquid crystal polymer content whole with respect to laminated film is more than the 3 weight %, network structure or space can be fully formed, the effect of improvement etc. can be obtained as described later as the giving of the proportion of laminated film and resiliency, flexibility, flatness.In addition, by becoming below the 30 weight % generation of breakage in the time of can suppressing to stretch.

As the composite number of laminated film of the present invention, preferred 2-1000.As compound position relation, with the thin layer that has cancellated thin layer or non-ductility resin combination to constitute is the A layer, when being B layer, C layer with thin layer of the biaxial tension of thermoplastic resin composition's system etc., consider from the viewpoint of the processability that presents effect of the present invention and film and production efficiency, preferably, make it to become the multilayer formation of B/A/B, C/B/A/B/C, C/B/A/B etc. at the resinous biaxial tension layer of two outside composite thermoplastics of A layer.Especially, the distortion when being conceived to suppress processing film, keep flatness, 3 layers of compound formation (B/A/B) of the layer of the same thickness that forms particularly preferably in the compound identical resin in two outsides of A layer.

Laminated film of the present invention also can add nucleator, solar heat protection distintegrant, heat stabilizer, antioxidant, ultra-violet absorber, antistatic additive, fire retardant, pigment, dyestuff etc. in the scope that does not influence effect of the present invention.

In addition, especially at the outermost layer of laminated film, for the surface being given easy sliding property, abrasion performance, marresistance etc., also preferably add the organic lubricant or the surfactant of fatty acid ester, wax etc. or form inorganic particulate or the organic filler that protrusion of surface is used.In addition, also can so-called internal particle be separated out by adding catalyst etc. when the polymerisation.

As inorganic particulate, for example, can use the composite oxides of the oxide of silica, aluminium oxide, titanium oxide, magnesia, zirconia etc. or clay, mica, kaolin, talcum, imvite etc. or carbonate or the sulfate of calcium sulfate, barium sulfate etc. or the titanate of barium titanate, potassium titanate etc. of calcium carbonate, brium carbonate etc., or the phosphate of calcium phosphate etc. etc.As silica, wet type or dry type silica or colloid shape silica are arranged, both can be that spherical shape also can be a porous matter.

In addition, as organic filler, so long as among the part of constituent particle at least a portion to constituting insoluble the getting final product of resin of film, for example, can use the particle of the ethene base system particle of polystyrene or crosslinked polystyrene particle or styrene-propene acid system and acrylic acid series crosslinked particle, styrene-metha crylic crosslinked particle etc. or benzoguanamine-formaldehyde, silicon, polytetrafluoroethylene (PTFE) etc.

Form the particle diameter, use level, shape of inorganic particulate that protrusion of surface uses or organic filler etc. by suitable selection, can adjust the surface roughness of laminated film.As the preferred 0.01-3 μ of the average grain diameter of particle m, as the preferred 0.001-3 weight of addition %.In addition, can use a kind particle individually, particle that also can average grain diameter is different is used in combination more than 2 kinds.

The thickness of laminated film of the present invention, general whole preferred 500 μ m are following, more preferably 0.5-400 μ m, consider preferred 10-300 μ m, preferred 20-200 μ m again from the viewpoint of thin film application or operation etc. again.In addition, according to the difference of purposes, be preferably 2.0-10 μ m in the tape purposes, the capacitor purposes is preferably 0.5-15 μ m, circuit material purposes or release materials purposes and is preferably 12-250 μ m, and the electrically insulating material purposes is preferably 75-400 μ m.

The thin layer thickness whole that cancellated thin layer or non-ductility resin combination system are arranged with respect to laminated film, lower limit is preferred more than 1%, more preferably more than 10%, preferred more than 15%, preferred more than 20%, preferred more than 30% more again.And higher limit is preferred below 90%, more preferably below 80%, preferred below 75%, preferred below 70%, preferred below 60% more again.By becoming more than 1%, can obtain to improve the effect of thermal dimensional stability, by becoming more than 10%, owing to having reduced the proportion of laminated film, so can give resiliency.In addition, by becoming below 90%, can prevent the multiple of breakage of thin film applied.

The 2nd group laminated film of the present invention, importantly proportion is 0.2-1.2.In addition, the 1st group laminated film of the present invention, preferred specific gravity is in this scope.As laminated film of the present invention, more preferably proportion is 0.3-1.0,0.4-0.7 preferably again.Proportion is below 1.2, this means that the space in the film is abundant, can obtain the effects of the present invention such as resiliency of film.And, be more than 0.2 by making proportion, the space in the film is not increased and can be obtained the balance of intensity and dimensional stability.

Laminated film of the present invention, it is the equal 2-7GPa preferably of Young's modulus of (MD) and laterally (TD) vertically.As lower limit more preferably 2.5GPa, 3GPa preferably again.And as higher limit more preferably 6GPa, preferred 5GPa again.By becoming below the 7GPa, can suppress distortion, crimping, raising morphological stability.And by becoming more than the 2GPa, keep well-pressed, do not destroy operability.

Laminated film of the present invention, from film add man-hour or stable on heating viewpoint when using considers that vertical (MD) of preferred laminated film and horizontal (TD) percent thermal shrinkage under 150 ℃ of temperature all are 0-2%.As higher limit more preferably below 2.0%, more preferably below 1.0%, preferred less than 1.0%, preferred below 0.5% more again.By becoming below 2%, can guarantee hear resistance, obtain thermal dimensional stability.In addition, be below 1.0% by making percent thermal shrinkage, can keep good flatness.And as lower limit, be more preferably more than 0.01%.By becoming more than 0.01%, can prevent the deterioration of the crinkled or flatness that the film expansion causes.

Laminated film of the present invention, it is all preferably 3-45ppm/ ℃ of the thermal coefficient of expansion of (MD) and laterally (TD) vertically.As lower limit, more preferably more than 4ppm/ ℃, preferred more than 5ppm/ ℃, more preferably more than 10ppm/ ℃ again.As higher limit, more preferably below 35ppm/ ℃, preferred below 30ppm/ ℃, preferred below 25ppm/ ℃, more preferably below 20ppm/ ℃ more again.By becoming in such scope, can prevent man-hour because of thermal deformation generation crimping with adding in the purposes of film, mould release film or printing material etc. at circuit material.

Laminated film of the present invention, preferred rate buffer be 10-50%, more preferably 15-45%, more preferably 20-40%, be more than 10% by making rate buffer, improve the flexibility of film, for example improve the processability when using in the building materials purposes of wallpaper etc., also can expect to reduce the cost of same units area in addition.And, be below 50% by making rate buffer, the balance of THIN COMPOSITE film strength and dimensional stability can be obtained, and production efficiency can be kept.

Laminated film of the present invention, 30 ℃ of temperature, the dielectric constant under the frequency 10KHz is 1.3-3.0, more preferably 1.5-2.7,1.7-2.5 preferably more preferably.By making dielectric constant is below 3.0, is being used for the occasion of electrically insulating material, can suppress power loss that leakage current etc. causes or the heating that is caused, and can obtain effect of the present invention.In addition, if consider the intensity of appropriateness control voidage, acquisition and film or the balance of production efficiency, then dielectric constant is more abundant as if dropping to about 1.3.

In addition, laminated film of the present invention, except as above-mentioned formation, can also be directly or utilize the layer of adhesive etc. to make other for example layer compound use of formations such as Merlon, polyolefin, polyamide, Vingon or acrylic acid series polymeric compounds of polymeric layer.

In addition, laminated film of the present invention also can be a laminated film of implementing the processing of heat treatment, moulding, surface treatment, lamination, coating, printing, embossing processing, etching etc. according to purposes.

Laminated film of the present invention can be suitable for the purposes of the various industrial materials of engineering material, release materials, printing material, moulding material, building materials, magnetic recording medium material, circuit material, electrically insulating material etc.

Network structure in the laminated film of the present invention or space can make as follows.Promptly, the manufacture method of laminated film of the present invention is the manufacture method with the laminated film of at least 2 layers resin combination coextrusion, is that at least 1 layer of this laminated film uses thermoplastic resin composition, other at least 1 layer to use non-ductility resin combination, use the layer of the resin combination of non-ductility to produce the manufacture method of the laminated film of be full of cracks by biaxial tension.

As thermoplastic resin composition and non-liquid crystalline polyester, for example PETG can adopt following any technology manufacturing.

(1) is raw material with terephthalic acid (TPA) and ethylene glycol, directly makes low-molecular-weight PETG or oligomer, the technology that adopts the catalyst of antimony trioxide or titanium compound etc. to carry out polycondensation again by esterification.

(2) be raw material with dimethyl terephthalate (DMT) and ethylene glycol, make the low-molecular-weight thing, the technology that adopts the catalyst of antimony trioxide or titanium compound etc. to carry out polycondensation again by ester exchange reaction.

The esterification of technology (1) also can be reacted even without catalyst, and the ester exchange reaction of technology (2), can use the compound of manganese, calcium, magnesium, zinc, lithium, titanium etc. to react as catalyst, in addition in fact after ester exchange reaction finishes, catalysqt deactivation for this reaction is used also can add phosphorus compound.Can enumerate phosphorous acid, phosphoric acid, phosphotriester, phosphonic acids, phosphonate ester etc. as phosphorus compound, can also will also use more than 2 kinds.

Aforementioned esterification or ester exchange reaction are preferably carried out under 130-260 ℃ temperature conditions, and polycondensation reaction is preferably carried out under 220-300 ℃ of condition under high vacuum.

As the example of PETG method for making more specifically, can make bis-(BHT) by making terephthalic acid (TPA) and ethylene glycol carry out esterification or making dimethyl terephthalate (DMT) and ethylene glycol carries out ester exchange reaction.Then this BHT is transplanted in the polymerization tank, under vacuum, is heated to 280 ℃ and carries out polymerisation.Here, owing to obtain the polyester of inherent viscosity about 0.5,,, under the decompression about 190-250 ℃, 133Pa (1mmHg), carried out solid phase 10-50 hour again under the temperature below 180 ℃ in advance behind the crystallization so this polyester is granulated.

In addition, can add various as the aforementioned additives in stage arbitrarily from esterification or ester exchange reaction to polycondensation reaction.

In addition, as making the method that contains particle in the PETG, preferably the form with slurries is dispersed in the ethylene glycol particle, makes this ethylene glycol and terephthalic acid (TPA) carry out the method for polymerization.As the method for adding particle, for example, if the state of the hydrosol that obtains during from compound particle or alcosol does not carry out primary drying and adds, then dispersion of nano-particles is good.In addition, the slurries of particle are mixed with the direct particle of the PETG of regulation, use exhaust twin-screw mixer extruder, the method for sneaking in the PETG is also effective.

As the method for regulating particle content, adopt said method to make the masterbatch of high concentrations of particles in advance, when the system film, use the sheet stock dilution masterbatch that is substantially free of particle and to regulate the method for particle content effective.

As the PPS of thermoplastic resin, for example, can make vulcanized sodium and paracide is to react under 230-280 ℃, high pressure in the polar solvent to make at the acid amides of N-N-methyl-2-2-pyrrolidone N-(NMP) etc.At this moment, can add caustic potash, carboxy acid alkali's slaine etc. as degree of polymerization conditioning agent.With the polymer cooling, make polymer become water slurry after the polymerization, after filtering with filter, obtain granular polymer.In the aqueous solution of acetate etc., under 30-100 ℃ this polymer is carried out 10-60 minute stir process, use ion exchange water for several times, obtain the PPS powder after the drying 30-80 ℃ of washing.This PPS powder below partial pressure of oxygen 1.3MPa (10 torr), after the following NMP of use of preferred 66Pa (5 torr) washs, is used 30-80 ℃ ion-exchange water washing several, under the decompression below the 665Pa (5 torr), carry out drying.The PPS that makes like this is actually the polymer of wire, and owing to the scope of fusion-crystallization temperature T mc at 160-190 ℃, so the system film that can stably stretch.

The aforesaid copolyester of the example of the liquid-crystalline polymer as the aforementioned that preferably contains as the resin combination of non-ductility, for example, in the aforementioned structure unit (I)-(IV), do not contain the occasion preferably following (3) of construction unit (III) or the method for (4), contain the method for the occasion preferably following (5) of construction unit (III).

(3) by to acetoxy-benzoic acid and 4,4 '-diacetoxy biphenyl, 4,4 '-aromatic dicarboxylic acid of two acylates of the aromatic dihydroxy compound of diacetoxy benzene etc. and terephthalic acid (TPA) etc. is by taking off the method that the acetic acid polycondensation reaction is made.

(4) make P-hydroxybenzoic acid and 4,4 '-aromatic dicarboxylic acid and the aceticanhydride reaction of the aromatic dihydroxy compound of dihydroxybiphenyl, hydroquinones etc. and terephthalic acid (TPA) etc., after the phenolic hydroxyl group acidylate, by taking off the method that the acetic acid polycondensation reaction is made.

(5) method of making in the method for employing above-mentioned (1) or (2) down of two (beta-hydroxyethyl) esters of the aromatic dicarboxylic acid of two (beta-hydroxyethyl) esters of polymer, oligomer or the poly terephthalic acid of polyester such as PETG etc.

The polycondensation reaction of said method (3)-(5) is also carried out under catalyst-free, but preferably add stannous acetate sometimes, the metallic compound of butyl titanate, potassium acetate, sodium acetate, antimony trioxide, magnesium metal etc.

In addition, said structure unit (I) for example can be by P-hydroxybenzoic acid and/or 6-hydroxyl-generations such as 2-naphthoic acid.And, construction unit (II) for example, can be by 4,4 '-dihydroxybiphenyl, 3,3 ', 5,5 '-tetramethyl-4,4 '-dihydroxybiphenyl, hydroquinones, TBHQ, phenyl hydroquinones, 2,6-dihydroxy naphthlene, 2,7-dihydroxy naphthlene, 2,2 '-two (4-hydroxyphenyl) propane, 4,4 '-generations such as aromatic dihydroxy compound of dihydroxy diphenyl ether etc.In addition, construction unit (III) for example can be by generations such as ethylene glycol.In addition, construction unit (IV) for example can be by terephthalic acid (TPA), M-phthalic acid, 4,4 '-diphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acids, 1, two (phenoxy group) ethane-4,4 of 2-'-dicarboxylic acids 1, two (2-chlorophenoxy) ethane-4 of 2-, 4 '-dicarboxylic acids and 4,4 '-aromatic dicarboxylic acid of diphenyl ether dicarboxylic acids etc. generates.

Among the present invention, the occasion that liquid-crystalline polymer is mixed with other polymer, as mixed method, have before melt extruding and in advance liquid-crystalline polymer and other polymer are carried out carrying out the method for master sliceization after the pre-fusion mixing (granulation), or when melt extruding, mix method that makes it melting mixing etc.Carry out the method for master sliceization, owing to obtain uniform dispersity, it is good and preferred to be conceived to quality, the system film of film.

With use PETG (PET) as thermoplastic resin, uses system liquid crystalline polyester " the u'eno LCP " 5000 of u'eno drugmaker to be example as the occasion of liquid-crystalline polymer, to make master slice to formation not the laminated film of stretching describe.Moreover " u'eno LCP " 5000 has (I) as the aforementioned structure unit.

As above-mentioned liquid-crystalline polymer in the master slice and the weight ratio of PET, be preferably 95/5-50/50.

As liquid-crystalline polymer being mixed with thermoplastic resin/mixing method, for example can each after melt extruding the machine fusion, mix respectively, can also use the mixer of Henschel mixer, ball mill, blending machine, rotary drum etc. in advance powder material to be carried out the dry type premixed, then, use the melting mixing machine to carry out melting mixing.

As the melting mixing machine, for example preferred twin-screw mixer extruder.

For example, the pellet of the pellet of liquid crystal polymer and PET etc. in after making desired ratio that master slice uses and mixing, is supplied with the twin-screw mixer extruder of exhaust, under 280-320 ℃, carry out melting mixing.In addition,, disperse bad viewpoint to consider, the extruder of the screw rod of 3 twin-screws or 2 twin-screw types preferably is housed, at this moment preferred 1-5 of the time of staying minute from reducing as the exhaust double screw extruder.

After making the desired content of the corresponding liquid-crystalline polymer of the master slice that makes like this with respect to non-ductility resin combination, the sheet of hybrid PET etc. again after 180 ℃ of left and right sides vacuum drying are more than 3 hours, is thrown in the extruder that the compressional zone is heated to 270-320 ℃ of temperature.When mixing with PET, more preferably the temperature of compressional zone is 290-310 ℃.

On the other hand, the raw material that is mixed with suitable particle among the PET etc. is thrown into after drying in the other extruder.

And, when these are melt extruded, also in extruder, remove the filtration of foreign matter or rotten polymer, preferably reduce the foreign matter of sneaking in the film as far as possible.As the filter that uses this moment for example, preferably use sintering metal, porous ceramics, molding sand, wire netting etc.

In addition, in order to improve weight feed, also preferably establish gear pump.

Make various molten polymers through extruder at feed zone afflux, compound, be emitted into sheet from the narrow slit of T font die head, this tablet is close on surface temperature 20-70 ℃ the chill roll (casting roller) carries out cooling curing, can make the non-stretched film of essentially no state of orientation.

Then, this non-stretched film is carried out biaxial tension, use thermoplastic resin composition's layer double orientation, and use the layer of non-ductility resin combination to produce be full of cracks.As drawing process, can use biaxial tension method one by one (behind longitudinal stretching, carrying out the drawing process that the stretching of each direction of the method etc. of cross directional stretch is made up again), the method for biaxial tension simultaneously (vertically with the method that laterally side by side stretches) or with the method for these combinations.

Can suitably set according to the formation of multilayer or the composition that constitutes the resin combination of each layer stretching condition etc., but always roughly be preferably as follows.

Stretching ratio to vertically going on foot by respectively or above multistep of two steps with horizontal of film, is preferably 1.2-6.0 times, is more preferably 2.5-4.5 doubly.

Draft temperature is preferably 90-180 ℃, in addition, use the thermoplastic resin composition the layer the thermoplastic resin composition glass transition temperature as Tg (℃) time, be preferably Tg～Tg+40 (℃).

In addition, can stretch again according to purposes or desired film characteristics.As the multiplying power that stretches again, vertical and/or laterally preferred more than 1.1 times.

The temperature of stretching after-baking, when the thermoplastic resin composition's of the layer that uses the thermoplastic resin composition fusing point as Tm (℃) time, be preferably 150-Tm (℃), be more preferably 200-245 ℃, be preferably 0.3-30 second as time of stretching after-baking.

In addition, obtaining aspect the effect of the present invention, also preferred during to heat treatment and/or the film after the heat treatment when cooling off, to vertically and/or laterally also implement the loose processing of 1-10%, the more preferably loose processing below 9%.

In addition, to the laminated film after batching, also preferably under 50-120 ℃ temperature conditions, carried out burin-in process 5 minutes-500 hours.

Below, uses with two outsides configuration of the layer of the non-ductility resin combination that contains liquid-crystalline polymer in use the thermoplastic resin composition layer 3 layers of formation occasion by vertically, the biaxial tension method one by one that laterally stretches describes as example.

Use the warm-up mill group that oriented polyester film is not heated, in this example, stretching is preferably multi-step tension, particularly preferably in before the longitudinal stretching earlier to the little stretching of vertical enforcement.This little stretching is removed in the strand of polymer and the distortion of being accumulated between strand, carry out thereafter stretching easily, and the layer that uses non-ductility resin combination is helped forming network structure or space.As the stretching ratio of this little stretching, preferred 1.05-1.8 doubly, more preferably 1.1-1.5 doubly, preferably 1.15-1.3 is doubly again.In addition as the draft temperature of this little stretching, if uses the thermoplastic resin composition layer the thermoplastic resin composition glass transition temperature as Tg (℃) time, preferably Tg+10～Tg+70 (℃), more preferably Tg+15～Tg+60 (℃), more preferably Tg+20～Tg+50 (℃).

As the stretching ratio that vertically (MD direction) stretches, contain the stretching ratio of above-mentioned little stretching, preferred 2-5 doubly, more preferably 2.5-4.5 preferred 3-4 is doubly doubly, again.Moreover this stretching ratio does not comprise the stretching ratio of longitudinal stretching more described later.Draft temperature as longitudinal stretching, if uses the thermoplastic resin composition layer the thermoplastic resin composition glass transition temperature as Tg (℃), then preferably Tg-Tg+60 (℃), more preferably Tg+5-Tg+55 (℃), more preferably Tg+10-Tg+50 (℃).

Behind the longitudinal stretching, preferably use 20-50 ℃ chill roll group to cool off.

Drawing process as horizontal (TD direction) for example, preferably uses stenter.Can use the both ends of clamp clamps film, the guiding stenter carries out horizontal stretching.As this cross directional stretch multiplying power, preferred 2.0-6.0 doubly, more preferably 3.0-5.0 doubly, preferably 3.5-4.5 is doubly again.Moreover this stretching ratio does not comprise the stretching ratio of longitudinal stretching more described later.In addition, as this draft temperature, if uses the thermoplastic resin composition layer the thermoplastic resin composition glass transition temperature as Tg (℃) time, preferably Tg-Tg+80 (℃), more preferably Tg+10-Tg+70 (℃), more preferably Tg+20-Tg+60 (℃) scope.

Behind the cross directional stretch, preferably use 20-50 ℃ chill roll group to cool off.

In addition, can carry out again longitudinal stretching and/or cross directional stretch again according to desired film characteristics.

By using the warm-up mill group that film is heated, to vertically implementing longitudinal stretching again.As longitudinal stretching multiplying power again, if uses the thermoplastic resin composition layer the thermoplastic resin composition glass transition temperature as Tg (℃), then be preferably 1.1-2.5 doubly, more preferably 1.2-2.4 doubly, preferably 1.3-2.3 times again.In addition, as this longitudinal stretching temperature again, preferred Tg-Tg+100 (℃), more preferably Tg+20-Tg+80 (℃), more preferred Tg+40-Tg+60 (℃).

Can use stenter to horizontal enforcement cross directional stretch again.As this cross directional stretch multiplying power again, preferred 1.1-2.5 doubly, more preferably 1.15-2.2 doubly, preferably 1.2-2.0 is doubly again.In addition as this cross directional stretch temperature again, if uses the thermoplastic resin composition layer the thermoplastic resin composition glass transition temperature as Tg (℃), then preferably Tg～250 (℃), more preferably Tg+20～240 (℃), Tg+40～220 ℃ preferably again.

After the stretch processing, film can be relaxed under anxiety or to widthwise edge, heat fixation is carried out on the limit.As the preferred 150-250 of heat fixation temperature ℃, more preferably 170-245 ℃, preferably 190-240 ℃ again.Preferred 0.2-30 of the time second that heat fixation needs.

The preferred in addition temperature field at 40-180 ℃ cools off the horizontal loose limit of this film side.As the relaxation rate of this moment, consider to be preferably 1-10%, more preferably 2-8%, 3-7% preferably again from the viewpoint that reduces horizontal percent thermal shrinkage.

In addition, batching behind the film cool to room temperature, can obtain laminated film of the present invention.

Embodiment

[mensuration, determination methods]

(1) inherent viscosity

By using Ostwald viscosimeter, in o-chlorphenol, 25 ℃ of solution viscosity and solvent viscosities of measuring down, adopt following formula to calculate inherent viscosity [η].

With 3 samples each sample is carried out the mensuration of viscosity, calculate, average.

ηsp/C＝[η]+K[η] ²·C

In the formula, η sp=(solution viscosity/solvent viscosity)-1, C are that dissolve polymer weight (g/100ml, common 1.2), the K of every 100ml solvent is He Jin constant (0.343).

(2) glass transition temperature (Tg)

Adopt the simulation isothermal method under following apparatus and condition, compare heat determination according to JIS K7121.

Device: TA Instrument corporate system temperature modulation DSC

Condition determination:

Heating-up temperature: 270-570K (RCS cooling method)

Temperature correction: the fusing point of high-purity indium and tin

Temperature modulation amplitude: ± 1K

The temperature modulation cycle: 60 seconds

Intensification step: 5K

Sample weight: 5mg

Sample container: the opening container (22mg) of aluminum

To container: the opening container (18mg) of aluminum

Glass transition temperature (Tg) adopts following formula to calculate.Use 3 samples, to each test portion carry out glass transition temperature mensuration, calculate, average.

Tg=(the extrapolation glass transition begins temperature+extrapolation glass transition end temp)/2

(3) melting temperature (Tm)

Use セ ィ コ one ィ Application ス Star Le メ Application Star corporate system DSC (RDC220) as differential scanning calorimeter, use above-mentioned corporate system デ ィ ス Network ス テ one シ ョ Application (SSC/5200) as data analysis device, under on the aluminum pallet 300 ℃, sample 5mg fusion was kept 5 minutes, chilling heats up from room temperature for 20 ℃/minute by programming rate after solidifying.This moment the fusion endothermic peak that observed peak temperature as melting temperature (Tm).Use 3 samples, to each sample carry out melting temperature mensuration, calculate, average.

(4) the non-ductility of resin combination

With resin combination place Kapton (Dong Li E.I.Du Pont Company system " カ プ ト Application ") above, use pressure forming machine at 300 ℃ of temperature (fusing point more than 300 ℃ time, be 400 ℃), pressure 10kg/cm ²In 10 seconds of condition lower compression, per 0.2 millisecond outgases, and implements 8 times, makes sheet material.According to ASTM-D882, under dividing, 100 ℃ of temperature, draw speed 100mm/ measure the wide 10mm of the sheet material that makes, the fracture strength of long 20mm sample.Using 3 samples, is being judged as below 50% " non-ductility " with the mean value of percentage elongation.

The time of staying of polymer when (5) melt extruding

Add carbon black 1 weight % to the feed portion of extruder,, observe the appearance that indicator is extruded with polymer from the front end of T font die head through extruder, short tube, filter as indicator.The moment from indicator to the feed portion of extruder that supply with is t ₁, carbon black begins to discharge from die orifice with polymer, then, by the polymer of discharging in becoming the process that does not have carbon black as define t constantly followingly ₂, with (t ₂-t ₁) as the time of staying.

Moment t ₂, use the spectrophotometer U-3410 of Hitachi's system to measure the total light transmittance of casting film central portion to the light of wavelength 550nm, adopting following function F (t) is that 0.98 moment t defines.

F (t)=(total light transmittance of the casting film of the moment t behind the input carbon black)/(dropping into the total light transmittance of the preceding casting film of carbon black)

Damaged frequency when (6) making film

Breakage of thin film applied when observing the system film is judged by following standard

◎: do not have breakage of thin film applied fully.

Zero: seldom produce breakage of thin film applied.

△: produce breakage of thin film applied constantly.

*: breakage of thin film applied takes place frequently.

(7) proportion of film

Test portion is cut into the size of 4cm * 5cm, uses densimeter (the system SD-120L of ミ ラ one ジ ュ trading company), after adopting displacement method in the water of JISK7112 regulation, under 230 ℃, being immersed in the water, measure the proportion after 1 minute.This measured value is converted into 25 ℃ of proportions.

(8) dielectric constant of film

Measure according to JISC2318.Behind the AM aluminum metallization of the two sides of film, use dielectric constant determinator (TA ィ Application ス Star Le メ Application Star system DEA2970) under 30 ℃ of temperature, frequency 10KHz, to measure, use 3 test portions, each sample is measured dielectric constant, average.

(9) Young's modulus

According to the method for ASTM-D882 regulation, use Ying Site youth's type cupping machine (オ リ エ Application テ Star Network Co., Ltd made membrane strength and elongation apparatus for automatically measuring " テ Application シ ロ Application AMF/RTA-100 ") to measure.Be determined under the following condition and carry out.Use 10 samples, each sample is measured Young's modulus, averaged.

Specimen size: width 10mm * tighten up is 100mm at interval

Draw speed: 10mm/ branch

Measure environment: 23 ℃ of temperature, humidity 65%RH

(10) percent thermal shrinkage

According to JIS C2318, under following condition, measure.Use 10 samples, each sample is measured percent thermal shrinkage, average.

Specimen size: width 10mm, graticule be 200mm at interval

Condition determination: 150 ℃ of temperature, 30 minutes processing times, no load state

Obtain 150 ℃ of percent thermal shrinkages by following formula.

Percent thermal shrinkage (%)=[(L0-L)/L0] * 100

L0: the graticule before the heat treated at interval

L: the graticule after the heat treated at interval

(11) thermal coefficient of expansion

Use hot mechanical determinator (セ ィ コ one ィ Application ス Star Le メ Application Star corporate system TMA/SS6100).To specimen width 4mm, the sample of specimen length (spacing jig from) 20mm applies loading 3g, is raised to 170 ℃ by 10 ℃/minute of programming rates from room temperature, keeps 10 minutes.By 10 ℃/component velocity temperature is dropped to 40 ℃ then, kept 20 minutes.150 ℃ to 50 ℃ change in size amount when lowering the temperature when adopting following formula is thus obtained thermalexpansioncoefficient (1/ ℃).Use 3 samples that each sample is measured thermal coefficient of expansion, average.

α＝{(L150-L50)/L0}/ΔT

Initial stage specimen length under L0:23 °

L150: the specimen length during cooling under 150 ℃

L50: the specimen length during cooling under 50 ℃

Δ T: temperature variation (150-50=100)

(12) film dimensions stability

In the film side of the described copper-surfaced Kapton of JIS C6472, use the film of the adhesive applying determination object of general vinyl chloride-based resin and plasticizer system, at 160 ℃ of temperature, pressure 2.9MPa (30kg/cm ²), use roller to press sticking under the condition of 30 minutes time.Glue the sample that film cuts out MD direction 25cm * TD direction 25cm by the pressure that obtains, place on the price fixing, under this state, observe foursquare crimped configuration, ask the mean value of foursquare deflection (mm), estimate by following standard.

◎ and zero is qualified

◎: the not enough 5mm of amount of warpage

Zero: more than the amount of warpage 5mm, not enough 10mm

*: more than the amount of warpage 10mm.

(13) film rate buffer

To being cut into the sample of 5cm * 5cm, use the dial type indicator (Mitutoyo Mfg. Co., Ltd.'s system) of standard test (No.2109-10) that φ 3mm hard sphere is housed, apply the loading of 50g on pressures partially top, read the thickness when keeping for 30 seconds under this state.In addition, other positions to same sample similarly apply the loading of 500g, read the film thickness when keeping 30 seconds under this state.Calculate rate buffer by following formula then.Use 5 samples, each sample is measured rate buffer, average.

Rate buffer (%)=[1-(film thickness during the 500g loading)/(film thickness during the 50g loading)] * 100

(14) flatness

Film sample is cut into MD to the size of 25cm * TD to 25cm, and the state that is no loading places on the somoothing board, handles 30 minutes down for 160 ℃ in temperature.On the cork platform, expand then, use the surface with nonwoven fabric roll around handful film surface is flattened, remove the air between film and the platform fully.Place after 3 minutes, the state of viewing film calculates the number from platform upper film bump." ◎ " of number below 5 of protuberance, more than 6, below 10 be " zero ", being more than 11, below 15 " △ ", more than 16 is " * ".

(15) leakage current of electrically insulating material

Film is made slot liner and wedge pack in the engine, combination AC9000 measures with refrigerant, the oil of VG32 and leaks electricity, and carries out following judgement.

Zero: not enough 0.8mA leaks electricity.

△: electric leakage 0.8-1mA.

*: electric leakage surpasses 1mA.

(16) Ceng thickness ratio

Film sample is embedded in the epoxy resin, vertical and thickness direction along film cuts off, produce the infiltration type electron micrograph of this section, measure the specific layer thickness whole, calculate the thickness ratio of certain layer with respect to the laminated film full depth with laminated film from photo.

(17) voidage in the layer, the diameter of wire inscape

Cut off film sample abreast with film surface, the section of the layer in space etc. is exposed, production infiltration type electron micrograph.Use image analysing computer software to resolve the image of this photo, measure the voidage in the layer.

In addition, this section is observed cancellated occasion, measure minor axis Di, obtain average diameter D by following formula, as the diameter of wire inscape to forming 100 positions of at random extracting out among this cancellated wire inscape.

D＝∑Di/100

[embodiment 1]

(PET's is synthetic)

In the mixture of dimethyl terephthalate (DMT) 100 weight portions and ethylene glycol 60 weight portions, at 140 ℃ of calcium acetates that add down as catalyst for ester exchange reaction, heat to 230 ℃, distillate methyl alcohol and carry out ester exchange reaction.Then, in the product of this ester exchange reaction, add, be transplanted in the polycondensation reaction groove as the antimony trioxide of polymerization catalyst, as the phosphoric acid of heat stabilizer.Then, the limit heats to 290 ℃ of limits slowly with the 0.1kPa that reduces pressure in the reaction system from 230 ℃, at 290 ℃, decompression is stirred inner down, the limit distillates the polymerization of methyl alcohol limit, composite character viscosity 0.62,78 ℃ of glass transition temperatures, 255 ℃ of fusing points, do not add the PETG (PET) (yet claim no particle PET) of particle basically.

(manufacturing of resin combination B)

In above-mentioned no particle PET sheet, add the cohesion silicon dioxide granule of average diameter 2.5 μ m, making content is 2 weight %, make the master slice that particle adds usefulness, again this master slice is mixed with aforesaid no particle PET sheet, making particle is 0.1 weight %, after 3 hours, supply with the extruder I that the compressional zone is heated to 280 ℃ 180 ℃ of vacuum drying.

Complete each such embodiment, the resin combination common name " resin combination B " that comparative example makes, the layer that resin combination B is constituted is generally called " B layer ".

(manufacturing of resin combination A)

Above-mentioned no particle PET sheet 50 weight portions with as the u'eno pharmaceutical Co. Ltd system " u'eno LCP " 5000 of liquid-crystalline polymer (claiming LCP1) 50 weight portions 180 ℃ of vacuum drying after 3 hours, throw in the exhaust co-rotating twin screw mixing extruder (screw diameter 25mm, spiro rod length/screw diameter=28) that mixing district is heated to 290 ℃, under 200 rev/mins of screw rod rotation numbers, 2 minutes time of staying condition, melt extrude, being strip discharges, after in cold water, cooling off, section obtains the alloyed polymer sheet immediately.The percentage elongation of judging non-ductility is 20%.This alloyed polymer sheet after 3 hours, is supplied with the extruder II that the compressional zone is heated to 280 ℃ 180 ℃ of vacuum drying.

Each so fully embodiment, the resin combination common name " resin combination A " that comparative example makes, the layer that resin combination A is constituted are generally called " A layer ".

(manufacturing of the laminated film that do not stretch)

Resin combination A, the B of each extruder fusion are filtered with filter respectively, and 3 layers of rectangle afflux mould (feeding mould) the formation B/A/B of 3 layers of usefulness of use are compound.The flow of the polymer by the afflux mould utilizes and regulates the rotation number that is arranged at the gear pump in each pipeline, the control extrusion capacity, and the interflow, making whole thickness of the final laminated film after elongation/relaxation is handled is 50 μ m, composite thickness is than being B/A/B=1/1/1.

Extrude compound like this molten polymer, on the casting roller of 25 ℃ of surface temperatures, the limit applies the static limit makes polymer be adjacent to the roller cooling curing, batches by draw ratio (ratio of die orifice interval of slit/non-stretched film thickness) 8, makes the laminated film that do not stretch.

(elongation/relaxation processing)

Use the longitudinal stretching machine of heated a plurality of roller compositions, utilize the difference of roller, under 100 ℃ of draft temperatures, 3.5 times of conditions of stretching ratio, this laminated film vertically stretching that do not stretch along film.Then with the both ends of this film of clamp clamps, the guiding stenter is laterally stretching of the condition lower edge film of 105 ℃ of draft temperatures, 3.7 times of stretching ratios.

Then after carrying out heat treatment in 3 seconds under 235 ℃ the temperature, laterally carry out 3% relaxation processes on the edge, cooling zone that controls to 150 ℃, then, laterally implement 1% relaxation processes on the edge, cooling zone that controls to 100 ℃, then behind the cool to room temperature, remove film edge, make the laminated film of thickness 50 μ m (every layer thickness of A layer and B layer is 16.7 μ m, and promptly the thickness ratio of A layer is 33%).

The film of present embodiment had not both had breakage of thin film applied when the system film, production efficiency is also good.

The formation of the laminated film that makes and rerum natura are shown in table 1-3.The laminated film of present embodiment, the A layer that is made of the resin combination A that contains liquid-crystalline polymer has network structure, and thermal coefficient of expansion is little, and rigidity is also little, and the dimensional stability when using as circuit material might as well.In addition, low dielectric property might as well.As the fibriilar average diameter that forms cancellated wire inscape is 3.5 μ m.

[embodiment 2]

Except the thickness ratio with B/A/B among the laminated film thickness 50 μ m made 12.5/25/12.5 into, other made laminated film similarly to Example 1.

[embodiment 3]

In the manufacturing of resin combination A, use the liquid crystalline polyester (claiming LCP2) of following composition and 265 ℃ of fusing points, molecular weight 18000 as liquid-crystalline polymer.

(copolymerization of LCP2 is formed)

56.8 moles of % of P-hydroxybenzoic acid

4,4 '-5.9 moles of % of dihydroxybiphenyl

15.7 moles of % of ethylene glycol

21.6 moles of % of terephthalic acid (TPA)

In addition, the weight ratio of PET/LCP2 changes 30/70 among the resin combination A.The percentage elongation of judging non-ductility is 15%.

Except that these, other make laminated film similarly to Example 1.

[embodiment 4]

(PPS resin)

The no particle PET that replaces embodiment 1, the line style PPS resin (" ラ ィ ト Application " T1881,92 ℃ of glass transition temperatures, 285 ℃ of fusing points) of employing Dong Li Co., Ltd system.

(manufacturing of resin combination B)

In above-mentioned PPS resin, add SiO 2 powder 0.2 weight %, the calcium stearate 0.05 weight % of average grain diameter 0.7 μ m, evenly disperseing the mixture of cooperation as resin combination B, after 3 hours, supply with the extruder I that the compressional zone is heated to 295 ℃ 180 ℃ of vacuum drying.

(manufacturing of resin combination A)

3 little above-mentioned PPS resin (" ラ ィ ト Application " T1881) 50 weight portions and LCP150 weight portion in 180 vacuum drying, the time after, throw into exhaust co-rotating twin screw mixing extruder (the screw diameter 25mm that mixing district is heated to 305 ℃, spiro rod length/screw diameter=28) in, under 200 rev/mins of screw rod rotation numbers, 90 seconds time of staying condition, melt extrude, being strip discharges, after the cold water cooling, section immediately makes the alloyed polymer sheet.The percentage elongation of judging non-ductility is 10%.

This alloyed polymer sheet after 3 hours, is supplied with the extruder II that the compressional zone is heated to 300 ℃ 180 ℃ of vacuum drying as resin combination A.

(manufacturing of the laminated film that do not stretch)

Except using above-mentioned resin combination A, B and draw ratio is 5, and other make the laminated film that do not stretch similarly to Example 1.

(elongation/relaxation processing)

Use longitudinal stretching machine similarly to Example 1, under 105 ℃ of draft temperatures, 3.1 times of conditions of stretching ratio with this non-stretched film vertically stretching along film.Then, use stenter similarly to Example 1, along film laterally 115 ℃ of draft temperatures, stretch under 3.2 times of conditions of stretching ratio.

Then after carrying out heat treatment in 3 seconds under 255 ℃ the temperature, laterally carry out 4% relaxation processes on the edge, cooling zone that controls to 150 ℃, laterally implement 1% relaxation processes on the edge, cooling zone that controls to 100 ℃ then, then behind the cool to room temperature, remove film edge, make the laminated film of thickness 50 μ m (every layer thickness of A layer and B layer is 16.7 μ m, be that the thickness ratio of A layer is 33%).The film of present embodiment does not have breakage of thin film applied, production efficiency good when the system film yet.

The formation of the laminated film that makes and rerum natura are shown in table 1-3.The laminated film of present embodiment, the A layer that is made of the resin combination A that contains liquid-crystalline polymer has network structure, and the thermal coefficient of expansion PPS film than individual layer shown in the comparative example 2 significantly is little, and rigidity is also little, has the characteristic that is suitable as circuit material.In addition, low dielectric property might as well.The average fibrillation diameter that forms cancellated wire inscape is 3 μ m.

[comparative example 1]

Except only using the resin combination B same with embodiment 1 compositions for use, making the PET film of monofilm of thickness 50 μ m, other make film similarly to Example 1.

[comparative example 2]

Except only using the resin combination B same with embodiment 4 compositions for use, making the PPS film of monofilm of thickness 50 μ m, other make film similarly to Example 4.

[comparative example 3]

Change the weight ratio of PET/LCP1 among the resin combination A into 95/5.The percentage elongation of judging non-ductility is 500%.

In addition, make laminated film similarly to Example 1.

Resin combination A is not the laminated film of the comparative example 3 of non-ductility, does not have network structure in the A layer, and it is little that the characteristic of the film that makes and the PET film of comparative example 1 are compared difference.

[comparative example 4]

Except the weight ratio with the PET/LCP1 among the resin combination A changes into 5/95, other manufacture experimently laminated film similarly to Example 1.

Yet, owing to repeatedly breakage of thin film applied takes place, thus steady customised films, and also the film that makes do not have network structure in the A layer, and film surface is also bad.

The results are shown in table 1 with what the layer of embodiment 1-4, comparative example 1-4 constituted.

Table 1

	Layer constitutes	The B layer	The A layer		The amount (weight %) that liquid-crystalline polymer is whole with respect to laminated film
						Resin is formed (weight ratio)	Thickness ratio (%)
			Embodiment 1	B/A/B				PET	PET/LCP1(50/50)	33	6
Embodiment 2	B/A/B	PET			PET/LCP1(50/50)	50	10
			Embodiment 3	B/A/B				PET	PET/LCP2(30/70)	33	9
Embodiment 4	B/A/B	PPS			PPS/LCP1(50/50)	33	8
			Comparative example 1	B				PET	-	0	0
Comparative example 2	B	PPS			-	0	0
			Comparative example 3	B/A/B				PET	PET/LCP1(95/5)	33	2
Comparative example 4	B/A/B	PET			PET/LCP1(5/95)	33	25

In addition, the evaluation result of embodiment 1-4, comparative example 1-4 is shown in table 2,3.

Table 2

	The network structure of A layer	Damaged frequency during the system film	Proportion	Dielectric constant
					Embodiment 1	Have	◎	0.80	2.6
Embodiment 2	Have	◎	0.70	1.7
					Embodiment 3	Have	○	0.61	1.9
Embodiment 4	Have	◎	0.78	2.1
					Comparative example 1	Do not have	○	1.39	3.3
Comparative example 2	Do not have	○	1.40	3.0
					Comparative example 3	Do not have	◎	1.38	3.2
Comparative example 4	Do not have	×	-	-

Table 3

	Young's modulus (MD/TD) (GPa)	Percent thermal shrinkage (MD/TD) (%)	Thermal coefficient of expansion (MD/TD) (ppm/ ℃)	Dimensional stability	Electric leakage
						Embodiment 1	3.2/3.4	0.4/0.2	24/22	◎	△
Embodiment 2	3.0/3.2	0.2/0.2	18/17	◎	○
						Embodiment 3	3.2/3.4	0.4/0.2	21/20	◎	○
Embodiment 4	3.1/3.3	0.3/0.2	28/24	◎	○
						Comparative example 1	4.4/4.5	1.6/0.9	34/32	×	×
Comparative example 2	4.2/4.3	1.5/0.6	53/52	×	×
						Comparative example 3	4.2/4.4	1.5/0.5	35/31	×	×
Comparative example 4	-	-	-	-	-

[embodiment 5]

(PET's is synthetic)

Add magnesium acetate 4 water salt 0.1 weight portion in dimethyl terephthalate (DMT) 194 weight portions and ethylene glycol 124 weight portions, heat to 230 ℃, the limit distillates the methyl alcohol limit and carries out ester exchange reaction.Add then trimethyl phosphate 0.05 weight portion ethylene glycol solution, with antimony trioxide 0.05 weight portion, stirs after 5 minutes, adopt stirring oligomer limit, 30 rev/mins of limits that reaction system slowly is raised to 290 ℃ from 230 ℃, meanwhile pressure is dropped to 0.1kPa.The time that arrives final temperature, final pressure is 60 minutes.Polymerisation 3 hours, in the moment of the stirring moment of torsion that becomes regulation, nitrogen purges reaction system, turn back to normal pressure, stop polycondensation reaction, be strip and be extruded in the cold water, section immediately makes the particle of the PETG (PET) that does not add particle basically (also claiming no particle PET) of inherent viscosity 0.62.78 ℃ of the glass transition temperatures of this no particle PET, fusing point are 255 ℃.

(manufacturing of resin combination B)

In above-mentioned no particle PET pellet, add the cohesion silicon dioxide granule of average diameter 2.5 μ m, making content is 2 weight %, make particle interpolation master slice, again this master slice being become particle with the compounding of aforesaid no particle PET pellet is 0.1 weight %, 180 ℃ of vacuum drying after 3 hours, become resin combination B, supply is heated to the compressional zone 280 ℃ extruder I.

(manufacturing of resin combination A)

Above-mentioned no particle PET sheet 50 weight portions and LCP150 weight portion 180 ℃ of vacuum drying after 3 hours, put into exhaust co-rotating twin screw mixing extruder (the screw diameter 25mm that mixing district is heated to 290 ℃, spiro rod length/screw diameter=28) in, under 200 rev/mins of screw rod rotation numbers, 2 minutes time of staying condition, melt extrude and be the strip discharge, after the cooling, section immediately obtains the alloyed polymer sheet in cold water.The percentage elongation of judging non-ductility is 20%.

This alloyed polymer sheet after 3 hours, is become resin combination B 180 ℃ of vacuum drying, supply with the extruder II that the compressional zone is heated to 280 ℃.

(manufacturing of the laminated film that do not stretch)

The resin combination A of each extruder fusion, B filters with filter respectively, and 3 layers of rectangle afflux mould (feeding mould) the formation B/A/B of 3 layers of usefulness of use are compound.The flow of the polymer by the afflux mould, utilize and regulate the rotation number that is arranged at the gear pump in each pipeline, the control extrusion capacity, the interflow, the whole thickness that makes the final laminated film after the stretching relaxation processes is that 50 μ m, composite thickness are than being B/A/B=20/60/20.

Extrude so compound molten polymer, on the casting roller of 25 ℃ of surface temperatures, the limit applies the static limit makes polymer be adjacent to the roller cooling curing, batch by draw ratio (ratio of die orifice interval of slit/non-stretched film thickness) 8, make the laminated film that do not stretch.

(elongation/relaxation processing)

Use the roll-type stretching-machine under 105 ℃ of draft temperatures, 1.2 times of conditions of stretching ratio, this not to be stretched laminated film, then under 85 ℃ of draft temperatures, 3.0 times of conditions of stretching ratio, stretch again along vertically the stretching of film.Re-use stenter 100 ℃ of draft temperatures, laterally the stretching of stretching ratio 4.0 times of condition lower edges film.

Then, under fixed length, after 10 seconds of 230 ℃ of heat treatment of temperature, laterally implement 1% loose processing on 200 ℃ of edges, make the laminated film of thickness 50 μ m.

The formation of gained laminated film and characteristic are shown in table 4-6.This laminated film is low dielectric property, resiliency or the good film of flexibility, low heat expansion and flatness.

[embodiment 6-9]

Except the thickness ratio of change liquid-crystalline polymer LCP1 as shown in table 4 with respect to the content of resin combination A or A layer, other make laminated film similarly to Example 5.

The formation of gained laminated film and characteristic are shown in table 4-6.These laminated film also is low dielectric property, resiliency and the good film of flexibility, low heat expansion and flatness.The percentage elongation of judging non-ductility is 25% (embodiment 6), 40% (embodiment 7), 5% (embodiment 8).Among the embodiment 6-8, the A layer that constitutes by resin combination A, the space company of passing through longitudinally on the face parallel, or the plan network structure that has the key element that constitutes mesh to interrupt halfway with film surface.And embodiment 9 has network structure at the A layer.

[embodiment 10]

As liquid-crystalline polymer, replace LCP1, use LCP2.The percentage elongation of judging non-ductility is 30%.In addition, other make laminated film similarly to Example 5.

The formation of gained laminated film and characteristic are shown in table 4-6.This laminated film also is low dielectric property, resiliency and the good film of flexibility, low heat expansion and flatness.

[embodiment 11]

As liquid-crystalline polymer, use the liquid crystalline polyester (claiming LCP3) of 220 ℃ of following composition and fusing points.

The copolymerization of LCP3 is formed

31.2 moles of % of P-hydroxybenzoic acid

4,4 '-4.9 moles of % of dihydroxybiphenyl

29.5 moles of % of ethylene glycol

34.4 moles of % of terephthalic acid (TPA)

The percentage elongation of judging non-ductility is 45%.

In addition other make laminated film similarly to Example 5.

The characteristic of gained laminated film is shown in table 4-6.This laminated film is low dielectric property, low heat expansion and the good film of flatness.

[embodiment 12]

In the manufacturing of the resin combination A of embodiment 4, as liquid-crystalline polymer, replace LCP1, use the liquid crystal liquid crystal property resin (" シ ベ ラ ス " (registration mark) of Dong Li Co., Ltd system, 315 ℃ of fusing points) (claim LCP4), and to make the heating-up temperature in the mixing district of exhaust co-rotating twin screw mixing extruder be 325 ℃.The percentage elongation of judging non-ductility is 15%.Except that these, other make laminated film similarly to Example 4.

The characteristic of gained laminated film is shown in table 4-6.This laminated film is low heat expansion and the good film of dielectric property.

[embodiment 13]

(manufacturing of resin combination B)

Make resin combination B similarly to Example 5, supply with extruder I.

(manufacturing of resin combination A)

The liquid-crystalline polymer LCP1 that replaces embodiment 5, use (PMP) 40 weight portions of polymethylpentene (Mitsui Chemicals system DX820), in addition, the no particle PET that replaces embodiment 5, use is as the PET60 weight portion of polyethylene glycol (PEG) the 6 weight % copolymerization of the molecular weight 4000 of dispersant, with these mixing, 180 ℃ of vacuum drying after 3 hours, put into exhaust co-rotating twin screw mixing extruder (the screw diameter 25mm that mixing district is heated to 290 ℃, spiro rod length/screw diameter=28) in, 200 rev/mins of screw rod rotation numbers, melt extrude under 2 minutes time of staying condition and be the strip discharge, after the cooling, section immediately obtains the alloyed polymer sheet in cold water.The percentage elongation of judging non-ductility is 45%.This alloyed polymer sheet after 3 hours, is supplied with extruder II that compressional zone be heated to 280 ℃ as resin combination A 180 ℃ of vacuum drying.

(manufacturing of the laminated film that do not stretch)

Resin combination A, the B of each extruder fusion are filtered with filter respectively, use the pipe die that gathers materials (nozzle is compound) of 3 layers of usefulness more, 3 layers of forming B/A/B are compound.The flow of the polymer by the pipe die that gathers materials more, utilize and regulate the rotation number that is arranged at the gear pump in each pipeline, control extrusion capacity, interflow, making whole thickness of the final laminated film after the stretching relaxation processes is 50 μ m, and composite thickness is than being B/A/B=20/60/20.

Extrude compound like this molten polymer, on the casting roll of 25 ℃ of surface temperatures, the limit applies the static limit makes polymer be close to the roller cooling curing, batches by draw ratio (ratio of die orifice interval of slit/non-stretched film thickness) 8, makes the laminated film that do not stretch.

(elongation/relaxation processing)

Similarly to Example 5 this non-stretched film is stretched etc., make laminated film.

The characteristic of gained laminated film is shown in table 4-6.This laminated film be low dielectric property good, about low heat expansion and the also qualified level of flatness.

[embodiment 14]

The liquid-crystalline polymer LCP1 that replaces embodiment 5 uses the PEI (" ゥ Le テ system " 1010) of GE Plastics Company system (PEI), in addition to make laminated film similarly to Example 5.

The characteristic of gained laminated film is shown in table 4-6.This laminated film be low dielectric property good, about low heat expansion and the also qualified level of flatness.

[comparative example 5,6]

Except the thickness ratio of change liquid-crystalline polymer LCP1 as shown in table 4 with respect to the content of resin combination A, A layer, other make laminated film similarly to Example 5.

The characteristic of gained laminated film is shown in table 5,6.Be proportion outside scope of the present invention, low dielectric property, resiliency, flexibility, low heat expansion and the inadequate film of flatness.

[comparative example 7]

Except only using the same resin combination B used with embodiment 5, make beyond the monofilm PET film of thickness 50 μ m, other make film similarly to Example 5.

The characteristic of gained film is shown in table 5,6, be low dielectric property, resiliency, flexibility and the inadequate film of low heat expansion.

Table 4

	Layer constitutes	The B layer	The A layer		The amount (weight %) that liquid-crystalline polymer is whole with respect to laminated film
						Resin is formed (weight ratio)	Thickness ratio (%)
			Embodiment 5	B/A/B				PET	PET/LCP1(50/50)	60	12
Embodiment 6	B/A/B	PET			PET/LCP1(65/35)	75	10
			Embodiment 7	B/A/B				PET	PET/LCP1(72/28)	80	10
Embodiment 8	B/A/B	PET			PET/LCP1(10/90)	15	3
			Embodiment 9	B/A/B				PET	PET/LCP1(50/50)	50	6
Embodiment 10	B/A/B	PET			PET/LCP2(50/50)	60	12
			Embodiment 11	B/A/B				PET	PET/LCP3(50/50)	60	12
Embodiment 12	B/A/B	PPS			PPS/LCP4(50/50)	60	12
			Embodiment 13	B/A/B				PET	PET/PMP(60/40)	60	-
Embodiment 14	B/A/B	PET			PET/PEI(50/50)	60	-
			Comparative example 5	B/A/B				PET	PET/LCP1(70/30)	15	2
Comparative example 6	B/A/B	PET			PET/LCP1(50/50)	80	32
			Comparative example 7	B				PET	-	0	0

Table 5

	The network structure of A layer	Proportion	Rate buffer (%)	Dielectric constant
					Embodiment 5	Have	0.56	30	1.7
Embodiment 6	Have	0.66	21	2.6
					Embodiment 7	Have	0.72	17	2.8
Embodiment 8	Have	1.05	12	2.7
					Embodiment 9	Have	0.68	23	1.6
Embodiment 10	Have	0.58	27	2.0
					Embodiment 11	Have	0.70	18	2.7
Embodiment 12	Have	0.72	21	2.0
					Embodiment 13	Have	0.45	35	1.5
Embodiment 14	Have	0.82	15	2.3
					Comparative example 5	Do not have	1.23	7	2.9
Comparative example 6	Do not have	0.18	55	1.5
					Comparative example 7	Do not have	1.38	5	3.3

Table 6

	Young's modulus (MD/TD) (GPa)	Percent thermal shrinkage (MD/TD) (%)	Thermal coefficient of expansion (MD/TD) (ppm/ ℃)	Flatness	Electric leakage
						Embodiment 5	2.7/2.8	0.3/0.2	17/16	◎	○
Embodiment 6	3.1/3.2	0.4/0.2	18/17	◎	○
						Embodiment 7	3.6/3.8	0.5/0.2	22/23	○	△
Embodiment 8	3.8/4.2	0.7/0.3	26/25	△	△
						Embodiment 9	3.0/3.0	0.3/0.2	18/17	○	○
Embodiment 10	3.3/3.5	0.3/0.2	17/16	◎	○
						Embodiment 11	3.7/3.8	0.2/0.2	24/22	○	△
Embodiment 12	3.2/3.4	0.3/0.2	24/23	○	○
						Embodiment 13	2.4/2.3	0.4/0.2	32/31	△	○
Embodiment 14	3.0/3.2	0.2/0.2	38/36	△	○
						Comparative example 5	4.1/4.6	1.2/0.5	31/31	×	×
Comparative example 6	1.4/1.5	0.4/0.3	13/12	×	○
						Comparative example 7	4.5/5.0	2.1/0.9	35/33	×	×

[comparative example 8]

Except using and embodiment 5 used same resin combination A, B, its layer formation reversed to beyond the A/B/A, other manufacture experimently laminated film similarly to Example 5.

Yet, breakage of thin film applied repeatedly takes place during stretching, can not obtain the laminated film of biaxial tension.

[comparative example 9]

Except using and embodiment 5 used same resin combination A, B, make thin layer constitute 2 layers of formation of A/B, the composite thickness ratio is for beyond the A/B=1/2, and other manufacture experimently laminated film similarly to Example 5.

Yet, breakage of thin film applied repeatedly takes place when stretching, can not obtain the laminated film of biaxial tension.

Claims (13)

1. laminated film, it is the laminated film that is made of at least 3 layers film, at least 1 layer is that cancellated film is arranged, and is compounded with the layer of the biaxial tension that thermoplastic resin makes in two outsides of this layer.

2. the described laminated film of claim 1 is characterized in that, aforementioned have cancellated thin layer to be made of the resin combination of non-ductility.

3. the described laminated film of claim 1 is characterized in that, aforementioned have cancellated thin layer to contain liquid-crystalline polymer.

4. the described laminated film of claim 3 is characterized in that, aforementioned have cancellated thin layer also to contain non-liquid crystalline polyester.

5. the described laminated film of claim 4 is characterized in that, non-liquid crystalline polyester is PETG, PEN or its modifier.

6. the described laminated film of claim 3 is characterized in that, the content of cancellated thin layer is arranged is 20-90 weight % to liquid-crystalline polymer with respect to aforementioned.

7. the described laminated film of claim 3 is characterized in that, the liquid-crystalline polymer content whole with respect to laminated film is 3-30 weight %.

8. the described laminated film of claim 1 is characterized in that, aforementioned the thickness of cancellated thin layer is arranged is the 1-90% of the whole thickness of laminated film.

9. the described laminated film of claim 8 is characterized in that, aforementioned the thickness of cancellated thin layer is arranged is the 10-80% of the whole thickness of laminated film.

10. the described laminated film of claim 1 is characterized in that, the thermoplastic resin composition of the thin layer of biaxial tension is contained at least a kind that is selected from polyester, polyphenylene sulfide, PEI, Merlon, polyether-ketone, polyether sulfone, polysulfones, PLA.

11. the described laminated film of claim 1 is characterized in that, the vertical and horizontal Young's modulus of laminated film all is 2-7GPa.

12. the described laminated film of claim 1 is characterized in that, the vertical and horizontal percent thermal shrinkage under 150 ℃ of temperature of laminated film all is 0-2%.

13. the described laminated film of claim 1 is characterized in that, the vertical and horizontal thermal coefficient of expansion of laminated film all is 3-45ppm/ ℃.

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