CN100439098C - Shape-memory polybutylene terephthalate laminated film, and its production method and use, and polybutylene terephthalate film producing method - Google Patents

Shape-memory polybutylene terephthalate laminated film, and its production method and use, and polybutylene terephthalate film producing method Download PDF

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Publication number
CN100439098C
CN100439098C CNB038253011A CN03825301A CN100439098C CN 100439098 C CN100439098 C CN 100439098C CN B038253011 A CNB038253011 A CN B038253011A CN 03825301 A CN03825301 A CN 03825301A CN 100439098 C CN100439098 C CN 100439098C
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film
pbt
polybutylene terephthalate
temperature
shape
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CN1700983A (en
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加川清二
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined

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  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

A laminated polybutylene terephthalate film having an excellent shape memory and high dimensional stability under heat, which is obtained by (1) bonding a polybutylene terephthalate film to another film or a laminated film and forming the obtained laminate at a temperature (T1) not higher than the glass transition temperature of the polybutylene terephthalate while keeping it in the first shape, (2) forming the obtained shaped laminate into the second shape at a temperature (T2) exceeding the above glass transition temperature, and (3) cooling the obtained shaped laminate to a temperature (T3) not higher than the above glass transition temperature.

Description

The manufacture method of shape memory polybutylene terephthalate (PBT) laminate film and Manufacturing approach and use thereof and polybutylene terephthalate (PBT) film
Technical field
The present invention relates to can be used as the manufacture method of the good polybutylene terephthalate (PBT) film of the shape memory polybutylene terephthalate (PBT) laminate film of packaging material and manufacture method thereof and purposes, film thickness uniformity and heat-resisting shrinkage and tearability or warping property good can be as the functional polyalkylene mutual-phenenyl two acid bromide two alcohol ester film of packaging material etc.
Background technology
, as the lid material that the peristome to container for fast food seals, for example use in the container at instant noodles, known have successively with easy-to-rupture sealing film, aluminium foil, the folded material that forms of ply of paper all the time.
Lid material with aluminium foil layer is good to the shielding of steam etc., dimensional stability, filling machine adaptability (filling content and lid material crimping not when sealing in container), light-proofness etc. to heat etc.In addition, the lid material with aluminium foil layer has the character (stationary state (dead hold) property) that can be maintained the state of starting when shelling to approximate centre portion from container.Utilize stationary state, for example when instant hand-pulled noodles etc., can then lid sealed once more keeping easily injecting hot water under the half-open state after peeling off, be retained to instant noodles and reach edible state, Kaifeng is edible more afterwards.
But, having in the burning disposal of lid material after use of aluminium foil, aluminium foil can damage incinerator as block the gathering in incinerator, will bring the problem that reduces firing efficiency thus.So, consider from the viewpoint of environmental protection, preferably do not use lid material as far as possible with aluminium foil.In addition, when the instant food of edible bowl face and so on, consider from the viewpoint of foodsafety, need to check in the container whether be mixed with the metal species foreign matter, but just can not utilize the detection of metal detector after will having the lid heat seal of aluminium foil, be to check before with the lid heat seal at present therefore.In addition, using under the situation of aluminium foil as lid, also having lid to become heavy problem.
As the lid material that does not comprise aluminium foil, proposed for example have ply of paper successively/adhering resin layer/PETG layer/easily peel off the laminate film of resin bed.PETG (PET) film has shielding, the dimensional stability to heat, the filling machine adaptability characteristics such as (not having crimping) of steam.But, because the stiffness of PET film is bigger, therefore lid is maintained aspect the character (stationary state) of Kaifeng state relatively poor.Thus, lid will be closed behind Kaifeng easily, thereby has the problem that is difficult to inject hot water.
For constituting instant noodles for the laminate film of employed lid material in the container etc., require it can crimping when container is sealed and when peeling off from container, can keep the state (having stationary state) of crimping.Usually the lid material is to be thermally sealed on the container, as long as the heat when therefore having before heat seal crimping not and can utilize heat seal and the shape memory of crimping is just very useful.
But the packaging material of being made by the laminate film with shape memory are not up to now also by known to the people.In general, the spring rate of the resin with shape memory before and after glass transition temperature changes greatly.Shape memory mechanism for example is following situation: (1) at first makes shape M arbitrarily, heating under the state of this shape M and crystallization (winding of crystalline portion) or utilize intermolecular cross-linking and produce fixing point, make it shape memory, (2) more than the glass transition temperature and be lower than and apply external force under the temperature of described heating-up temperature and be deformed into shape N, under this state, make it to reach the temperature that is lower than glass transition temperature and be fixed as shape N, (3) can return to shape M by being heated to more than the glass transition temperature under the condition that does not apply external force at this moment.Though PET is the material with shape memory because glass transition temperature is about 70～80 ℃, so shape to recover needed temperature too high.
Polybutylene terephthalate (PBT) (PBT) uses if therefore can be used as packaging material owing to have about 20～45 ℃ glass transition temperature, then can utilize the shape memory under applied temps.For example special opening records the shape memory resin of being made by the block copolymer of PBT and aliphatic poly lactone in flat 2-123129 number.In addition, the spy open record in flat 2-269735 number by for the crystallization entropy of melting is reached below the 3cal/g and copolymerization the shape memory copolyester formed body made of the PETG of the 3rd composition.In addition, the spy opens flat 2-240135 number and records the shape memory resin of being made by the block copolymer of PBT and polyethylene glycol.But these documents are not all with PBT class shape memory resin filmization.
Proposed inherent viscosity is satisfied following formula at the PBT resin more than 1.0 at resin temperature for special fair 7-33048 number:
Fusing point (℃)＜the extrusion resin temperature (℃)＜fusing point-26+53 * inherent viscosity (℃) condition under utilize expansion-molded method to carry out the method for filming.But, in this method, and to be unrealized and to expand (blow up) than the optimization of the combination of, extrusion resin temperature and extrusion resin pressure, the PBT film of gained has bigger percent thermal shrinkage.
For the function of packaging material, because the PBT film is good aspect gas-barrier property or fragrance protectiveness, as long as it is just more satisfactory therefore can to give functions such as tearability, warping property.As the tearability polyester film, the spy opens and announces that the double-shaft extension polyester film that is made of PETG (PET) 80～95 quality % and modified PBT (modified PBT) 20～5 quality % is arranged for 2002-80705 number.But the tearability of this double-shaft extension polyester film is insufficient.
Te Kaiping 5-104618 conduct has the manufacture method of the polyester film of good warping property, record the stacked resin (B) that has than the high fusing point more than 10 ℃ of fusing point of (A) on the single face at least of polyester resin layer (A), make to reach 5～60% thickness the method for under the temperature that is being lower than behind the uniaxial extension than the fusing point of low (B) more than 10 ℃ of fusing point of (A), heat-treating with respect to film thick entirely (B).But this manufacture method of polyester film with warping property is because operation is very miscellaneous, so cost is very high.
Summary of the invention
Therefore, the objective of the invention is to, polybutylene terephthalate (PBT) laminate film with good shape memory and heat-resisting dimensional stability, its manufacture method and uses thereof are provided.
Another object of the present invention is, to make be the method for the good polybutylene terephthalate (PBT) film of the uniformity of film thickness and heat-resisting shrinkage though provide.
Another purpose of the present invention is, provides tearability good polybutylene terephthalate (PBT) film.
Another object of the present invention is, the polybutylene terephthalate (PBT) film that warping property is good and can make with low cost is provided.
The result who furthers investigate in view of described purpose, the inventor have found the following fact.
(A) (1) laminate film that film or thin-film laminate with described PBT film and other are laminated, under the condition that keeps first shape, the temperature T below the glass transition temperature Tg of PBT film 1Under carry out figuration and handle, (2) with the figuration duplexer of gained in the temperature T that surpasses Tg 2Following deformation processing is second shape, and (3) are by being cooled to the temperature T below the Tg 3, the PBT laminate film that can obtain to have good shape memory and heat-resisting dimensional stability.
(B) (1) (i) makes the film of described PBT film and other or the laminate film of thin-film laminate in advance, to its keep first shape condition under, the temperature T that (is not containing Tg) more than the Tg～(do not containing fusing point) below the fusing point 4Carry out down that figuration is handled or (ii) to described PBT film under the condition that keeps first shape, in described temperature T 4Carry out figuration down and handle the back by stacked with other film or thin-film laminate, make the laminate film with first shape, (2) are cooled to temperature T below the Tg with the figuration duplexer of gained 5And be fixed as first shape, (3) (are not containing Tg)～described temperature T with described figuration duplexer then more than described Tg 4Below (do not contain T 4) temperature T 6After following deformation processing was second shape, (4) were by being cooled to the temperature T below the Tg 7And be fixed as second shape, the PBT laminate film that can obtain to have good shape memory and heat-resisting dimensional stability.
(C) polybutylene terephthalate (PBT) (PBT) resin is being utilized the expansion-molded method of air cooling (air-cooled) carry out in the manufacture method of PBT film of filming, spray humidifying air near first air ring being located at annular die, to steep the neck cooling of (bubble), blow-up ratio is made as 1.5～2.8, the extrusion resin temperature is made as 210～250 ℃, extrusion resin pressure is made as 9.8～13.7MPa (100～140kgf/cm 2), be the uniformity and the good polybutylene terephthalate (PBT) film of heat-resisting shrinkage of film thickness though just can make.
(D) by at least one side's of polybutylene terephthalate (PBT) film face, forming many parallel in fact wire traces all sidedly, just can give can be from position arbitrarily along described wire trace in fact along the straight line tearability of smooth tearing.
(E) by on the polybutylene terephthalate (PBT) film, being formed uniformly a plurality of fine through holes and/or through hole not, just can give tearability and warping property.
The application is based on this invention and finishes.
Promptly, the feature of shape memory polybutylene terephthalate (PBT) laminate film of the present invention is, have (1) polybutylene terephthalate (PBT) film, (2) by from paper sheet, other resin film and metal forming at least a other film or the thin-film laminate of making selected, and in the temperature province of regulation, remembered first shape.
Even shape memory polybutylene terephthalate (PBT) laminate film of the present invention is deformed in the temperature province different with the temperature province of described regulation and is processed as second shape, when being exposed on the temperature of having remembered described first shape when above, will get back to described first shape in fact.
In the preferred example of shape memory polybutylene terephthalate (PBT) laminate film, the temperature of getting back to described first shape is below the Tg of described polybutylene terephthalate (PBT).The temperature of getting back to described first shape is more preferably below 35 ℃.
Shape memory polybutylene terephthalate (PBT) laminate film is got back to the fusing point following (not containing fusing point) of above (not containing the Tg)～described polybutylene terephthalate (PBT) of Tg of the described polybutylene terephthalate (PBT) of temperature of described first shape.Get back to more preferably 75～100 ℃ of the temperature of described first shape.
Described first shape is preferably crimping (curl) shape, and described second shape is preferably the shape or the inverse hemming shape of general planar.
What be preferably in described polybutylene terephthalate (PBT) film forms many parallel in fact wire traces on the one side at least all sidedly, so just shape memory polybutylene terephthalate (PBT) laminate film can be torn along straight line basically along described wire trace.The degree of depth of described wire trace be preferably described polybutylene terephthalate (PBT) thin layer thickness 1～40%.Specifically, the degree of depth of best described wire trace is 0.1～10 μ m, and the width of described wire trace is 0.1～10 μ m, and is spaced apart 10～200 μ m between the described wire trace.Also can described polybutylene terephthalate (PBT) film at least the one side on evaporation pottery or metal.
The example that the preferred layer of shape memory polybutylene terephthalate (PBT) laminate film of the present invention constitutes is for having the formation of described polybutylene terephthalate (PBT) film, described paper sheet, sealing film successively.The example of other that the preferred layer of shape memory polybutylene terephthalate (PBT) laminate film of the present invention constitutes is for having the formation of described polybutylene terephthalate (PBT) film, described paper sheet, stiffness films, sealing film successively.The example of other that the preferred layer of shape memory polybutylene terephthalate (PBT) laminate film of the present invention constitutes is for having the formation of described polybutylene terephthalate (PBT) film, stiffness films, sealing film successively.Also can on the face of the described sealing film side of the face of the described paper sheet side of described polybutylene terephthalate (PBT) film or described stiffness films, the light-proofness ink lay be set.
Shape memory polybutylene terephthalate (PBT) laminate film of the present invention is very useful as packaging material, and is particularly very useful as the packaging material that constitute the cap for container body.
The manufacture method of the first shape memory polybutylene terephthalate (PBT) laminate film of the present invention is, has (a) polybutylene terephthalate (PBT) film, (b) by from paper sheet, select in other resin film and the metal forming at least a make other film or the manufacture method of the shape memory polybutylene terephthalate (PBT) laminate film of thin-film laminate, it is characterized in that laminate film temperature T below the Tg at described polybutylene terephthalate (PBT) when keeping first shape that (1) is laminated film or thin-film laminate with described polybutylene terephthalate (PBT) film and other 1Under carry out figuration and handle, (2) with the figuration laminate film of gained in the temperature T that surpasses described Tg 2Following deformation processing is second shape, and (3) are then by being cooled to the temperature T below the described Tg 3And be fixed as described second shape.
Preferably described first be shaped as the crimping shape, described second is shaped as the shape or the inverse hemming shape of general planar.Preferably by with the roller conveyance with described polybutylene terephthalate (PBT) film and described other film or the bonding laminate film that obtains of thin-film laminate, thus along the periphery of described roller in described temperature T 1Under handle, make and to have given the laminate film of crimping shape.Preferably with described temperature T 2Under deformation processing carried out 30～60 seconds.Preferred described temperature T 1Be below 35 ℃, described temperature T 2Be (do not contain 45 ℃) more than 45 ℃～below 65 ℃, described temperature T 3It is 15～25 ℃.Described temperature T 1More preferably 15～25 ℃.Be preferably in the laminate film that to have given described crimping shape and be cooled to described temperature T 3After, reel to its inverse hemming direction.Be preferably in when described polybutylene terephthalate (PBT) film applied tension force more than the 4kgf/m width, described polybutylene terephthalate (PBT) film and described other film or thin-film laminate is bonding.Described tension force is 10～20kgf/m width more preferably.
The manufacture method of the second shape memory polybutylene terephthalate (PBT) laminate film of the present invention is, has (a) polybutylene terephthalate (PBT) film, (b) by from paper sheet, select in other resin film and the metal forming at least a make other film or the manufacture method of the shape memory polybutylene terephthalate (PBT) laminate film of thin-film laminate, it is characterized in that, (1) make the film of described polybutylene terephthalate (PBT) film and other or the laminate film of thin-film laminate in advance by (i), to its when keeping first shape in described temperature T 4Carry out down that figuration is handled or (ii) to described polybutylene terephthalate (PBT) film temperature T of (not containing Tg) more than the Tg at described polybutylene terephthalate (PBT)～(do not contain fusing point) below the fusing point when keeping first shape 4Under carry out after figuration handles, stacked with other film or thin-film laminate, make figuration laminate film with described first shape, (2) are cooled to temperature T below the described Tg by the figuration laminate film with gained 5And be fixed as described first shape, (3) (are not containing Tg)～described temperature T with described figuration laminate film then more than described Tg 4Below (do not contain T 4) temperature T 6After following deformation processing was second shape, (4) were by being cooled to the temperature T below the Tg 7And be fixed as described second shape.
Preferably described first be shaped as the crimping shape, described second is shaped as the shape or the inverse hemming shape of general planar.Best described temperature T 4Be 75～100 ℃, described temperature T 5Be below 40 ℃, described temperature T 6Be 45～65 ℃, described temperature T 7Be below 40 ℃.
When by described figuration polybutylene terephthalate (PBT) film and described other film or thin-film laminate bonding when making described figuration laminate film, be preferably in to make under described polybutylene terephthalate (PBT) film and the condition that a side's of a pair of warm-up mill periphery contacts and carry out conveyance, and along the periphery of described warm-up mill in described temperature T 4Under carry out heat treated, give the crimping shape to described polybutylene terephthalate (PBT) film thus, afterwards with the edge-rolling polybutylene terephthalate (PBT) film of gained and described other film or thin-film laminate by between described a pair of warm-up mill and bonding continuously.
When to described polybutylene terephthalate (PBT) film and described other film or thin-film laminate bonding and described polybutylene terephthalate (PBT) laminate film carry out figuration when handling, preferably with described polybutylene terephthalate (PBT) laminate film warm-up mill conveyance, along the periphery of described warm-up mill in described temperature T 4Under handle, give the crimping shape.
Be preferably in when described polybutylene terephthalate (PBT) film applied tension force more than the 4kgf/m width, described polybutylene terephthalate (PBT) film and described other film or thin-film laminate is bonding.Described tension force is 10～20kgf/m width more preferably.The laminate film of having given described crimping shape is being cooled to described temperature T 5After, preferably reel to its inverse hemming direction, and in described temperature T 6Under reach described temperature T 7Under handle.
The manufacture method that has possessed the container of shape memory polybutylene terephthalate (PBT) laminate film system lid of the present invention is, by the lid heat seal on container that will make by shape memory polybutylene terephthalate (PBT) laminate film, manufacturing has possessed the method for the container of described lid, it is characterized in that, in the temperature T of the Tg that surpasses described polybutylene terephthalate (PBT) 8Down, when described shape memory polybutylene terephthalate (PBT) laminate film maintenance is smooth, anneal, carry out heat seal when the shape memory polybutylene terephthalate (PBT) laminate film utilization lid material sealing mechanism of the general planar of gained is carried out stamping-out processing, make the lid and container adhesion made by described shape memory polybutylene terephthalate (PBT) laminate film thus.
Preferably described annealing was carried out 30～60 seconds.Described temperature T 8Be preferably 80～120 ℃.
The manufacture method of polybutylene terephthalate (PBT) film of the present invention is, the polybutylene terephthalate (PBT) resin is utilized the manufacture method of the polybutylene terephthalate (PBT) film of the expansion-molded method filming of air cooling, it is characterized in that, near first air ring ejection humidifying air of annular die is located in utilization, neck cooling with bubble, blow-up ratio is made as 1.5～2.8, the extrusion resin temperature is made as 210～250 ℃, extrusion resin pressure is made as 9.8～13.7MPa.
Preferably utilize the cooling air that slightly leans on second air ring of the position of top to spray from the frost line of being located at than described bubble (frostline), described bubble is further cooled off, and the temperature on every side that will be located at the net cylindraceous between described first air ring and described second air ring is cooled to certain value, makes the chilling temperature stabilisation of the bubble that utilizes described first air ring and the acquisition of described second air ring.
Preferably by blowing afloat along the outside of described cylindric net from the humidifying air of the cooling air blowing out device ejection of the bottom of being located at described net, carry out described net around cooling.In addition, preferably utilize and be located at the 3rd air ring that slightly leans on the position of top than described second air ring, described bubble is further cooled off.In addition, the cooling air as described second air ring and described the 3rd air ring preferably uses humidifying air.Preferably the temperature with described humidifying air is made as 15～25 ℃.
The feature of the tearability polybutylene terephthalate (PBT) film of straight line of the present invention is, on at least one side's of polybutylene terephthalate (PBT) film face, be formed with many parallel in fact wire traces, can begin along described wire trace in fact along smooth tearing from position arbitrarily thus.
The degree of depth of described wire trace is preferably 1～40% of film thickness.The degree of depth of best described wire trace is 0.1～10 μ m, and the width of described wire trace is 0.1～10 μ m, is spaced apart 10～200 μ m between the described wire trace.
The tearability polybutylene terephthalate (PBT) film of described straight line also can adopt any one form in single thin film or the laminate film.When adopting laminate film, the layer that preferably has at least 1 layer of making, makes by the heat seal film by film with described wire trace.Also can evaporation pottery or metal on the tearability polybutylene terephthalate (PBT) film of straight line of the present invention, can improve gas-barrier property thus.Packaging material of being made by straight line tearability polybutylene terephthalate (PBT) film of the present invention and packaging bag are applicable to the purposes that needs tearability.
The feature of porous polybutylene terephthalate (PBT) film of the present invention is, is formed uniformly a plurality of fine through holes and/or through hole not, has tearability and warping property thus.
Best described minute aperture has the average pore size of 0.5～100 μ m, and its density is at about 500/cm 2More than.The packaging material of being made by porous polybutylene terephthalate (PBT) film of the present invention are applicable to the purposes that needs warping property.
Description of drawings
Fig. 1 is the sectional view of the layer configuration example of expression shape memory polybutylene terephthalate (PBT) (PBT) laminate film.
Fig. 2 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.
Fig. 3 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.
Fig. 4 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.
Fig. 5 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.
Fig. 6 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.
Fig. 7 is the schematic diagram of an example of the expression device of making shape memory PBT laminate film.
Fig. 8 is other the schematic diagram of example of the expression device of making shape memory PBT laminate film.
Fig. 9 is other the schematic diagram of example of the expression device of making shape memory PBT laminate film.
Figure 10 is other the schematic diagram of example of the expression device of making shape memory PBT laminate film.
Figure 11 is other the schematic diagram of example of the expression device of making shape memory PBT laminate film.
Figure 12 is the schematic diagram of an example of the expression device of making the container that has a lid of the present invention.
Figure 13 is the stereogram of the container for fast food in the lid Kaifeng that will be made by shape memory PBT laminate film of the present invention in order to inject hot water of expression.
Figure 14 is that expression will be blocked the stereogram of the container for fast food in Kaifeng by the cap portion that shape memory PBT laminate film of the present invention is made in order to inject hot water.
Figure 15 is that expression is with the stereogram that has the container of lid as the example of semi-solid containers for food use use of the present invention.
Figure 16 is the stereogram of representing the state behind the container Kaifeng that has lid of Figure 15.
Figure 17 is expression food recovers the state of shape with employed shape memory PBT laminate film in the pallet a schematic diagram.
Figure 18 is the schematic diagram of operation that expression utilizes the method for expansion-molded manufactured PBT film.
Figure 19 is the diagrammatic side view that expression will be steeped an example of the device that cools off.
Figure 20 (a) is the vertical view of an example of expression cowling panel.
Figure 20 (b) is the vertical view of another example of expression cowling panel.
Figure 20 (c) is the vertical view of another example of expression cowling panel.
Figure 21 is the schematic diagram that the system of humidifying air is supplied with in expression.
Figure 22 is the schematic diagram of example that expression utilizes the operation of uniaxial extension manufactured PBT film.
Figure 23 is other the schematic diagram of example of the expression operation of utilizing uniaxial extension manufactured PBT film.
Figure 24 is other the schematic diagram of example of the expression operation of utilizing uniaxial extension manufactured PBT film.
Figure 25 is the schematic diagram that is illustrated in an example of the device that forms the wire trace on the direct of travel of film.
Figure 26 is illustrated in the device shown in Figure 25, send the partial enlarged drawing of compressed-air actuated state to the top blast of film and pattern (パ one Application) roller sliding-contact.
Figure 27 is illustrated in the device shown in Figure 25, the partial cross section view of the state of film and pattern roller sliding-contact.
Figure 28 (a) is the front view and the right view of an example of expression nozzle.
Figure 28 (b) is other the front view and the right view of example of expression nozzle.
Figure 28 (c) is that the expression use has the schematic diagram of the nozzle of cover to the state of pattern roller compressed-air blows.
Figure 29 is other the diagrammatic side view of example that is illustrated in the device that forms the wire trace on the direct of travel of film.
Figure 30 is the stereogram of expression formation with respect to an example of the device of the wire trace of the direct of travel inclination certain angle of film.
Figure 31 (a) is illustrated in the device shown in Figure 30, the local amplification plan view of the state of film and the sliding-contact of pattern endless belt.
Figure 31 (b) is the schematic section of seeing from the D direction in Figure 31 (a).
Figure 32 is that expression forms other the schematic diagram of example with respect to the device of the wire trace of the direct of travel inclination certain angle of film.
Figure 33 is illustrated in the device shown in Figure 32, the local amplification plan view of the state of film and roller formation (train) sliding-contact.
Figure 34 (a) is that expression forms other the local amplification plan view of example with respect to the device of the wire trace of the direct of travel inclination certain angle of film.
Figure 34 (b) is the schematic diagram of seeing from the E direction in Figure 34 (a).
Figure 35 is the local amplification plan view of expression with respect to an example of the device of the wire trace of the direct of travel formation width of film.
Figure 36 is other the local amplification plan view of example of the device of the expression wire trace that forms width with respect to the direct of travel of film.
Figure 37 is other the local amplification plan view of example of the device of the expression wire trace that forms width with respect to the direct of travel of film.
Figure 38 (a) is other the local amplification plan view of example of the device of the expression wire trace that forms width with respect to the direct of travel of film.
Figure 38 (b) is the schematic diagram of seeing from the F direction in Figure 38 (a).
The specific embodiment
[1] layer of shape memory polybutylene terephthalate (PBT) laminate film constitutes
Shape memory polybutylene terephthalate (PBT) of the present invention (PBT) laminate film have (a) PBT thin layer, (b) by from paper sheet, other resin film and metal forming at least a (being designated hereinafter simply as " other film or thin-film laminate ") selected.
(1) polybutylene terephthalate (PBT) film
The PBT film is basically by 1, the saturated polyester film that 4-butanediol and terephthalic acid (TPA) are made.But in the scope of not damaging rerum natura such as heat-resisting shrinkage, also can be with 1, diol component beyond the 4-butanediol or the carboxylic acid composition beyond the terephthalic acid (TPA) are contained as copolymer composition.As this kind diol component, for example can enumerate ethylene glycol, diethylene glycol (DEG), neopentyl glycol, 1,4-cyclohexane methanol etc.In addition, as the dicarboxylic acids composition, for example can enumerate M-phthalic acid, decanedioic acid, adipic acid, azelaic acid, butanedioic acid etc.As the concrete example of the PBT resin that constitutes the PBT film, for example can enumerate the homogeneous PBT resin of selling with trade name " ト レ コ Application " by east beautiful (Co., Ltd.).
The PBT resin is not limited to situation about only being made of PBT, also can be in the scope that does not hinder effect of the present invention contains other thermoplastic resin according to purpose.As other resin, can enumerate PETG (PET), PEN polyester such as (PEN); Polyphenylene sulfide (PPS); Polyamide (PA); Pi (PI); Polyamidoimide (PAI); Polyether sulfone (PES); Polyether-ether-ketone (PEEK); Merlon; Polyurethane; Fluorine resin; Polyethylene; Polyolefin such as polypropylene; Polyvinyl chloride; Elastomer etc.When containing other resin, if its ratio is counted 100 quality % with PBT resin integral body, then preferred 5～20 quality %, more preferably 5～15 quality %, preferred especially 5～10 quality %.So if be not particularly limited, employed in this manual term " PBT resin " should be understood to comprise other these two kinds of implications of composition of resin of PBT and PBT+.
The PBT film also can suitably contain colouring agents such as stabilizing agents such as plasticizer, antioxidant or ultra-violet absorber, antistatic agent, surfactant, dyestuff or pigment, the lubricant that is used to improve liquidity, crystallization promoter (nucleus), inorganic filling material etc. according to the purposes of shape memory PBT laminate film.
Though the thickness for the PBT film is not particularly limited, in practicality, preferably be made as about 5～50 μ m.Very difficult technically as if the thickness of PBT film being made as less than about 5 μ m, cost can uprise.In addition, when the thickness that makes the PBT film surpassed about 50 μ m, because the film price raises, so the purposes of the shape memory PBT laminate film of gained will be restricted.
Manufacture method for the PBT film is not particularly limited, and can utilize any one manufacturing in expansion-molded method or the casting.Preferably utilize in expansion-molded method described later or the casting any one to make.
(2) other film or thin-film laminate
(a) paper sheet
When shape memory PBT laminate film is used for the lid of container for fast food, preferably gives layer and also have the layer that constitutes by paper sheet as stationary state.The kind of the paper of paper sheet is unqualified, also comprises synthetic fibre paper.The thickness of paper sheet preferably is made as about 60～110g/m 2More preferably be made as about 75～90g/m 2When the thickness of paper sheet less than about 60g/m 2The time, the hardness of paper sheet is low excessively, can't give enough stationary states.On the other hand, even make the thickness of paper sheet surpass about 110g/m 2, also only can cause cost to uprise, can't obtain the raising of stationary state.
(b) sealing film
When shape memory PBT laminate film is used for the lid of container for fast food, be provided with thermosealed sealing film in the upper end flange portion of container body.Sealing film can be made by polyethylene film, no extended polypropylene film, ionomer resin film, polystyrene film etc.In addition, peel off from container body easily in order to make lid, sealing film preferably has easy fissility.For this reason, sealing film preferably has more weak thermal bonding.In addition, as the heat seal material, also can use known PUR (hot melt).
As sealing film, for example can use the laminate film of low molecular weight polyethylene film of upper end flange portion side of polyethylene substrate film, the container body of paper sheet side.The thickness of this polyethylene substrate film is 10～40 μ m preferably approximately, more preferably about 20～30 μ m.In addition, the thickness of low molecular weight polyethylene film is 5～20 μ m preferably approximately, more preferably about 7～15 μ m.The stacked polyethylene film of this kind for example is used as 760FD (eastern beautiful built up membrane (strain) system) and sells.In addition, as sealing film, also can use the film that constitutes by ethylene-vinyl acetate copolymer (EVA) and poly mixture.In the film that constitutes by this mixture, as the preferred wire low density polyethylene (LDPE) of polyethylene (LLDPE).The thickness of the film that is made of this mixture is 10～40 μ m preferably approximately also, more preferably about 20～30 μ m.In addition, preferred 10～50 μ m of the thickness of hot melt adhesive layer, more preferably 20～40 μ m.
As sealing film, also can use special material of being willing to announcement in 2002-183197 number in addition.Special be willing to that the sealing film of being announced in 2002-183197 number is the alpha-olefin copolymer of ethene and carbon number 3～18 to be obtained and density (JIS K6922) is 0.870～0.910g/cm by comprising 3, MFR (JIS K6921,190 ℃, 2.16kg load) is the material that the resin combination of 1～100g/10 minute straight chain shape ethylene and polystyrene constitutes.Like this, even the sealing surface of container body is polyethylene or polystyrene any one, also can be by lid heat seal of the present invention being formed the multi-layer sealed layer that can have sealing and easily openable simultaneously.
(c) stiffness films
In order to improve the rigidity of shape memory PBT laminate film, stiffness films can be set.Can enumerate PET film, biaxial stretched polypropylene film (OPP film), nylon film etc. as stiffness films.As the PET film, when using the PET film of the different biaxial orientation of the uniaxial orientation or the degree of orientation, needing under the situation of tearability at shape memory PBT laminate film is favourable.As the PET film of the different biaxial orientation of uniaxial orientation or the degree of orientation, for example can enumerate " エ Application Block レ Starト PC " (ユ ニ チ カ (strain)).
(b) light-proofness ink lay
When shape memory PBT laminate film need possess light-proofness, light-proofness ink lay or metal foil layer are set.Light-proofness printing ink just is not particularly limited so long as comprise black or the dark-coloured pigment or the printing ink of dyestuff of carbon black and so on for example.When using the light-proofness ink lay, just can avoid the harmful effect when burning disposal to environment, and under the situation of the lid that shape memory PBT laminate film is used for container for fast food, can after sealing, utilize the detection of the metal species foreign matter of metal detector.Like this, not only can improve the security of instant food greatly, and, therefore can reduce the inspection cost significantly owing to can utilize metal detector.When the shape memory PBT laminate film that will have metal foil layer is used for the lid of container for fast food, as the preferred aluminium foil of metal forming.By using aluminium foil layer, except good light-proofness, can also obtain gas-barrier property, fragrance protectiveness etc.
Though the thickness of light-proofness ink lay depends on the black pigment in the printing ink or the concentration of dyestuff, in general so long as the degree that ultraviolet ray and luminous ray can be blocked fully get final product.In addition, preferred 3～15 μ m of the thickness of aluminium foil, more preferably 7～12 μ m.
(3) layer configuration example
The example that layer when Fig. 1～Fig. 4 has enumerated shape memory PBT laminate film used with packaging material as the lid of container for fast food constitutes.Laminate film 1 expression shown in Figure 1 constitutes as the layer that basic comprising has PBT thin layer 2, paper sheet 3, sealing film 4.Between PBT thin layer 2 and paper sheet 3, have by bond layer 6 and the adhesive linkage (I) that the polyethylene layer (I) 5 that is extruded lamination constitutes, the adhesive linkage (II) that is made of bond layer 6 ' and the polyethylene layer (II) 5 ' that is extruded lamination is arranged between paper sheet 3 and sealing film 4.Under the situation of layer configuration example shown in Figure 1, by PBT film 2 and adhesive linkage (I) (5 and 6) constitute outside layer, the bed thickness of the la m that is made of adhesive linkage (II) (5 ' and 6 ') and sealing film 4 is than preferred outside layer/la m=100/35～100/100.The edge-rolling of PBT film 2 and stationary state are played a role effectively.Here so-called " outside " and " inboard " be meant, the outside and inboard with respect to container with shape memory PBT laminate film during as the lid use of container for fast food etc.
Fig. 2 represents to be provided with between paper sheet 3 and sealing film 4 for the rigidity that improves shape memory PBT laminate film the example of stiffness films 7.And, in Fig. 2,5 " expression is extruded the polyethylene layer (III) of lamination, 6 " expression bond layer (III).
Fig. 3 represents to be provided with on the medial surface of PETG layer 7 in order to give good light-proofness the example of light-proofness ink lay 8.Light-proofness ink lay 8 preferably is printed on PETG (PET) film in advance.In addition, light-proofness ink lay 8 can be arranged on the inboard of PBT thin layer 2, or be arranged on a side's of paper sheet 3 the face (for example inboard of paper sheet 3).Has metal foil layer 9 as the layer of giving light-proofness in the laminate film shown in Figure 4.
The example that layer when Fig. 5 and Fig. 6 have enumerated shape memory PBT laminate film used with packaging material as the lid of the container that places semi-solid food such as jelly, pudding constitutes.Laminate film shown in Figure 5 has PBT thin layer 2, stiffness films 7, sealing film 4 as basic comprising.Bond layer (for example hot melt adhesive layer) 6 is arranged between PBT thin layer 2 and stiffness films 7, bond layer (for example hot melt adhesive layer) 6 ' is arranged between paper sheet 3 and sealing film 4.Fig. 6 represents to be provided with on the medial surface of stiffness films 7 in order to give good light-proofness the example of light-proofness ink lay 8.
Employed lid owing to require unlike the lid that is used for container for fast food possesses the resealability that injects behind the hot water in the container that places semi-solid food, therefore scarcely has stronger paper sheet of stationary state or aluminium foil.But, when only that 2 layers of PBT film and polyethylene films is bonding and when constituting laminate film, even the PBT film wants to recover first shape because distortion is easy to be absorbed by polyethylene film, therefore will have shape recover inadequate may.Thus, when manufacturing has the shape memory PBT laminate film of PBT thin layer and polyethylene layer, be preferably in described stiffness films is set between PBT thin layer and the film layer.
[2] manufacture method of shape memory polybutylene terephthalate (PBT) laminate film
Manufacture method to shape memory PBT laminate film is elaborated below with reference to accompanying drawings.
(1) first manufacture method
First manufacture method of shape memory PBT laminate film comprises: (a) laminate film temperature T below the Tg at described PBT when keeping first shape that film or thin-film laminate with described PBT film and other are laminated 1Under carry out figuration and handle (cold working), (b) with the figuration laminate film of gained in the temperature T that surpasses described glass transition temperature Tg 2Following deformation processing is second shape, (c) by being cooled to the temperature T below the glass transition temperature 3Fixing is the operation of second shape.
Below, so that first shape is made as the crimping shape, the situation that second shape is made as even shape is that example describes.Fig. 7 is the diagrammatic side view of an example of the expression device of making shape memory PBT laminate film.Through guiding rollers 100, utilize gravure roll 101,101 coating adhesive (for example PUR) 6 on a side face from the PBT film 2 that is wound with the raw-material spool of PBT film (リ one Le) 20 uncoilings, in drying oven 102 with the bond layer drying., through excess pressure adjust roller 103,, will overlap on the bond layer from other film or thin-film laminate 13 of spool 12 uncoilings across the molten polyethylene of from mould 104, extruding 5 thereafter, simultaneously, by (extruding lamination) between chill roll 105 and the rubber rollers 105 '.Temperature T when the laminate film of gained is used 106 conveyances of cold working roller below the Tg of PBT 1Under carry out figuration and handle.So just can give edge-rolling to the PBT thin layer of laminate film.Utilize heater 108 in the temperature T that surpasses Tg the laminate film (edge-rolling laminate film) 10 of having given the crimping shape 2Annealing hastily simultaneously, is flat condition with deformation processing between two niprolls 107,107, then by making it to contact the temperature T that is cooled to below the described Tg with chill roll 109 down 3So just can be fixed as smooth shape.Edge-rolling laminate film to its inverse hemming direction with spool reeled, form coiled film 11 (shape memory PBT laminate film 1) thereafter.In this specification, so-called edge-rolling is meant, be different from the stationary state that to keep this state when shape memory PBT laminate film 1 curved, by shape memory PBT laminate film 1 is exposed to more than the temperature of having given the crimping shape, and can be from having given the character that second shape (smooth shape, inverse hemming shape) that is obtained after the crimping shape returns to crimping shape (can make 1 perk of shape memory PBT laminate film).
The cold working temperature T 1Must be made as below the Tg of PBT, preferred below 35 ℃, more preferably 15～25 ℃.The temperature T of the edge-rolling laminate film 10 after the cooling annealing 3Must be below described Tg, preferred 15～25 ℃.The PBT film generally has about 20～45 ℃ Tg.Tg can utilize JISK7121 to measure.
In the temperature T that surpasses Tg 2Down, be the annealing in process of flat condition with edge-rolling laminate film deformation processing, need proceed to the degree that the edge-rolling that utilizes cold working to give is disappeared.Thus, temperature T 2Preferably (do not contain 45 ℃) below 45 ℃～below 65 ℃, after being heated to this temperature range hastily, carry out deformation processing, annealed 30～60 seconds.Tension force that apply is made as 5～10kgf/m width in order to keep smooth between two niprolls 107,107 '.In addition, in temperature T 2Under annealing in process after, preferably be chilled to temperature T 3Among Fig. 7,, also can only heater 108 be set in the PBT of edge-rolling laminate film 10 thin layer side though utilize heater 108,108 to heat from the two sides of edge-rolling laminate film 10.Also can use nozzle to blow the hot-air that adds that from heater 108, comes out to the PBT of edge-rolling laminate film 10 thin layer.
In the example shown in Figure 7, edge-rolling laminate film 10 is being cooled to temperature T 3After, to its inverse hemming direction (with other film or the thin-film laminate layer as the inboard) reel, but utilize the edge-rolling of cold working acquisition to disappear in order not make, and in order to do one's utmost to suppress the recovery of crimping shape, the temperature of coiling temperature and keeping under the state behind the coiling is preferably T 1Near temperature.Like this, shape memory PBT laminate film 1 can be remained smooth state, the edge-rolling laminate film 10 during therefore with coiled film 11 (shape memory PBT laminate film 1) uncoiling is smooth basically.
When shape memory PBT laminate film is used for the lid of container for fast food or semi-solid containers for food use, other film or the thin-film laminate that is layered on the PBT film can be made in advance, constitutes so that shape memory PBT laminate film becomes as described the layer shown in [1] (3).Though other film or thin-film laminate 13 also can utilize in extruding layer platen press or the dry lamination method any one to form, and preferably utilize the extruding layer platen press to form.
For the method that laminate film is reeled, preferably as shown in Figure 7, make involving in direction and rolling out direction angulation θ of laminate film on cold working roller 106 1In 45～60 ° scope.So just can give enough edge-rollings to PBT film 2.If angle θ 1 will be made as required value, as long as the position relation of cold working roller 106 and pressure adjustment roller 103 ' is suitably adjusted.Preferred 20～the 80cm of the diameter of cold working roller 106.So just can give enough edge-rollings to PBT film 2.Usually the peripheral speed of cold working roller 106 was made as 30～100m/ minute.
PBT film 2 and other film or thin-film laminate 13 passed between chill roll 105, the rubber rollers 105 ' and when bonding, utilizing pressure to adjust roller 103, apply usually to PBT film 2 and under the condition of the tension force more than the 4kgf/m width, carry out.Particularly by apply the tension force of 10～20kgf/m width to PBT film 2, when PBT film 2 is extended in the longitudinal direction with ductility that can elastic telescopic and other film or thin-film laminate 13 bonding.Like this, just can be bonding with other film or thin-film laminate 13 under the elongation state that makes PBT film 2 maintenance elastic restoring forces.What is called has kept the elongation state of elastic restoring force to be meant when the power of the fixedly extension of PBT film 2 is removed, and keeps making the state of PBT film 2 to the power of original shape contraction.Thus, the edge-rolling of shape memory PBT laminate film 1 is further improved.So-called ductility that can elastic telescopic generally is meant and extends about 1～3% ductility with the degree that does not produce apparent fold because of extension on the PBT film.
In the example shown in Figure 7, though bonding other film or thin-film laminate 13 on the single face of PBT film 2 only also can be given edge-rolling behind bonding other film or thin-film laminate 13 on the two sides of PBT film 2.
Fig. 8 is other the diagrammatic side view of example of the expression device of making shape memory PBT laminate film.And, used identical reference marks for member identical or part with embodiment shown in Figure 7.In this example, except PBT film 2 and other film or thin-film laminate 13 are utilized the dry lamination method bonding, other is identical with example shown in Figure 7.The PBT film 2 that is provided with bond layer is adjusted roller 103 through excess pressure, with other film or thin-film laminate 13 overlap on the bond layer in by between a pair of warm-up mill 110,110.But when needing stronger adhesive strength, preferably utilize extruding layer platen press shown in Figure 7 that PBT film 2 and other film 2 or thin-film laminate 13 is bonding.
Below, first shape as shape memory PBT laminate film is adopted the pallet shape, adopt the example of the situation of smooth shape to describe as second shape.Fig. 9 represents to make an example of the device of this kind shape memory PBT laminate film.And, used identical reference marks for member identical or part with embodiment shown in Figure 7.At first, utilize extruding layer platen press or dry lamination method bonding the film of PBT film and other or thin-film laminate, be formed on the single or double of PBT film and have other the film or the laminate film of thin-film laminate.The laminate film 14 usefulness pressure of gained are adjusted roller 103,103 send, when the extrusion die 111 of pallet shape is given in pushing, in described temperature T 1Under carry out cold working, give shape according to the profile of extrusion die 111 discontinuously.The figuration laminate film 15 of gained is used between the roller 112,112, in described temperature T by a pair of annealing 2Following annealing and general planarization utilizes cooling device 113,113 to be cooled to described temperature T then 3With the general planar change the coating of deformation layer laminate film 15 and uncoiling from spool 16 with film 17 stackedization in, use with the identical shaped take up roll 114 of extrusion die 111 and reel, form coiled film.Like this, just can form the laminate film that will be corresponding to potentialization of distortion of the profile of extrusion die 111 have distortion on apparent.In the temperature T of in PBT film 2 pushing extrusion dies 111, carrying out 1Under cold working carry out getting final product in 10～60 seconds.And, in the example shown in Figure 9,, also can suitably use extrusion die with the required form that needs memory though use hypocraterimorphous extrusion die 111.
(2) second manufacture methods
Second manufacture method of shape memory PBT laminate film comprises: (a) make the film of described PBT film and other or the laminate film of thin-film laminate in advance by (i), when keeping first shape to its temperature T that (is not containing Tg) more than Tg～(do not containing fusing point) below the fusing point 4Carry out down that figuration is handled or (ii) to described PBT film when keeping first shape in described temperature T 4Under carry out after figuration handles, stacked with other film or thin-film laminate, make laminate film with first shape, (b) be cooled to temperature T below the Tg by figuration laminate film with gained 5And be fixed as first shape, (c) then described figuration laminate film (is not being contained Tg)～temperature T more than Tg 4Below (do not contain T 4) temperature T 6After following deformation processing is second shape, (d) by being cooled to the temperature T below the Tg 7And be fixed as the operation of described second shape.
The Tg of PBT resin is 22～45 ℃, near room temperature, is heated to that Tg is above, to be cooled to the operation that is lower than Tg very easy.And because the fusing point height is approximately 230 ℃, therefore the temperature range from Tg to the fusing point is very wide, can increase temperature T 4And temperature T 5Poor.Thus, just can easily carry out the operation of described (A)～(D).
Below, to adopt the crimping shape as first shape, adopting the situation of smooth shape as second shape is that example describes.
Figure 10 is that expression utilizes second manufacture method to make an example of the device of shape memory PBT laminate film.In this example, giving bonding other film or thin-film laminate on the figuration PBT film of edge-rolling in advance.Until coating adhesive 6 on the one side of PBT film 2 and in drying oven 102 operation with the bond layer drying identical with example shown in Figure 7.As shown in figure 10, with drying the PBT film 2 usefulness pressure behind the bond layer adjust roller 103 and send, with the face that do not have adhesive linkage as contact-making surface, warm-up mill 115 conveyances of using with figuration, simultaneously, by in described temperature T 4Under handle, give edge-rolling.Thereafter, with other film or thin-film laminate 13 with the adhesive linkage of PBT film 2 overlapping in, between the roller 115 ' that passes warm-up mill 115 and contact with it, that both are bonding.Contact with chill roll 109 by the edge-rolling laminate film 10 that makes gained, be cooled to the following temperature T of described Tg 5, then, utilize spool to reel to the inverse hemming direction, form coiled film 11.The coiled film 11 of gained (is not contained Tg)～temperature T more than described Tg 4Below (do not contain T 4) temperature T 6Under carry out heat treated, then by being cooled to the temperature T below the described Tg 7, obtain shape memory PBT laminate film 1.After having formed coiled film 11, in temperature T 6Under carry out heat treated, be cooled to temperature T then 7And, be formed on the apparent laminate film of going up general planar with potentialization of crimping shape of described laminate film.In the mechanism of coiled film 11 being heated or cooling off, do not limit, for example can enumerate coiled film 11 is put into groove, to around the groove with the heater heating or with the method for cooling device cooling.
The heating-up temperature T of warm-up mill 115 4Be necessary for the temperature of above (not containing the Tg)～PBT fusing point of Tg following (not containing fusing point) of PBT, preferred 75～100 ℃, more preferably 90～100 ℃.The chilling temperature T of chill roll 109 5Be necessary for the following temperature of described Tg, preferred below 40 ℃.Also can not use chill roll 109 in the cooling of edge-rolling laminate film 10, and use the cooling air.The heating-up temperature T of coiled film 11 6Be necessary for above (not containing the Tg)～temperature T of described Tg 4Below (do not contain T 4), preferred 45～65 ℃, more preferably 45～50 ℃.In addition, temperature T 6Under heat treated preferably carry out about 24 hours.Coiled film 11 has been carried out the chilling temperature T after the heat treated 7Be necessary for below the described Tg, preferred below 40 ℃.In the example shown in Figure 10,, reel, so just can make thin film planarization effectively to the inverse hemming direction (film or thin-film laminate layer with other are the inboard) of edge-rolling laminate film in order to form the shape of general planar as second shape.
For with regard to the encirclement method of warm-up mill 115, preferably make involving in direction and rolling out direction angulation θ of PBT film 112 shown in Figure 10 with regard to PBT film 2 2Be in 45～60 ° scope.So just can give enough edge-rollings to PBT film 2.If will be with angle θ 2Be made as required value, as long as the position relation of warm-up mill 115 and pressure adjustment roller 103,103 is suitably adjusted.Preferred 60～the 80cm of the diameter of warm-up mill 115.So just can give enough edge-rollings to PBT film 2.Usually the peripheral speed of warm-up mill 115 was made as 30～100m/ minute.
As described in (1) to the explanation of first manufacture method, with PBT film 2 and other film or thin-film laminate 13 and when bonding, apply under the condition that is generally the tension force more than the 4kgf/m width and carry out utilizing a pair of pressure to adjust 103,103 pairs of PBT films 2 of roller by making it to pass between warm-up mill 115 and the touch roll 115 '.Identical with first manufacture method, preferably PBT film 2 is applied the tension force of 10～20kfg/m width.
Figure 11 represents to utilize second manufacture method to make other example of the device of shape memory PBT laminate film.And, used identical reference marks for member identical or part with embodiment shown in Figure 7.In this example, after making contains the laminate film of PBT film in advance, give edge-rolling to this PBT thin layer.Operation till PBT film 2 and other film or thin-film laminate 13 being utilized a pair of warm-up mill 110,110 bonding is identical with example shown in Figure 8.When the laminate film of gained is used warm-up mill 115 conveyances, the temperature T that (is not containing Tg) more than the Tg of PBT～(do not containing fusing point) below the PBT fusing point 4Following figuration.So just can give edge-rolling to the PBT thin layer of laminate film.Contact with chill roll 109 by the edge-rolling laminate film 10 that makes gained, be cooled to the following temperature T of described Tg 5, utilize spool to reel then to the inverse hemming direction, form coiled film 11.Coiled film 11 to gained (does not contain Tg)～temperature T as described above more than described Tg 4Below (do not contain T 4) temperature T 6Under carry out heat treated, then by being cooled to the temperature T below the described Tg 7, obtain shape memory PBT laminate film 1.
In the embodiment shown in fig. 11, about temperature T 4～T 7Requirement identical with embodiment shown in Figure 10.The involving in direction and roll out direction angulation θ of laminate film 10 3Preferably be in 45～60 ° scope.In the example shown in Figure 11, though bonding other film or thin-film laminate 13 on the single face of PBT film 2 only behind also can be on PBT film 2 two-sided bonding other the film or thin-film laminate 13, given shape memory.
Utilize second manufacture method, also can make as first formation and adopt the pallet shape, adopted the shape memory PBT laminate film of smooth shape as second shape.The manufacturing installation of this moment can be identical with device shown in Figure 9, therefore utilizes Fig. 9 to describe.At first, the film or the thin-film laminate of PBT film and other is bonding, be produced on the single or double of PBT film and have other the film or the PBT laminate film of thin-film laminate.The laminate film 14 of gained is adjusted roller 103,103 through a pair of pressure, when the extrusion die 111 of pallet shape is given in ejection, and the temperature T that (is not containing Tg) more than the Tg of PBT～(do not containing fusing point) below the PBT fusing point 4Under carry out heat treated, give shape according to the profile of extrusion die 111 discontinuously.The figuration laminate film 15 of gained is contacted with hypocrateriform extrusion die or cooling air with the cooling of the back segment of being located at extrusion die 111, be cooled to the following temperature T of described Tg 5, by passing between a pair of warm-up mill 112,112, more than described Tg, (do not contain Tg)～temperature T then 4Below (do not contain T 4) temperature T 6Under carry out heat treated, the temperature T by utilizing cooling device 113,113 to be cooled to below the described Tg then 7, make it planarization.The temperature T of when pressing against extrusion die 111 on the laminate film 14, carrying out 4Under heat treated carry out getting final product in 10～60 seconds.
[3] shape memory polybutylene terephthalate (PBT) laminate film
The shape memory PBT laminate film that utilizes described first method acquisition is at T 1Utilize the shape recovery capability can revert to first shape in fact under the above temperature.Even the PBT film also can be at T be fixed to second shape in described annealing and refrigerating work procedure after 1Also do not determine though recover the reason of first shape under the above temperature, can think, for example in temperature T 1Under cold working in maintain distortion in the winding of macromolecular chain, the major part of this distortion is in temperature T 2Under the annealing of short time in can be by lax, therefore at T 1Will recover first shape under the above temperature.
The shape memory PBT laminate film that utilizes described second method acquisition is at T 4Utilize the shape recovery capability can revert to first shape in fact under the above temperature.Even the PBT film also can be at T be fixed to second shape in described heating deformation processing and refrigerating work procedure after 4Also do not determine though recover the reason of first shape under the above temperature, can think, for example in temperature T 4More than, owing to be the rubber-like zone, therefore be easy to be carried out the heating figuration and handle, and in temperature T 5Owing to be glassy zone, therefore distortion is fixed, though utilize temperature T down 6Under the heating deformation processing can be with temperature T 4Under the part of distortion lax and become second shape, but since the orientation of most strand do not change, therefore at T 4Will recover first shape under the above temperature.
Shape memory PBT laminate film with shape recovery capability of recovering first shape is very useful as various packaging material.Particularly utilize described [2] though in narration the method manufacturing memory the shape memory PBT laminate film of crimping shape owing to do not use metal such as aluminium foil, also can make lid crimping fully, therefore be suitable for the packaging material that use in the lid as container for fast food.When easily manufactured containers for food use, utilize and cover the material sealing device and shape memory PBT laminate film is carried out stamping-out process, with the lid of gained immediately heat seal on container.When heat seal, the seal head of the sealing tegmentum material sealing device of lid is heated to 120～160 ℃ usually, but this moment owing on the part beyond the sealing of lid, also applied heat, so lid is at T 1Or T 4Processed under the above temperature conditions.Thus, lid just recovers the crimping shape, though on being sealed in container during in keep smooth, will show the crimping shape by peeling off from container.Particularly as mentioned above when under the elongation state of the elastic restoring force that has kept the PBT film with paper sheet when bonding, edge-rolling can be further improved.
[4] possessed the manufacture method of the container of shape memory polybutylene terephthalate (PBT) laminate film system lid
Below the manufacture method of the container that possessed shape memory PBT laminate film system lid is narrated.Utilize shape memory PBT laminate film 1 that the method for record in described [2] obtains since in its manufacturing process from the apparent general planar that is made into, and then be used as coiled film 11 keepings, therefore when it is rolled out on apparent general planar.But, the storage time lower at shape recovery temperature grown, is exposed under the inferior situation of room temperature in the megathermal period in summer, slowly recover the crimping shape in the time of will occurring in keeping, or because of the coiling in when keeping, the situation of problem such as warpage appears in an opposite side with the crimping shape that forms by shape memory.
The container that has possessed shape memory PBT laminate film system lid can be by after carrying out stamping-out processing to the shape memory PBT laminate film of having remembered the crimping shape, its heat seal is made on container, if but not be general planar when shape memory PBT laminate film rolled out, just can't heat seal on container, even or can seal its lid also can be crooked and become defective work.Thus when manufacturing has the container of lid, make that uneven shape memory PBT laminate film made general planar before heat seal when rolling out.
Figure 12 is the diagrammatic side view of an example of the expression device of making the container possessed shape memory PBT laminate film system lid.To use heater 117,117 from the shape memory PBT laminate film 1 that coiled film 11 rolls out, in the temperature T of the Tg that surpasses PBT 8Between two niprolls 116,116 ', keep annealing in smooth, from the apparent general planar that makes it down.To become smooth basically the shape memory PBT laminate film 1 lid material sealing device 120 that utilizes seal head 121 to move up and down carry out stamping-out processing, heat seal is on container 140 immediately.And can in container, be blown into inert gas as required.
Wherein, temperature T 8Under annealing so that the degree that the edge-rolling that shape memory PBT laminate film is remembered does not disappear carry out.Thus, temperature T 8Preferred 80～120 ℃, more preferably 90～100 ℃.Shape memory PBT laminate film is heated to temperature T hastily 8, annealed under the smooth condition 30～60 seconds remaining.In order to keep smooth between two niprolls 116,116 ', the tension force that is applied is made as 5～10kgf/m width.Usually the gait of march of shape memory PBT laminate film 1 was made as 30～100m/ minute.Among Figure 12, though utilize heater 117,117 to heat from the two sides of shape memory PBT laminate film 1, when shape memory PBT laminate film 1 only when single face has the PBT thin layer, also can only heater 117 be set in this PBT thin layer side.Also can use nozzle to blow the hot-air that adds that from heater 117, comes out to the PBT thin layer of shape memory PBT laminate film 1.
The stamping-out processing and the heat seal on container 140 of lid carry out off and on, therefore keep certain force of strain for fear of shape memory PBT laminate film 1 guiding bending between roller 119 and the touch roll 122, preferably as shown in figure 12, preventing of being provided with that easy on and off moves is crooked with roller 118.And in Figure 12,18 expressions are by the coiled film that the shape memory PBT laminate film 1 behind the lid stamping-out is constituted.
When heat seal, though the seal head 121 of the sealing tegmentum material sealing device of lid is heated to 120～160 ℃ usually, this moment is owing to also applied heat on the part beyond the sealing of lid, so lid is at T 1Or T 4Processed under the above temperature conditions.Thus, lid just can recover the crimping shape, though on being sealed in container during in keep smooth, can show the crimping shape by just peeling off from container.
[5] containers for food use
Shown the crimping shape of utilizing shape memory to obtain after utilizing the lid of the container that the manufacture method of narration in described [4] obtains to peel off from container.For example when shape memory PBT laminate film is used for the lid of container for fast food, just as shown in figure 13, when the joint of holding lid 1 ( Block) portion 130 peels off to mark 131 from container body 140 lid 1, the flap portion (flap) of exposing because of Kaifeng is not even have aluminium lamination, can be kept to be the abundant state of crimping yet.When particularly being bonded on the paper sheet under the elongation state of the elastic restoring force that has kept the PBT film as described above, edge-rolling can further improve.When shape memory PBT laminate film is used for the lid of container for fast food, constitute Fig. 1～formation shown in Figure 4 of narration in preferably described [1] (3) as its layer.
When the shape memory PBT laminate film that will have the PBT thin layer that has formed wire trace described later is used for the lid of container for fast food, as shown in figure 14, by both sides otch 132,132 is set in connector portions 130, just can be with the easily local Kaifeng of lid 1.When the connector portions 130 of clamping lid 1 with finger and when the opposite layback of lid 1, lid 1 will be torn from otch 132,132 upper edge straight lines, shows peristome 133 on lid 1.Be kept abundant crimping because of tearing the flap portion 134 that reveals.Get final product so directly hot water is injected in peristome 133.
After having injected hot water, when flap portion 134 is returned to original position, because the jagged 134a of portion, the 134a of breaking of paper arranged on the outer rim of the one-sided or both sides of flap portion 134, therefore itself and the jagged 133a of portion that breaks, the 133a interlock of the paper of peristome 133, flap portion 134 just can not lift.And this moment peristome 133 area not only less than the peristome of in the past comprehensive Kaifeng formula, and because flap portion 134 is in the state that combines with peristome 133, even therefore mistake also can reduce the amount that hot water spills with container body 140 reversings.And in Figure 14,150 expression dried noodles.
Container body 140 for example can utilize synthetic resin such as paper, foamed styrene to make.Adopt under the situation of paper-made vessel main body, it is very easy not only to burn, and does not produce the advantage that environment is caused dysgenic gas but also have when burning.In addition, adopt under the situation of foamed styrene container made main body, have the good advantage of heat insulating ability.The shape of container body 140 is not limited to illustrated shape, can carry out various changes according to the kind of content.
Figure 15 and Figure 16 represent shape memory PBT laminate film is used to place the example of lid of the container of semi-solid food such as jelly, pudding.When shape memory PBT laminate film is used for the lid of semi-solid containers for food use, constitute Fig. 5 of narration and shown in Figure 6 constitute representational formation in described [1] (3) as its layer.As shown in figure 15, under sealing state, the lid 10 minutes that is sealed on the container 140 is smooth.But because lid 1 has recovered crimping shape (but being smooth) on being heat-sealed to container 140 time on apparent, therefore the lid of being made by the shape memory PBT laminate film that does not have paper sheet or aluminium foil 1 is by being peeled off from container 140, will be as shown in figure 16, because of shape memory crimping consumingly.Container body 140 for example can utilize synthetic resin such as polypropylene, polyethylene to make.The shape of container body 140 is not limited to illustrated embodiment, can carry out various changes according to the kind of content.Lid with the strong edge-rolling of this kind also is suitable for portable bag (the Port one シ ヨ Application パ of coffee milk etc. StarNetwork) purposes such as lid of usefulness.
By with the memory of narration in described [2] the shape memory PBT laminate film of pallet shape under smooth state with each pallet shape unit length cutting, just can be used as food and use with pallet.For example as shown in figure 17, the food of gained held on pallet 123 make things convenient for quick-frozen food 124 after, utilize packaging film 125 packings, make package goods 1226.As shown in figure 17, packaged food 126 utilizes microwave oven 127 grades to heat in order to eat, and pass through in temperature T this moment 1Or T 4Carry out the heat treated of appropriateness time under the above temperature, food will recover the pallet shape that formed by extrusion die 111 with pallet 123.When like this shape memory PBT laminate film being used for food with pallet 123, following convenience is arranged, promptly, under the state of package goods 126 because smooth basically, therefore volume is little, be convenient to transportation or display, utilize heat treated just can recover the pallet shape, become the state that is easy to eat.
With on the packaging film 125 of pallet 123, preferably utilize method described later at food, forming many parallel in fact wire traces on the one side at least.Like this, no matter how packaging film 125 just can its orientation all has the tearability to the straight line of a direction, can begin along wire trace smooth tearing from position arbitrarily.When edible, just packaging film 125 easily can be broken a seal the part thus.This kind wire trace is not owing to run through film, even so packaging film 125 after forming the wire trace, also very good aspect gas-barrier property.
[6] manufacture method of polybutylene terephthalate (PBT) film
As employed PBT film in the shape memory PBT laminate film of the present invention, the preferred expansion-molded method of following explanation or the film of uniaxial extension manufactured of utilizing.By the PBT film that use utilizes these manufacture methods to obtain, just can obtain stably to recover the shape memory PBT laminate film of the shape of being given.
(1) raw material polybutylene terephthalate (PBT)
Raw material PBT resin as the explanation in described [1] (1), therefore will illustrate omission.
(2) expansion-molded method
Figure 18 represents to utilize the operation of the method for expansion-molded manufactured PBT film.The tubular film of extruding the annular die 201 on being installed in extruder 212 is admitted to the film that air is expanded to required width lentamente because of its inside, is pulled under the state that is pulled 213 clampings of machine niproll, is reeled by wireline reel 214.
When making the PBT film, at first under 240～260 ℃ resin temperature, carry out the mixing of PBT resin and required additive etc.When melting temperature is higher than 260 ℃, then might make resin generation heat ageing.Thus, when carrying out in the extruder at biaxial extruder and so on when mixing, using has the extruder of athermic spiral structure, or has the extruder of suitable cooling device.And when the lower limit of melting temperature is lower than 240 ℃, because extrusion capacity becomes unstable and not ideal enough.
Be made as 210～250 ℃ from expanding with the resin temperature of extruding the annular die 201.When the temperature of the resin of extruding from annular die 201 surpasses 250 ℃, can't utilize first air ring 202 will steep 207 coolings fully.Preferably the resin temperature of extruding from annular die 201 is 220～230 ℃.In addition, be 9.8～13.7MPa (100～140kgf/cm from expanding with the resin pressure of extruding the annular die 201 2).Preferred 9.8～11.8MPa (100～the 120kgf/cm of extrusion resin pressure 2).Expand with the preferred 120～300mm of diameter of annular die 201.
The bubble of extruding from annular die 201 207 not only extends to the MD direction but also to the TD direction in the device cooling that is cooled.It is shown schematically among Figure 19.
Among Figure 19, the bubble cooling device have annular die be located at 201 near first air ring 202, be located at the top of first air ring 202 second air ring 203, be located at than second air ring 203 slightly by the 3rd air ring 204 of the position of top, be located at net cylindraceous 205 between first air ring 202 and second air ring 203, be located at the cooling air blowing out device 206 of the bottom of net 205.
In the device of above formation, the temperature control that utilizes the bubble 207 that the air cooling plavini forms is depended in the configuration of each air ring, therefore followingly describes steeping 207 shape and Temperature Distribution.
From the annular aperture (orifice) 211 of mould 201, extrude the PBT resin or the PBT resin combination of fusion, form bubble 207, become thin footpath shape owing to fusion tension force is lower, form so-called neck 271 but just be extruded the bubble 207 that comes.On neck 271, bubble 207 mainly extends along the MD direction.Then, bubble 207 expands sharp, reaches the bubble diameter of regulation.On this bulge 272, bubble 207 not only extends towards the MD direction, and extends towards the TD direction.Bulge 272 roughly above near frost line 274 is arranged, here the PBT resin combination becomes the cooling curing state.Owing to be located at second air ring 203 and the 3rd air ring 204 in the bubble zone 273 of frost line 274 tops, bubble 207 is further cooled.
In order to utilize this kind air cooling plavini to obtain the PBT film, the temperature of steeping each one of 207 is carried out following control.
(a) temperature of just extruding from annular die 201 is below 170 ℃.
(b) be cooled to below 130 ℃ at neck 271 places.
(c) be cooled to below 100 ℃ at frost line 274 places.
(d) utilize second air ring 203 to be cooled to below 80 ℃.
Above-mentioned condition (a) for condition (b), when uncolled to below 130 ℃ at neck 271 places, just can't bulge 272 below realizes the extension of TD direction as mentioned above fully.That is,, just can not have enough fusion tension force, make the master that extends to the MD direction at bulge 272 places when uncolled to below 130 ℃ the time at neck 271 places.
And, in order to satisfy this kind temperature conditions, blow-up ratio is made as 1.5～2.8.Preferably blow-up ratio is made as 2.0～2.8.
For condition (c), be reduced to below 100 ℃ by bubble temperature frost line 274 places, just can realize steeping 207 freezing extension.Thus, when when frost line 274 places bubble temperature is higher than 100 ℃, will be insufficient in the MD direction and the extension on the TD direction twocouese of bulge 272 places bubble 207.
For condition (d),, just can make evenly and the formation stabilisation of thin bubble 207 by being cooled to below 80 ℃ will steeping 207 above the frost line 274.When second air ring 203 is not set the temperature of the bubble 207 of frost line 274 tops is remained on when being higher than 80 ℃ state, might cause uneven extension, steep 207 integral body thus and just become unstable.
After the cooling that utilizes second air ring, and then, preferably utilize the 3rd air ring 204 to be cooled to below 50 ℃ as condition (e).When will be only steeping 207 when cooling off fully, might produce uneven cooling with second air ring 203.Preferably utilize the 3rd air ring 204 to be cooled to 30～40 ℃.Because the existence of these second air rings 203 and the 3rd air ring 204 just can not cause extension on the bubble 207 above it.
In order to carry out the temperature control of aforesaid bubble 207, the configuration of first air ring 202, second air ring 203, the 3rd air ring 204, net 205 and cooling air blowing out device 206 is as follows.
(A) first air ring 202
Be located at the very near position from annular die 201, ejection cooling air is so that the temperature of neck 271 is reduced to 130 ℃.Like this, on the later frost line 274 of bulge 272, the temperature of bubble 207 just is in below 100 ℃.
(B) second air ring 203
Be configured in from the be separated by position of top of 5～10 times distance H 1 of bore of annular die 201 of annular die 201, ejection cooling air reaches below 80 ℃ so that steep 207 temperature.
(C) the 3rd air ring 204
Be configured in from be separated by 0.5～5.0 times the distance H of bore of annular die 201 of second air ring 203 2The position of top, ejection cooling air reaches below 50 ℃ so that steep 207 temperature.
(C) net 205
Have shape cylindraceous, between first air ring 202 and second air ring 203, surround bubble 207.By cooling air blowing out device 206 coolings described later, temperature around the bubble 207 is kept evenly, so that the cooling that utilizes first air ring 202 and second air ring 203 to carry out is not subjected to the influence in outside ring territory (temperature temperature etc.), always carry out under the same conditions, make that thus the temperature maintenance of bubble 207 is described condition (b)～(d).
(E) cooling air blowing out device 206
Be located at the outside, bottom of net 205, the cooling air blow-off outlet along the bottom of net 205 has circle will cool off air and spray obliquely upward, so that the temperature on every side of net 205 reaches 30～40 ℃, the stable temperature in preferred 30～35 ℃ scope.The cooling air that is blown out obliquely upward is blown to the top along net 205, with net 205 whole coolings (arrow among Figure 19).
In above method,, preferably use humidifying air as utilizing first air ring 202 to the cooling air that bubble 207 sprays.Humidifying air contains the roughly moisture of saturation state for utilizing the chilled air of cold water humidification, and cooling effect is compared approximately big 5 ℃ with simple cooling air.In addition, as utilizing second and third air ring 203,204,, also preferably use humidifying air from the viewpoint of cooling effectiveness to the cooling air that bubble 207 sprays.In addition, because in the time can't obtaining stable cooling effect, it is unstable that bubble 207 becomes, therefore the temperature and the humidity of cooling air are remained unchanged as far as possible by controlling.
In addition, the cooling air that sprays to net 205 from cooling air blowing out device 206 is with identical from the situation of described first～the 3rd air ring 202-204, both can use humidifying air, and also can use common air to be adjusted into the air of required temperature indoor.
Figure 21 represents to supply with the system of humidifying air.The air of being supplied with by blower B has been possessed 15 humidifications coolings of humidifier of water chiller R and cold water circulation pump P, supplies with to first～the 3rd air ring 202～204 and cooling air blowing out device 206 respectively.
As net 205, can use metal members such as plastic member such as nylon, polypropylene, polyester or stainless steel, copper, brass, nickel, but its mesh is preferably 5～20 orders, preferred especially 8～10 orders in addition.
In addition, as shown in figure 19,, also can next door 220 be set according to the mode of surrounding bubble zone 273 in the outside of net 205.Because by next door 220 is set, just can isolating bulb zone 273 and be not subjected to the influence of outside atmosphere (temperature temperature etc.), therefore the cooling that utilizes first air ring 202, second air ring 203, the 3rd air ring 204 and cooling air blowing out device 206 to carry out just can always be carried out under the same conditions, just the temperature around the bubble 207 can be kept evenly maintain foregoing condition (b)～(d) thus thereby will steep 207.
Though the material for next door 220 is not particularly limited, in order to observe the bubble zone 273 that is surrounded by next door 220, preferred acrylic resins.If can surround bubble zone 273 from the four directions, then the shape for next door 220 is not particularly limited, and for example can enumerate the shape of cylinder type structure or the shape of rectangular build structure, but preferably drum type structure.
Also can be as required, the inboard of next door 220 is provided with heating arrangements 230.As heating arrangements 230, for example can enumerate bar-shaped or banded electric heater.Bar-shaped electric heater preferably is provided with a plurality of.Thereby the inner face that also can adopt next door 220 is laid aluminium foil and is blocked thermal-radiating structure.As required, bottom that also can next door 220 (cooling air blowing out device 206 directly over) is provided with the mechanism that blows out the cold wind about room temperature.So not only the temperature adjustment of 220 inboards, next door becomes more easy, and the air mass flow adjustment of 220 inboards, next door is also more easy.
As shown in figure 19, the top that is preferably in next door 220 is provided with cooling air outlet 221.By cooling air outlet 221 is set, just can carry out rectification to the cooling air of ejection from first air ring 202, second air ring 203, the 3rd air ring 204 and cooling air blowing out device 206.Just can prevent teeter thus by the bubble 207 that causes of cooling air.Cooling air outlet 230 preferably is provided with more than 2, more preferably is provided with 2～4.Though in the example shown in Figure 19, the top of the side 222 of next door 220 is provided with cooling air outlet 221, also can be arranged on top 223 of next door 220.Wherein, the number of cooling air outlet 221 and bore can be made as the amount of the degree that can not damage the heat insulating ability that utilizes next door 220 acquisitions.
As shown in figure 19, the inside upper part that is preferably in next door 220 is provided with the cowling panel 240 of ring-type.By cowling panel 240 is set, just can improve the ability that the cooling air that sprays is carried out rectification from first air ring 202, second air ring 203, the 3rd air ring 204 and cooling air blowing out device 206, the teeter that prevents of bubble 207 is further improved.As shown in figure 19, cowling panel 240 is preferably from extending near the cylindric net 205 near the medial surface in next door 220.For the structure of cowling panel 220 without limits, can enumerate structure that the quilt shown in Figure 19 and Figure 20 (a) separates along a direction sheet material arranged side by side, shown in Figure 20 (b), be separated into cancellate structure, the flat form of the punching that is provided with a plurality of circular holes shown in Figure 20 (c), netted form etc.The percent opening of cowling panel 240 preferred 40～60%.Be not particularly limited for the material that constitutes cowling panel 240, can enumerate aluminium, synthetic resin etc.Though the sheet number that is provided with for cowling panel 240 also is not particularly limited, and a slice is set usually gets final product.
The system film that utilizes the plavini of PBT resin to carry out can realize that other condition can be suitable for the general condition of expansion fashion by keeping above necessary condition.Promptly, use the cross head mould, with tubulose fusion PBT resin upward or the below extrude, reeled continuously with the pinch roll clamping and when making it to be expanded to the size of regulation to wherein sending into air in the end, mould rotation or counter-rotating just can be prevented thick partially situation generation therebetween.
The percent thermal shrinkage value of the PBT film of Zhi Zaoing is roughly 0% up to 200 ℃ as described above, until 200 ℃ thermal contraction does not take place in fact.The variation of film dimensions is seldom in secondary operations such as heat seal, printing thus.In addition, extend under heating and two kinds of situations of non-heating and can both realize, for example under about 130 ℃, can easily extend to about 3.2 times, can obtain from milky to translucent extension film.Under the situation of extending under the non-heated condition, can obtain clear films.Utilize the manufacture method of above explanation, just can make more than the thickness 10 μ m, the PBT film of thin-film width 400～1200mm.
According to the manufacture method of above explanation, each one of bubble (just having extruded back, neck, bulge, frost line) always is maintained at required temperature respectively, so quality always can keep even.Owing to can increase cooling velocity, therefore just can realize making at a high speed film in addition.
(3) uniaxial extension method
Figure 22 represents to utilize the manufacturing process of the PBT film that the uniaxial extension method carries out.Casting rolls 301 draws, slow cooling by being heated with the molten resin 305 that is extruded the mould (T mould) 307 from thin slice, and forms crystallization thin slice 306.The crystallization thin slice 306 of gained becomes extension film by extending between second roller 302 that heats casting rolls 301 and be arranged in parallel with it.
(a) the crystallization thin slice forms operation
At first, with the additive of narration in PBT resin and described [1] (1), other melting mixings such as resin, modulation molten resin 305.Though the method for melting mixing is not particularly limited, usually by mixing equably carrying out in biaxial extruder.Preferred 230～260 ℃ of melting temperature.When melting temperature was higher than 260 ℃, the heat ageing of resin just might take place.When carrying out in the extruder at biaxial extruder and so on when mixing, use the extruder that has the extruder of the screw configuration that can not generate heat or have suitable cooling device thus.And when the lower limit of melting temperature was lower than 230 ℃, it is unstable that extrusion capacity will become, therefore not ideal enough.
With melting mixing molten resin 305 directly or by getting involved other extruder, perhaps cooling earlier and after the beadization once more by extruder from thin slice with extruding the mould 307.Thin slice is made as below the 5mm usually with the gap of mould 307.Preferably be made as 210～250 ℃ from thin slice with the resin temperature of extruding the mould 307, more preferably be made as 220～230 ℃.
Will be by aforesaid operations from thin slice with the molten resin of extruding the mould 307 305, with 301 tractions of heating casting rolls, slow cooling, form crystallization thin slice 306.Because can improve for the processability of extending by forming crystallization thin slice 306, therefore high extensionization and filming just become more easy.For before casting rolls 301 contact with heating, the temperature of the molten resin 305 that is extruded is not reduced to below 200 ℃, preferably thin slice is made as below the 20cm with mould 307 and the distance that heats between the casting rolls 301.Heating casting rolls 301 preferably is adjusted into temperature 150～200 ℃.When the temperature that makes heating casting rolls 301 surpasses 200 ℃, because fusion tension force step-down, so the formation of crystallization thin slice 306 just becomes difficult.On the other hand, when the temperature that makes heating casting rolls 301 is lower than 150 ℃, the crystallized temperature step-down of the crystallization thin slice 306 of gained, therefore the processability for follow-up extension can descend.
Preferably the thickness with crystallization thin slice 306 is made as 50～100 μ m.The filming of utilizing follow-up extension process to carry out like this is just more easy.For the thickness with crystallization thin slice 306 is made as 50～100 μ m, and the necking phenomenon when doing one's utmost to suppress to form crystallization thin slice 306 (phenomenon that the sheet width that is extruded from mould and has been poured into a mould becomes narrower than the effective width of mould) is made as the peripheral speed of heating casting rolls 301 5～15m/ minute.Preferred 35～the 70cm of external diameter of heating casting rolls 1.
(b) extension process
(i) once extend
Then as shown in figure 22, the crystallization thin slice 306 of gained between the heating casting rolls 301 and second roller 302, is utilized the difference of two rollers, extend (once extending) along operating direction.At this moment, preferably will heat casting rolls 301 as described in (a) narration such adjust its temperature to 150～200 ℃, and the roll gap (the common tangential spacings between two rollers) that will heat the casting rolls 301 and second roller 302 is made as below the 10cm.By once extending under this kind condition, the zone (elongated area) that crystallization thin slice 306 is extended is narrow, and the temperature of elongated area can be made as 130～150 ℃.Be made as 130～150 ℃ by temperature, just fusion tension force can be made as the scope that is suitable for more powerful extension, therefore just can realize the uniform extension that film is uneven less the elongated area.Along with dwindling the elongated area, can improve the inhibition effect of necking phenomenon in addition.And, for the temperature of elongated area is kept certain, also can use hot line heater etc. that the film between two rollers is heated.And, in Figure 22,309 expression guiding rollers, 308 expression wireline reels.
Though extension ratio is different because of the thickness of crystallization thin slice 306, preferably is made as more than 1.5 times, more preferably is made as 2～4 times.Make extension ratio high more, the transparency will improve more.Peripheral speed ratio by the suitable setting heating casting rolls 301 and second roller 302 just can extend to required multiplying power.External diameter for second roller 302 is not particularly limited, as long as be made as 35～70cm in the same manner with heating casting rolls 301.
Also carry out under the situation of extension (secondary extension) more described later after once extending, preferably the temperature with second roller 302 is adjusted to 100～150 ℃.On the other hand, under the situation of only once extending, be adjusted into below 40 ℃, just can implement the fixing processing of cooling the film of having implemented once to extend by temperature with second roller 302 as extension process.In this specification, the fixing processing of so-called cooling is meant, handles film under the temperature below the Tg of PBT (20～45 ℃).Cooling is fixing to be handled by implementing, just can be with in stable conditionization that is extended.In addition, further prolong under the fixing situation about handling of cooling, as shown in figure 23, with second roller 302 the 3rd roller 303 is set abreast, its temperature is adjusted to below 40 ℃, and makes it to rotate with same peripheral velocity with second roller 302, the film that traction has been implemented once to extend gets final product.And, in Figure 23, used identical reference marks for the part identical with the producing device shown in Figure 22.The external diameter of the 3rd roller 303 and second roller 302 are made as 35～70cm in the same manner and get final product.And in Figure 23,310 expression niprolls.
When utilizing the 3rd roller 303 to cool off fixing the processing, also the temperature of second roller 302 can be adjusted to more than the Tg of PBT below (not containing Tg)～PBT fusing point-50 ℃, the percent thermal shrinkage of film will further descend like this.
(ii) secondary extends
Preferably to extending (secondary extension) along operating direction again through once extending the extension film that obtains.Utilize secondary to extend the transparency is further improved, and further filming.When also carrying out the secondary extension, between second roller 302 shown in Figure 23 and the 3rd roller 303, difference is set, extend along operating direction.At this moment, preferably second roller, 302 temperature are adjusted to 100～150 ℃, and the roll gap of second roller 302 and the 3rd roller 303 is made as below the 10cm.By roll gap is made as below the 10cm, the reason that can suppress necking phenomenon is narrated in (i) as described.
After secondary extended, when also carrying out extension once more described later (three extensions), preferably the temperature with the 3rd roller 303 was adjusted to 40～100 ℃.On the other hand, not carrying out under the situation of extending for three times, by the 3rd roller 303 temperature are adjusted to below 40 ℃, just can be to having implemented fixing processing of film enforcement cooling that secondary extends.In addition, cooling fixed under the situation of handling further prolongation, as shown in figure 24, can the 4th roller 304 be set abreast with the 3rd roller 303, its temperature is adjusted to below 40 ℃, and makes it to rotate with same peripheral velocity with the 3rd roller 303, the film that the secondary extension has been implemented in traction gets final product.And, in Figure 24, used identical reference marks for the part identical with the producing device shown in Figure 22.The external diameter of the 4th roller 304 and the 3rd roller 303 are made as 35～70cm in the same manner and get final product.
And, when utilizing the 4th roller 304 to cool off fixing the processing,, also the temperature of the 3rd roller 303 can be adjusted to more than the Tg of PBT below (not containing Tg)～PBT fusing point-50 ℃ for the percent thermal shrinkage with film further reduces.
(iii) extend for three times
Also can extend (three extensions) along operating direction again to extend the extension film that obtains through secondary.When also carrying out extending for three times, between the 3rd roller 303 shown in Figure 24 and the 4th roller 304, difference is set, extend along operating direction.At this moment, preferably the 3rd roller 303 temperature are adjusted to 40～100 ℃, and according to described (i) in the identical reason of narration, the roll gap of the 3rd roller 303 and the 4th roller 304 is made as below the 10cm.By implementing the cold rolling extension of this kind, the transparency of film is further improved.In addition, the temperature of the 4th roller 304 preferably is adjusted to below 40 ℃, so just can implement the fixing processing of cooling to the film of having implemented to extend for three times.
(iv) horizontal expansion
To the PBT film made from any one method of described (i)～(iii), can continue the horizontal expansion of enforcement to TD (width).As the method for carrying out horizontal expansion, known method such as use tentering method get final product.
(v) heat treatment
Though the PBT film of Zhi Zaoing has good dimensional stability as described above, further improve in order to make percent thermal shrinkage, also can implement heat treatment again.As heat treatment method, can use heat fixation to handle or thermal contraction any one in handling.Carry out below above (not containing the Tg)～PBT fusing point-50 of the Tg of the best PBT of these heat treatment ℃.
Heat fixation processing and utilizing tentering mode, roller mode or calendering mode are carried out.In addition, use tentering mode, roller mode are handled in thermal contraction or the calendering mode is carried out or use conveyer belt or floating axle (floating) to get final product.Also heat fixation processing and thermal contraction treatment combination can be carried out.
The PBT film of Zhi Zaoing is translucent transparently as described above, compares with uniaxial extension film in the past, and the uniformity aspect of thickness is better, and percent thermal shrinkage is lower.Specifically, the film thickness difference of the film of average film thickness 8～20 μ m is 1～2 μ m, percent thermal shrinkage is that MD (operating direction) is below 0.1%, TD (width) is below 0.2% [in this specification, so-called film thickness difference is meant that with the central part of the width of PBT film and the thickness at both ends be that a unit measures 6 points altogether with 2 respectively, calculate wherein maximum and the value after the difference of minimum of a value.This value is more little, and then the result is just good more.In addition, so-called percent thermal shrinkage is meant MD and the shrinkage factor of TD the value respectively measure after of PBT film when down exposing 10 minutes for 150 ℃.]。Thus, just can form uneven less printed layers or metal evaporation layer.In addition, in secondary operations such as heat seal, printing, the variation of film dimensions is less.
According to the manufacture method of above explanation, because heating casting rolls and first～the 4th roller always is maintained at required temperature respectively, so quality just can keep evenly.In addition, owing in the making of extension film not, do not cool off earlier, therefore can carry out high speed system film.
[7] formation of the wire trace on the film
In order to make shape memory PBT laminate film have the tearability of straight line, be preferably in the middle of PBT film, stiffness films and the sealing film at least one comprehensively on, utilize the method for the following stated to form many parallel in fact wire traces.So just can be with shape memory PBT laminate film easily along smooth tearing, therefore for example under the situation that the packaging material that shape memory PBT laminate film is used as the lid of container for fast food use, just cap portion ground can be broken a seal.This kind wire trace is preferably formed especially on the PBT film.The wire trace can form by making the film that moves continuously form mechanism's sliding-contact with the wire trace with a plurality of fine projections.Be elaborated hereinafter with reference to the formation method of accompanying drawing to the wire trace.
(1) situation of the wire trace of formation direct of travel on film
Figure 25 is illustrated in an example that forms the device of wire trace on the direct of travel of film 401.Roller (hereinafter referred to as " pattern roller ") 402 that Figure 25 has represented to have on the surface a plurality of fine projections form mechanism as the wire trace and use, and used the example of nozzle 403 that can blow air as the film dipper crowding gear.By the film 401 process niprolls 412 that make uncoiling from be wound with the raw-material spool 411 of film, with pattern roller 402 sliding-contacts, form the wire trace, the straight line tearability film of gained is batched by wireline reel 416 through niproll 413, guiding roller 414 and 415.
Pattern roller 302 as shown in figure 26, its rotating shaft is fixed on the assigned position, makes it parallel with the width of film 401.Axis direction length is longer than the width of film 401, make the width of film 401 whole with the pattern roller sliding-contact.
By niproll 412 and 413 being arranged on the front and back of pattern roller 402, just can apply tension force to the film 401 of on pattern roller 402, advancing as the tension adjustment roller.In addition, as shown in figure 26, by on the position of film 401 and pattern roller 402 sliding-contacts, utilize nozzle 403 to blow the air of the blast that has regulation from an opposite side of pattern roller 402, just can be at the face of film 401 and pattern roller 402 sliding-contacts (if followingly do not particularly point out then be called " roller sliding contact surface ".) apply uniform contact force.So just can on pellicular front, form the uniform linear trace.By using nozzle 403 that film 401 is pressed against on the pattern roller 402, just can alleviate the contact inhomogeneities that the uneven thickness by the film on the roller sliding contact surface 401 causes.
Preferably make pattern roller 402 with the peripheral speed slower, along the direction rotation opposite with the direct of travel of film 401 than the gait of march of film 401.So just can prevent the generation of film fold, and the cutting chip that can prevent to follow the formation of wire trace to produce remains in the surface of pattern roller 402, therefore just can form the wire trace of the suitable length and the degree of depth.The gait of march of film 401 preferably was made as 10～500m/ minute among the present invention.In addition, the peripheral speed of pattern roller 402 (making it along the speed of the direction rotation opposite with the direct of travel of film 401) preferably was made as 1～50m/ minute.
As pattern roller 402, for example can use the spy to open the member of being put down in writing in 2002-59487 number.It has and utilizes electrodeposition process or utilize organic class or the mineral-type bonding agent has adhered to the structure of a plurality of Mohs' hardness at the particulate more than 5 on the surface of metal system roller main body.Metal system roller main body is for example made by iron, ferroalloy etc.Preferably utilize nickel coating or chromium coating surface coverage with metal system roller main body.As the particulate of Mohs' hardness more than 5, for example can enumerate superhard alloy particles such as tungsten carbide, carborundum particle, boron carbide particle, sapphire particle, cubic boron nitride (CBN) particle, natural or synthetic diamond particle etc.Bigger diamond synthesis particulates such as special preferred hardness, intensity.The particle diameter of particulate is suitably selected according to the degree of depth or the width of formed wire trace.Among the present invention, preferably the particle diameter of particulate is 10～100 μ m, and the deviation of particle diameter is below 5%.Particulate can suitably be selected, so that the interval between the formed wire trace reaches required degree attached to the degree on the surface of roller main body.In order to obtain the uniform linear trace, particulate is adhered to more than 50% in the roller body surfaces.As the concrete example of pattern roller 402, can enumerate the example that is fixed with a plurality of diamond synthesis particulates in roller body surfaces made of iron with the area occupation ratio more than 50% across the deposition layer combination of nickel class.Preferred 2～the 20cm of the external diameter of pattern roller 402, more preferably 3～10cm.
As pattern roller 402, can use on the surface of metal system roller main body and embed the pin discaling roll that metal system pin is arranged in length and breadth regularly with the slight gap edge.In addition, form mechanism, except pattern roller 402, also can use on the surface of tabular main body, to have the pattern flat board of a plurality of aforesaid Mohs' hardness at the particulate more than 5 as the wire trace.
Figure 27 represents film 401 and pattern roller 402 sliding-contacts, forms the state of wire trace.For example the roller sliding contact surface is cut in the bight of at least one particulate in the middle of the lip-deep particulate 404 of pattern roller 402, as mentioned above, the gait of march of film 401 is faster than the peripheral speed of pattern roller 402 reverse rotations, therefore the bight of the particulate 404 of incision can form long wire trace before leaving the roller sliding contact surface.
Blow mechanism as air, also can replace the nozzle (with the identical nozzle of nozzle shown in Figure 25～26) that shown in Figure 28 (a), has banded blow-off outlet 431, use the nozzle that shown in Figure 28 (b), has a plurality of blow-off outlets 431.In addition when using having as Figure 28 (c) shown in to cover 432 nozzle with the form compressed-air blows of coverage diagram table roll 402, the compressed air that blows out from blow-off outlet 431 was difficult to diffusion before the position that arrives film 401 and pattern roller 402 sliding-contacts, therefore can make the further homogenising of contact force of the film 401 and the pattern roller 402 of roller sliding contact surface.Utilize this kind air to blow the preferred 4.9～490kPa (0.05～5kgf/cm of pressure of the compressed air stream that mechanism blows 2).So just can make the contact force homogenising of the film 401 and the pattern roller 402 of roller sliding contact surface.The pressure of preferred compressed air stream is 9.8～196kPa (0.1～2kgf/cm 2).In addition, from blow-off outlet 431 to the preferred 10～50cm of the distance of roller sliding contact surface.As long as compressed air is piping and druming equably in the scope that covers the roller sliding contact surface at least.But, when the blow-off outlet 431 with air blast or nozzle increases to essential degree when above, obtains suitable blast and the amount of desired compression air can increase, thus not ideal enough.
With regard to regard to the encirclement of the film 401 that is fixed on the pattern roller 402 on the assigned position (the volume I is hung け) method, preferably make involving in direction and roll out direction angulation θ and being in 60～170 ° scope of the film 401 shown in Figure 28 (c).The length of wire trace and the degree of depth are just adjusted easily like this.More preferably make angle θ be in 90～150 ° scope.For angle θ is made as required value, can change the height and position of pattern roller 402 etc., the position of pattern roller 402 and niproll 412 and 413 relation is suitably adjusted got final product.In addition,, the blast that utilizes niproll 412 and 413 to offer the tension force of film 401 and to utilize nozzle 403 to provide is suitably adjusted, obtained the wire trace of the required length and the degree of depth according to encirclement method and external diameter for the film 401 of pattern roller 402.Among the present invention,, preferably be made as the scope of 0.01～5kgf/cm width for utilizing niproll 412 and 413 to be added in tension force (tension force on the per unit width) on the film.
By making the brush and the face sliding-contact of an opposite side of roller sliding contact surface replace air to blow the mode of mechanism, can on the roller sliding contact surface, apply uniform contact force.The rough lumber of brush preferably on the sliding contact surface of brush and film 401 (if following do not particularly point out then be called " brush sliding contact surface "), the material that can move along direct of travel rightabout with the speed slower than the gait of march of film 401 with film 401.Thus, as brush, preferably as shown in figure 29, use has the rotation roller brush 405 of many rough lumbers with radial configuration around brush axle (rotating shaft), according to making its rotating shaft mode parallel be fixed on the assigned position with the width of film 401, make axis direction length longer, so that the width of film 401 is whole and the brush sliding-contact than the width of film 401.
Preferred 5～the 10cm of external diameter of rotation roller brush 405.About the rough lumber 451 of rotation roller brush 405, preferred crooked recovery rate is more than 70%, the preferred 0.1～1.8mm of diameter, the preferred 1～5cm of length.Preferred 100～500/cm of the density of rough lumber 451 on the brush sliding contact surface of rotation roller brush 405 2In this specification, so-called " crooked recovery rate " is meant, making makes the ring of 21 group the chain that the rough lumber fiber of the about 26cm of length intersects, the top ring is fixed on the retainer, add 3 minutes load (weight of 1/2 load [g] of the fiber number of rough lumber fiber [danier]) by circulating application downwards, with the pair of curved that is formed on the crossing of ring is the sample of U type pressing plate shape, with the length cutting sampling of about 3cm, places and measures angle of release degree (θ after 60 minutes 4), thus according to formula: θ 4/ 180 * 100 (%) and the value calculated.Though the shape for the head end of rough lumber 451 is not particularly limited, preferred approximate U font or taper.Though the material for rough lumber 451 also is not particularly limited, the synthetic resin of optimization polypropylene, nylon, acrylic acid, polyethylene etc.
Rotation roller brush 405 preferably reaches 1～490kPa (0.01～5kgf/cm according to the pressure that makes the brush sliding contact surface 2) mode and film 401 sliding-contacts.The peripheral speed of rotation roller brush 405 (make it along with the speed of the direct of travel rightabout rotation of film 401) preferably was made as 1～50m/ minute.
For the degree of the tearability that satisfies required straight line, the length of wire trace and the degree of depth can by to the pressure of the blast of the external diameter of the particle diameter of the peripheral speed of the gait of march of film 401, pattern roller 402, diamond particle 404, pattern roller, nozzle 403, rotation roller brush 405, utilize tension force that niproll 412 and 413 provide etc. suitably to set to adjust.
(2) situation of the wire trace that formation is tilted on film
Figure 30 represents to form with respect to the direct of travel of film 401 example of the device of the wire trace that tilts.Used identical reference marks for member identical or part with Figure 25.Device shown in Figure 30 forms mechanism as the wire trace and possesses the pattern endless belt 406 that has connected a plurality of little pattern rollers 421, and possesses the Ring form brush 407 that has disposed many rough lumbers 471 on the endless belt as the film dipper crowding gear.Figure 31 (a) is illustrated in the device shown in Figure 30, makes the local amplification plan view of pattern endless belt 406 along the state of the width rotation of film 401, and Figure 31 (b) is the schematic section of seeing from the D direction in Figure 31 (a).
By make pattern endless belt 406 as Figure 31 (a) and (b) along the rotation of the width of film 401, make little pattern roller 421 continuously with film 401 sliding-contacts, just can form wire trace with respect to the direct of travel inclination of film 401.Preferably make the number of the pattern roller 421 that constitutes pattern endless belt 406 more, make the density of pattern roller 421 higher.The axis direction length of little pattern roller 421 and the preferred 5～10cm of external diameter.
The wire trace of incline direction can be by suitably adjusting pattern endless belt 406 with respect to the angle of film direct of travel peripheral speed and the gait of march of film 401 change.Usually the peripheral speed with pattern endless belt 406 was made as 1～100m/ minute.Little pattern roller 421 is rotated in opposite direction with respect to the direct of travel of pattern endless belt 406 on the roller sliding contact surface.Its peripheral speed is identical with the situation of the pattern roller 402 of described (1) middle narration, is 1～50m/ minute.
Ring form brush 407 preferably according to make its rough lumber 471 with film 401 sliding-contacts in the direction that moves and pattern endless belt 406 with film 401 sliding-contacts in the opposite mode of the direction that moves rotate.Make Ring form brush 407 and pattern endless belt 406 have identical direction of rotation like this.Preferred 4～the 8cm of length of the rough lumber 471 of Ring form brush 407.Situation about rotation roller brush 405 of narration in the optimum condition of density, head end shape and material on the crooked recovery rate of the rough lumber 471 of Ring form brush 407, diameter, the brush sliding contact surface and described (1) is identical.Pressure on the brush sliding contact surface of Ring form brush 407 is identical with the situation of the rotation roller brush 405 of described (1) middle narration, is 1～490kPa (0.01～5kgf/cm 2).The Ring form brush 407 and the pressure of film 401 sliding-contacts can be regulated by the upper-lower position that rotation height release handle 473 is suitably set Ring form brush 407.Preferred 1～the 50m/ of the peripheral speed of Ring form brush 407 minute.The peripheral speed of Ring form brush 407 can be regulated by the rotary speed of suitably setting motor 474.
Pattern endless belt 406 and Ring form brush 407 preferably make direct of travel length longer than the width of film 401, so that the width of film 401 is whole and pattern endless belt 406 and Ring form brush 407 sliding-contacts.
Figure 32 represents to form other example of the device of the wire trace that the direct of travel with respect to film 401 tilts.Member identical with Figure 25 or part have been used identical reference marks.Device shown in Figure 32 forms mechanism as the wire trace, possesses as shown in figure 33 a plurality of less pattern roller 422a to be installed in the roller formation 408a that forms on the guide rail 481a (supporter) side by side and a plurality of less pattern roller 422b to be installed in side by side the roller formation 408b that forms on the guide rail 481b (supporter).
Supporting the back shaft 491a of pattern roller 422a and 422b and 491b can free lifting, and roller formation 408a and 408b can be respectively width straight line along guide rail 481a and 481b along film 401 move.The guide mechanism that utilization is made of back shaft 491a that can free lifting and 491b and guide rail 481a and 481b, roller formation 408a and 408b can move independently along the width of film 401.Thus, can carry out following circulation repeatedly, promptly, make roller formation 408a and 408b from film 401 one distolateral to another distolateral with film 401 sliding-contacts in move, separate with film 401 after distolateral and get back to original position moving to another, pass through moving of control roll formation 408a and 408b at this moment, make the whole sliding-contact of the width that any one roller formation and film 401 are always arranged, form wire trace with respect to the direct of travel inclination of film.As guide mechanism, also can adopt not to be to make back shaft 491a and 491b, but make the formation of guide rail 481a and 481b free lifting with respect to guide rail 481a and not lifting of 481b.
The axis direction length of pattern roller 422a and 422b and external diameter are to get final product about 5～10cm.Gap between the pattern roller of pattern roller 422a and 422b is preferably narrower than the roller width of pattern roller at least, improves the density of pattern roller.The length separately of roller formation 408a and 408b is longer than the width of film 401.
In the device shown in Figure 32,, be provided with Ring form brush 407a and the 407b identical respectively abreast with respect to roller formation 408a and 408b with the mechanism that device had shown in Figure 30 across film 401 as the film dipper crowding gear.But the supporting member 472,472 that supports Ring form brush 407a and 407b can free lifting.Thus by its lifting of control, make Ring form brush 407a and roller formation 408a while and film 401 sliding-contacts, and, just can always provide certain contact force by the pair roller sliding contact surface according to making Ring form brush 407b and roller formation 408b side by side control its lifting with the mode of film 401 sliding-contacts.
Ring form brush 407a and 407b preferably according to make its rough lumber with film 401 sliding-contacts in the direction that moves and roller formation 408a and 408b with film 401 sliding-contacts in the opposite mode of the direction that moves rotate.Peripheral speed about pressure, Ring form brush 407a and the 407b of the brush sliding contact surface of the preferred necessary condition of density, head end shape and material on the crooked recovery rate of the rough lumber of Ring form brush 407a and 407b, diameter, length, the brush sliding contact surface and Ring form brush 407a and 407b is identical with the situation of the Ring form brush that device had 407 shown in Figure 30.
The wire trace of incline direction and the angle of film direct of travel can change by the gait of march of the speed that makes roller formation 408a and 408b sliding-contact and film 401 is suitably adjusted.In addition, pattern roller 422a and the 422b direction rotation opposite with respect to advancing of roller formation 408a and 408b in roller sliding contact surface upper edge.Its peripheral speed can be identical with the situation of described (1) middle pattern roller 402 of narrating.
Figure 34 (a) and Figure 34 (b) expression forms other example of the device of the wire trace that tilts with respect to the direct of travel of film 401.In this example, axis direction length is provided with before and after longer 2 the pattern roller 423a of the width of film 401 and 423b are on the direct of travel of film 401 abreast.More than 2 times of width of the axis direction length preferred film 401 of pattern roller 423a and 423b.
Supporting the back shaft 492a of pattern roller 423a and 423b and 492b can free lifting, and pattern roller 423a and 423b can move by straight line on the width of film 401 along guide rail 482a and 482b respectively.The guide mechanism that utilization is made of back shaft 492a that can free lifting and 492b and guide rail 482a and 482b, pattern roller 423a and 423b can move independently along the width of film 401.Thus, carry out following circulation repeatedly, promptly, make pattern roller 423a and 423b from film 401 one distolateral to another distolateral with film 401 sliding-contacts in move, separate with film 401 and get back to original position moving to other end rear flank, this moment the moving of control chart table roll 423a and 423b, make any one pattern roller always with the whole sliding-contact of the width of film 401, just can form wire trace with respect to the direct of travel inclination of film.The wire trace of incline direction can change by the gait of march of the speed that makes pattern roller 423a and 423b sliding-contact and film 401 is suitably adjusted with respect to the angle of film direct of travel.
In the device shown in Figure 34,, be provided with the Ring form brush 407a and the 407b of the energy free lifting identical respectively abreast with respect to pattern roller 423a and 423b across film 401 with the mechanism that device had shown in Figure 30 as the film dipper crowding gear.
And, in the device shown in Figure 30～Figure 34,, possess Ring form brush, but the air that also can possess narration in described (1) blows mechanism as the film dipper crowding gear.
(3) situation of the wire trace of formation width on film
Figure 35 is illustrated in an example of the device of the wire trace that forms width on the film 401.Used identical reference marks for member identical or part with Figure 30.Device shown in Figure 35 is tilted the setting identical with the device shown in Figure 30 and Figure 31 (Ring form brush is not shown) except pattern endless belt 406 with respect to the direct of travel of film.By using the device shown in Figure 35, the angle with respect to the direct of travel of film 401 of the gait of march of film 401, pattern endless belt 406, the operating conditions such as peripheral speed of pattern endless belt 406 are suitably set, just can on the width of film 401, be formed the wire trace.
Figure 36 is illustrated on the film 401 other example of the device of the wire trace that forms width.In this example, be symmetry axis and be provided with the pattern endless belt 406a that has connected a plurality of little pattern roller 421a obliquely and connected the pattern endless belt 406b of a plurality of little pattern roller 421b symmetrically and with respect to the direct of travel of film with the center line of film 401.As the film dipper crowding gear, preferably will with pattern endless belt 406a and 406b (not shown) be set abreast respectively across film 401 with the identical Ring form brush in the device shown in Figure 30.
By using the device of the formation shown in Figure 36, gait of march, pattern endless belt 406a and 406b to film 401 suitably set with respect to the operating conditions such as peripheral speed of angle, pattern endless belt 406a and the 406b of the center line 417 of film 401, just can form the wire trace on the width of film 401.
The width that Figure 37 is illustrated in film 401 forms other example of the device of wire trace.Device shown in Figure 37 except the roller array 408a shown in Figure 33 and 408b are obliquely installed with respect to the width of film 401, identical with the device shown in Figure 33 (Ring form brush is not shown).By using the device of the formation shown in Figure 37, gait of march, roller array 408a and 408b to film 401 suitably set with respect to the operating conditions such as sliding-contact speed of angle, roller array 408a and the 408b of the direct of travel of film 401, just can form the wire trace on the width of film 401.
Figure 38 (a) and Figure 38 (b) are illustrated in other example of the device that forms the wire trace on the width of film 401.The left surface of the device shown in Figure 38 (b) expression Figure 38 (a) (figure that sees from the F direction of Figure 38 (a)).In this example, possess 2 the pattern roller 424a and the 424b of axis direction that the direct of travel that has with respect to film 401 tilted.The axis direction length of pattern roller 424a and 424b preferably is at least more than 2 times of width of film 401.
Supporting the back shaft 493a of pattern roller 424a and 424b and 493b can free lifting, and pattern roller 424a and 424b can move along straight line when the center line 417 with respect to film 401 keeps the angle of regulation along guide rail 483a and 483b respectively.The guide mechanism that utilization is made of back shaft 493a that can free lifting and 493b and guide rail 483a and 483b, pattern roller 424a and 424b can keep at the center line 417 with film 401 moving independently in the angle of regulation.For axis direction length, pattern roller 424b is longer than pattern roller 424a, so pattern roller 424a and 424b just can interlock when opposite direction is advanced mutually.Thus, carry out following circulation repeatedly, promptly, make pattern roller 424a and 424b from film 401 one distolateral to another distolateral with film 401 sliding-contacts in move, separate with film 401 and get back to original position moving to other end rear flank, by moving of control chart table roll 424a and 424b at this moment, make any one pattern roller always with the whole sliding-contact of the width of film 401, thereby can form the wire trace that is positioned at width with respect to the direct of travel of film.
As the film dipper crowding gear, can be shown in Figure 38 (b), the rotation roller brush 405a and the 405b that are supported respectively by the back shaft 452a of can free lifting and can straight line moving and 452b are set, make it to move matchingly with the moving of roller sliding contact surface of pattern roller 483a and 483b and film 401.In addition, longer by a side who makes rotation roller brush 405a and 405b for axis direction length than the opposing party, just can make rotation roller brush 405a and 405b staggered when opposite direction is advanced mutually.Like this, just can apply contact force all the time to the roller sliding contact surface of pattern roller 483a and 483b and film 401.Brush the optimum condition of density, head end shape and material on the crooked recovery rate of the rough lumber 451 of 405a and 405b, diameter, length, the brush sliding contact surface about rotating roller, identical with the situation of rotation roller brush 405 of narrating in described (1).
And, in the device shown in Figure 35～Figure 38,, also can form the wire trace of inclination with respect to the direct of travel of film 401 by suitably changing operating condition etc.In addition, in the device shown in Figure 35～Figure 38, though the situation that possesses Ring form brush as the film dipper crowding gear is narrated, the air that also can possess narration in described (1) blows mechanism.
In the film of the tearability with straight line of the method manufacturing of narration, the degree of depth of described wire trace is preferably 1～40% of film thickness more than utilizing.So just can realize film strength and good straight line tearability simultaneously.Preferred 0.1～10 μ m of the degree of depth of wire trace, preferred 0.1～10 μ m of its width, preferred 10～200 μ m in the interval between the wire trace.
[8] minute aperture of film is processed
Form the tearability that memory PBT laminate film has straight line in order to make, also can in the middle of PBT film, stiffness films and the sealing film any one comprehensively on form fine through hole.Fine through hole is preferably formed on sealing film especially.Minute aperture preferably has the average pore size of 0.5～100 μ m, and distribution density 500/cm preferably approximately 2More than.When the distribution density of minute aperture less than about 500/cm 2The time, tearability is just insufficient.And as long as how many upper limits of minute aperture density can be provided with feasible technically, is not particularly limited.
When on film, forming minute aperture, for example can adopt Japan's special permission No. 2071842 or the special method of being announced in 2002-059487 number of opening.For example when utilizing Japan to specially permit the method for being announced in No. 2071842, a plurality ofly has the Mohs' hardness in sharp-pointed bight between second roller of first roller of the particle more than 5 (roller identical) and surface smoothing by film being passed adhered to from the teeth outwards with the pattern roller 402 of explanation in described [7], and regulate passing the pushing force of the film between each roller, the pellicular front that contacts with each roller is reached evenly on the whole, thereby can on film, form a plurality of described minute apertures with the sharp-pointed bight of a plurality of particles on the first roller surface.As second roller, for example can use iron class roller, the surface implemented the iron class roller, stainless steel-like roller, special steel rider etc. of plating Ni, plating Cr etc.
[9] evaporation of pottery or metal
In order to improve the gas-barrier property that forms memory PBT laminate film, can be to PBT film vapor deposition metal, pottery etc., or coated with resins.As the concrete example of the pottery of institute's evaporation, can enumerate silica, aluminium oxide etc.The evaporation of metal, pottery etc. can utilize known method to carry out.
[10] functional polyalkylene mutual-phenenyl two acid bromide two alcohol ester film
(1) straight line tearability polybutylene terephthalate (PBT) film
Straight line tearability PBT film of the present invention is the film that has formed many parallel in fact wire traces according to the method for narration in described [7] at least one face of PBT film.Thus, have straight line tearability, and the orientation of this and material film is irrelevant, thereby can begins along wire trace smooth tearing from position arbitrarily to a direction.When using straight line tearability PBT thin film fabrication packaging bag of the present invention, band shape that just can head end does not attenuate when can keep certain width breaks a seal.In addition, straight line tearability PBT film of the present invention does not run through owing to the wire trace, and is therefore good aspect gas-barrier property.
Though be not particularly limited for employed PBT film in the manufacturing of straight line tearability PBT film, preferably utilize the film of the manufacture method acquisition of narration in described [6].The PBT film that utilizes the manufacture method acquisition of narrating in described [6] is because percent thermal shrinkage is less, and therefore under the situation that has formed the evaporation layer, the evaporation layer is stable.
The degree of depth of the wire trace of straight line tearability PBT film is preferably 1～40% of film thickness.So just can realize film strength and good straight line tearability simultaneously.Preferred 0.1～10 μ m of the degree of depth of wire trace, preferred 0.1～10 μ m of its width, preferred 10～200 μ m in the interval between the wire trace.
The thickness of straight line tearability PBT film is 5～50 μ m preferably approximately, more preferably about 10～20 μ m, for example about 12 μ m.If the thickness of about 5～50 μ m then has enough fragrance protectiveness and gas-barrier property, and glossiness and printing characteristic are also good.
In addition, can evaporation metal on straight line tearability PBT film, pottery etc., or coated with resins.As concrete example, can steam coating silicon dioxide, aluminium oxide etc.By this kind of evaporation pottery, can improve the gas-barrier property of straight line tearability PBT film.The evaporation of metal, pottery etc. can utilize known method to carry out.But metal, pottery etc. also evaporation form on any one party of face or non-formation face at the wire trace of film.
In addition, straight line tearability PBT film can adopt the laminate film that has possessed the layer of being made by general purpose polyolefin and special polyolefin.Specifically, be low density polyethylene (LDPE) (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) (HDPE), no extended polypropylene (CPP), straight chain shape low density polyethylene (LDPE) (L-LDPE), ultra-low density polyethylene (VLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene acrylic acid co polymer (EAA), ethylene methacrylic acid copolymer (EMAA), ethylene ethyl acrylate copolymer (EEA), ethylene methacrylic acid methyl terpolymer (EMMA), ethylene methyl acrylate copolymer (EMA), ionomer (IO) etc.In addition, in order to improve moisture resistance, gas-barrier property, preferably possessed aluminium foil, evaporation the pet film of silica, the films such as pet film that evaporation has aluminium oxide have been arranged in the intermediate layer.
In addition, when forming laminate film, also can be by after the PBT film having been implemented the processing that the wire trace is set described later, with other film or stackedization of thin-film laminate or make with other film or stackedization of thin-film laminate across described intermediate layer.Stackedization compressed into capable after between each layer adhesive linkage being set by extruding layer.As adhesive linkage preferably polyethylene layer.
Purposes as the straight line tearability PBT film that has formed the wire trace on the direct of travel (length direction) of film has bar-shaped dessert packaging bag.The straight line tearability PBT film of the wire trace with length direction of the application of the invention, band shape Kaifeng that can head end can not attenuate when keeping certain width, so dessert just can be damaged.In addition, though rice dumplings etc. have used the packing of OPP film and Kaifeng width to be pasted with slitting (tear tape) matchingly, but therefore the straight line tearability PBT film that has formed the wire trace in the longitudinal direction of the present invention does not just need tear tape owing to can break a seal keeping under the condition of A/F.
Formed the purposes of the straight line tearability PBT film of the wire trace that tilts as direct of travel, the packaging bag that has pulverous medicinal, packed meal to use etc. with flavoring with respect to film.The straight line tearability PBT film of the wire trace with incline direction of the application of the invention just can easily be torn the bight inclination of packaging bag.
Formed the purposes of the straight line tearability PBT film of wire trace as width (laterally), the bar-shaped packaging bag of Powdered instant food has been arranged at film.The straight line tearability PBT film with horizontal wire trace of the application of the invention, the just bar-shaped packaging bag that can increase gradually with low-cost manufacturing demand.
The method of record in can be according to described [8] on straight line tearability PBT film is formed uniformly a plurality of fine through holes and/or through hole not again.So not only the tearability of straight line can further improve, and also can give tearability to the part beyond the wire trace direction.
(2) porous polybutylene terephthalate (PBT) film
Porous PBT film of the present invention is the method according to record in described [8], has been formed uniformly a plurality of fine through holes and/or the film of through hole not on the PBT film.The distortion retentivity height of porous PBT film of the present invention thus can not break during distortion, and warping property is good.Minute aperture preferably has the average pore size of 0.5～100 μ m, and density 500/cm preferably approximately 2More than.When the density of minute aperture less than about 500/cm 2The time, the distortion retentivity is just insufficient.
Though employed PBT film is not particularly limited in the manufacturing for porous PBT film, preferably utilize the film of the manufacture method acquisition of narration in described [6].
Porous PBT film of the present invention not forfeiture has been kept the characteristic of practical aspect as the hear resistance of the excellent characteristic of PBT film, fragrance protectiveness, resistance to water etc., and is very useful as the packaging material that possessed good tearing property and warping property.But when the packaging material of being made by porous PBT film of the present invention are required gas-barrier property, the film that uses minute aperture not run through.
As mentioned above, describe the present invention, but the present invention is not limited to these, only otherwise change purport of the present invention, can implements various changes with reference to accompanying drawing.
Utilize following embodiment that the present invention is further elaborated, but the present invention is not limited thereto.
Embodiment 1
(trade name " ト レ コ Application 1209X01 " reaches " ト レ コ Application 1200S " to use 2 kinds of PBT resins, be TORE (strain) system), the mould of the external diameter 150mm at mould edge (die lip) is installed, the extrusion resin temperature is made as 230 ℃, extrusion resin pressure is made as 11.8MPa (120kgf/cm 2), extrude tubular film with blow-up ratio 1.5～2.5, spraying humidifying air and traction when cooling off, obtained film from first～the 3rd air ring and cooling air blowing out device.Rerum natura to the film of gained is measured with following method.The results are shown in the table 1.
Average thickness: utilize amesdial to measure.
Average order is paid: utilize precision balance to measure the weight of the rectangle test film of 10 * 10cm.
Tensile break strength: with ASTM D882 is the tensile break strength that benchmark is measured the rectangle test film of wide 10mm.
The tension failure ductility: with ASTM D882 is the tension failure ductility that benchmark is measured the rectangle test film of wide 10mm.
Percent thermal shrinkage: measured respectively with the operating direction (MD) of film after respectively exposing 10 minutes under 100,130,160,175,200 ℃, the shrinkage factor of vertical direction (TD).
Table 1
Figure C0382530100541
Annotate: (1) east beautiful (strain) trade name " ト レ コ Application "
As shown in table 1, even the PBT film that utilizes manufacture method of the present invention to obtain is heated to 200 ℃, percent thermal shrinkage is 0 substantially also, has very good heat-resisting shrinkage.

Claims (36)

1. shape memory polybutylene terephthalate (PBT) laminate film, have (a) polybutylene terephthalate (PBT) film and (b) by from paper sheet, other resin film and metal forming at least a other film or the thin-film laminate of making selected, it is characterized in that the temperature T below the glass transition temperature of described polybutylene terephthalate (PBT) 1Be treated to first shape by figuration down, in the temperature T that surpasses described glass transition temperature 2Under be deformed and be processed as second shape, then by being cooled to the temperature T below the described glass transition temperature 3And be fixed to described second shape, by being exposed on described temperature T 1More than, get back to described first shape from described second shape.
2. shape memory polybutylene terephthalate (PBT) laminate film according to claim 1 is characterized in that described temperature T 1Be below 35 ℃, described temperature T 2Be more than 45 ℃～below 65 ℃, do not contain 45 ℃, described temperature T 3It is 15～25 ℃.
3. shape memory polybutylene terephthalate (PBT) laminate film according to claim 2 is characterized in that described temperature T 1It is 15～25 ℃.
4. shape memory polybutylene terephthalate (PBT) laminate film, have (a) polybutylene terephthalate (PBT) film and (b) by from paper sheet, other resin film and metal forming at least a other film or the thin-film laminate of making selected, it is characterized in that, more than the glass transition temperature of described polybutylene terephthalate (PBT) film～it is below fusing point and do not contain the temperature T of Tg and fusing point 4Be treated to first shape by figuration down, by being cooled to the temperature T below the described glass transition temperature 5And be fixed to described first shape, more than described glass transition temperature～described temperature T 4Below and do not contain glass transition temperature and T 4Temperature T 6Under be deformed and be processed as second shape, and by being cooled to the temperature T below the described glass transition temperature 7And be fixed to described second shape, by being exposed on described temperature T 4More than, get back to described first shape from described second shape.
5. shape memory polybutylene terephthalate (PBT) laminate film according to claim 4 is characterized in that described temperature T 4Be 75～100 ℃, described temperature T 5Be below 40 ℃, described temperature T 6Be 45～65 ℃, described temperature T 7Be below 40 ℃.
6. shape memory polybutylene terephthalate (PBT) laminate film according to claim 5 is characterized in that described temperature T 4It is 90～100 ℃.
7. according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6, it is characterized in that described first is shaped as the crimping shape, described second is shaped as smooth shape or inverse hemming shape.
8. according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6, it is characterized in that described first is shaped as the pallet shape, described second is shaped as smooth shape.
9. according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6, it is characterized in that layer has described polybutylene terephthalate (PBT) film, described paper sheet and sealing film in constituting successively.
10. according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6, it is characterized in that layer has described polybutylene terephthalate (PBT) film, described paper sheet, stiffness films and sealing film in constituting successively.
11., it is characterized in that layer has described polybutylene terephthalate (PBT) film, stiffness films and sealing film in constituting successively according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6.
12. according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6, it is characterized in that described polybutylene terephthalate (PBT) film is bonding with other film or thin-film laminate under the elongation state that has kept elastic restoring force.
13. shape memory polybutylene terephthalate (PBT) laminate film according to claim 12, it is characterized in that described polybutylene terephthalate (PBT) film is keeping with other film or thin-film laminate bonding under the elongation state of 1～3% ductility.
14. according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6, it is characterized in that, described polybutylene terephthalate (PBT) film is the film that utilizes the expansion-molded method of air cooling to obtain, from being located near first air ring ejection humidifying air the annular die, the neck of bubble is cooled to temperature below 130 ℃, spray humidifying air from being configured in from described annular die is separated by second air ring of position of top of 5～10 times distance of bore of annular die, described bubble is cooled to temperature below 80 ℃, and by will be located at net cylindraceous between described first air ring and described second air ring around be cooled to certain temperature, make the chilling temperature stabilisation of the bubble that utilizes described first air ring and the acquisition of described second air ring, blow-up ratio is made as 1.5～2.8, the extrusion resin temperature is made as 210～250 ℃, extrusion resin pressure is made as 9.8～13.7MPa.
15. packaging material is characterized in that, are made by any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～14.
16. a cap for container body is characterized in that, is made by any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～14.
17. the manufacture method of a shape memory polybutylene terephthalate (PBT) laminate film, be to have (a) polybutylene terephthalate (PBT) film and (b) by from paper sheet, select in other resin film and the metal forming at least a make other film or the manufacture method of the shape memory polybutylene terephthalate (PBT) laminate film of thin-film laminate, it is characterized in that, (1) laminate film that film or thin-film laminate with described polybutylene terephthalate (PBT) film and other are laminated, when keeping first shape, the temperature T below the glass transition temperature of described polybutylene terephthalate (PBT) 1Under carry out figuration and handle, (2) with the figuration laminate film of gained in the temperature T that surpasses described glass transition temperature 2Following deformation processing is second shape, and (3) are then by being cooled to the temperature T below the described glass transition temperature 3And be fixed as described second shape.
18. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 17 is characterized in that, described first is shaped as the crimping shape, and described second is shaped as smooth shape or inverse hemming shape.
19. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 18, it is characterized in that, by with the roller conveyance with described polybutylene terephthalate (PBT) film and described other film or the bonding laminate film that obtains of thin-film laminate, along the periphery of described roller in described temperature T 1Under handle, make and to have given the laminate film of crimping shape.
20. the manufacture method according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 17～19 is characterized in that, with described temperature T 2Under deformation processing carried out for 30～60 seconds.
21. the manufacture method according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 17～19 is characterized in that described temperature T 1Be below 35 ℃, described temperature T 2Be more than 45 ℃～below 65 ℃, do not contain 45 ℃, described temperature T 3It is 15～25 ℃.
22. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 21 is characterized in that, described temperature T 1It is 15～25 ℃.
23. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 18 is characterized in that, the described laminate film of having given the crimping shape is being cooled to described temperature T 3Afterwards, reel to its inverse hemming direction.
24. manufacture method according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 17～19, it is characterized in that, when the film of bonding described polybutylene terephthalate (PBT) film and other or thin-film laminate, described polybutylene terephthalate (PBT) film is applied tension force more than the 4kgf/m width.
25. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 24 is characterized in that, described tension force is 10～20kgf/m width.
26. the manufacture method of a shape memory polybutylene terephthalate (PBT) laminate film, be to have (a) polybutylene terephthalate (PBT) film and (b) by from paper sheet, select in other resin film and the metal forming at least a make other film or the manufacture method of the shape memory polybutylene terephthalate (PBT) laminate film of thin-film laminate, it is characterized in that, (1) by (i) when keeping first shape, more than the glass transition temperature of described polybutylene terephthalate (PBT)～it is below fusing point and do not contain the temperature T of this glass transition temperature and fusing point 4Down described polybutylene terephthalate (PBT) film being carried out figuration, to handle the back stacked with other film or thin-film laminate, or (ii) make in advance after the laminate film of described polybutylene terephthalate (PBT) film and other film or thin-film laminate, when keeping first shape, in described temperature T 4Down this is carried out figuration and handle, make the figuration laminate film with described first shape, (2) are cooled to temperature T below the described glass transition temperature by the figuration laminate film with gained 5And be fixed as described first shape, (3) then with described figuration laminate film more than described glass transition temperature～described temperature T 4Below and do not contain glass transition temperature and T 4Temperature T 6Following deformation processing is second shape, and afterwards, (4) are by being cooled to the temperature T below the described glass transition temperature 7And be fixed as described second shape.
27. the manufacture method of shape memory poly terephthalic acid fourth two diol ester laminate films according to claim 26 is characterized in that, described first is shaped as the crimping shape, and described second is shaped as smooth shape or inverse hemming shape.
28. the manufacture method according to claim 26 or 27 described shape memory polybutylene terephthalate (PBT) laminate films is characterized in that described temperature T 4Be 75～100 ℃, described temperature T 5Be below 40 ℃, described temperature T 6Be 45～65 ℃, described temperature T 7Be below 40 ℃.
29. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 27, it is characterized in that, by with described polybutylene terephthalate (PBT) film with conveyance when a side's of a pair of warm-up mill periphery contacts, along the periphery of described warm-up mill in described temperature T 4Under carry out heat treated, give the crimping shape to described polybutylene terephthalate (PBT) film, make afterwards gained edge-rolling polybutylene terephthalate (PBT) film and described other film or thin-film laminate through between described a pair of warm-up mill and bonding continuously, make and given the laminate film of crimping shape.
30. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 27, it is characterized in that, by with warm-up mill conveyance described polybutylene terephthalate (PBT) laminate film, along the periphery of described warm-up mill in described temperature T 4Under handle, make and to have given the laminate film of crimping shape.
31. manufacture method according to any described shape memory polybutylene terephthalate (PBT) laminate film in claim 26 or 27, it is characterized in that, with described polybutylene terephthalate (PBT) film and described other film or thin-film laminate when bonding, described polybutylene terephthalate (PBT) film is applied tension force more than the 4kgf/m width.
32. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 31 is characterized in that, described tension force is 10～20kgf/m width.
33. the manufacture method of shape memory polybutylene terephthalate (PBT) laminate film according to claim 27 is characterized in that, the described laminate film of having given the crimping shape is being cooled to described temperature T 5After, reel to its inverse hemming direction, in described temperature T 6Under carry out heat treated, be cooled to described temperature T 7
34. manufacture method with container of shape memory polybutylene terephthalate (PBT) laminate film system lid, it is characterized in that, be that the lid heat seal that will be made by any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～14 is on container, manufacturing has possessed the method for the container of described lid, in the temperature T of the glass transition temperature that surpasses described polybutylene terephthalate (PBT) 8Down, when making described shape memory polybutylene terephthalate (PBT) laminate film maintenance smooth, anneal, utilize and cover the material sealing mechanism and the smooth shape memory polybutylene terephthalate (PBT) laminate film of gained is carried out stamping-out process, and carry out heat seal, the lid of being made by described shape memory polybutylene terephthalate (PBT) laminate film is sticked on the container.
35. the manufacture method with container of shape memory polybutylene terephthalate (PBT) laminate film system lid according to claim 34 is characterized in that, described annealing was carried out for 30～60 seconds.
36., it is characterized in that described temperature T according to claim 34 or 35 described manufacture methods with container of shape memory polybutylene terephthalate (PBT) laminate film system lid 8It is 80～120 ℃.
CNB038253011A 2002-09-20 2003-09-22 Shape-memory polybutylene terephthalate laminated film, and its production method and use, and polybutylene terephthalate film producing method Expired - Fee Related CN100439098C (en)

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