CN100413673C - Method and apparatus for producing polybutylene terephthalate film, and shape-memory polybutylene terephthalate laminated film - Google Patents

Abstract

A method for producing a polybutylene terephthalate film by the air-cooling inflation method involving inflating a tube of a molten polybutylene terephthalate resin extruded from a ring die by means of the injection of air, characterized in that the resin is extruded under a resin pressure of 8.3 to 13.7 MPa and at a resin temperature of from the melting point of the above polybutylene terephthalate resin - 15 degree C to the above melting point - 5 degree C.

Description

The manufacture method of polybutylene terephthalate (PBT) film and manufacturing installation and shape memory polybutylene terephthalate (PBT) laminate film

Technical field

But be the method and the device of the good polybutylene terephthalate (PBT) film of the uniformity of film thickness, heat-resisting shrinkage and mechanical strength and the shape memory polybutylene terephthalate (PBT) laminate film that can be used as packaging material with this polybutylene terephthalate (PBT) film though the present invention relates to a kind of manufacturing.

Background technology

Polybutylene terephthalate (PBT) (PBT) resin is because aspects such as mechanical strength, hear resistance, resistance to chemical reagents, resistance to impact, electrical property are good, therefore receive concern as engineering with plastics all the time, can be used as the injection-molded article of automobile component, electrical and electronic parts etc.PBT is because also good aspect gas-barrier property or fragrance protectiveness, and is if therefore can make the good thin PBT film of the uniformity of thickness or heat-resisting shrinkage or comprise its laminate film, then very useful as packaging material.But in PBT, there is following problem, promptly, (a) behind crystallization, after the extension along its length, can't carry out, (b) because fusion tension force is lower to horizontal extension, therefore can't carry out extension rapidly, (c) because glass transition temperature near normal temperature, therefore the film fold takes place easily.Thus, it is very difficult the polybutylene terephthalate (PBT) resin being made the beautiful packaging film that has homogeneous thickness about 10～30 μ m.

The method of making the PBT film as the not extension film that utilizes the T modulus method to make being implemented twin shaft extend, the spy opens and has proposed for clear 49-80178 number under the temperature of regulation extension film not to be carried out the method that twin shaft extends simultaneously, and special public clear 51-40904 number and special opening have proposed for clear 51-146572 number under the temperature of regulation and speed extension film is not carried out the method that twin shaft extends successively.But in these methods, be to extend to carry out twin shaft by the not extension film that fusion polybutylene terephthalate (PBT) resin chilling is made, so the manufacturing procedure complexity, the percent thermal shrinkage of the film of gained is also very big.For extending, the twin shaft that makes the polybutylene terephthalate (PBT) film is more prone to, method of the method stacked with other resin film, mixed with resin that intermiscibilities such as polyethylene, polypropylene is good etc. has been proposed, but in all methods, all be difficult to filming extremely as the thickness about 10～30 μ m of packing film the best.

In general, compare with the T modulus method, the productivity ratio of expansion-molded method is higher, is suitable for the manufacturing of thin film.But in the polybutylene terephthalate (PBT) film made from (inflation) forming process that expands, there is the problem that the thickness inequality is more, percent thermal shrinkage is bigger.For example, special fair 7-33048 number proposition utilizes expansion-molded method inherent viscosity to be carried out the method for filming at the PBT resin more than 1.0.Wherein the extrusion resin temperature satisfies following formula:

Fusing point (℃)＜the extrusion resin temperature (℃)＜fusing point-26+53 * inherent viscosity (℃)

But, in this method, and the optimization of the combination of be unrealized extrusion resin temperature and extrusion resin pressure, the PBT film of gained has bigger percent thermal shrinkage.

Though PBT is a kind of of polyester, also has PETG (PET) as the representative polyester of another kind.The PET film has good gas-barrier property, the dimensional stability to heat, filling machine adaptability characteristics such as (not having crimping), and the laminate film that therefore contains the PET film for example is used as the lid material use of container for fast food.But,, therefore relatively poor aspect the character that lid is maintained the state in Kaifeng (stationary state (dead hold) property) because PET film stiffness is bigger.Thus, lid will be closed behind Kaifeng easily, thereby is difficult to inject hot water.

For constituting instant noodles for the laminate film of employed lid material in the container etc., requiring when container is sealed not can crimping and can keep the state (having stationary state) of crimping when peeling off from container.Usually the lid material is thermally sealed on the container, as long as therefore have before heat seal not crimping, and the heat when utilizing heat seal and the shape memory of crimping is just very useful.

But also do not find up to now by the packaging material that the laminate film with shape memory is made.In general, the spring rate of the resin with shape memory before and after glass transition temperature alters a great deal.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) then 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, be fixed as shape N by being made as the temperature that is lower than glass transition temperature, (3) by being heated to more than the glass transition temperature, under the condition that does not apply external force, return to shape M.Though PET is the material with shape memory, because glass transition temperature is approximately 70～80 ℃, therefore needed temperature is too high in shape is recovered.

Opposite with it, PBT has about 20～45 ℃ glass transition temperature, therefore just can make the packaging material that can utilize the shape memory under applied temps.For example the spy opens flat 2-123129 number and records the shape memory resin of being made by the block copolymer of PBT and aliphatic poly lactone.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 all are not the shape memory resin filmization with PBT.

Summary of the invention

Therefore, the objective of the invention is to, is the method and the device of the good polybutylene terephthalate (PBT) film of the uniformity of film thickness, heat-resisting shrinkage and mechanical strength though manufacturing is provided.

Another object of the present invention is, the laminate film of the polybutylene terephthalate (PBT) with good shape memory and heat-resisting dimensional stability is provided.

The result who furthers investigate in view of described purpose, the inventor have found the following fact.

(a) in the manufacture method of the PBT film that polybutylene terephthalate (PBT) (PBT) resin is utilized the expansion-molded method filming of air cooling (air-cooled), fusing point-15 by the extrusion resin temperature being made as the PBT resin ℃～described fusing point-5 ℃, and extrusion resin pressure is made as 8.3～13.7MPa, is the good PBT film of the uniformity of film thickness, heat-resisting shrinkage and mechanical strength though just can make.

(b) (1) laminate film of being laminated for film or thin-film laminate with described PBT film and other, when keeping 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, obtain PBT laminate film with good shape memory and heat-resisting dimensional stability.

(c) (1) makes described PBT film and other the film or the laminate film of thin-film laminate in advance by (i), when keeping first shape, and the temperature T that (is not containing Tg) more than the Tg～(do not containing fusing point) below the fusing point ₄Down it is carried out that figuration is handled or (ii) when keeping first shape in described temperature T ₄Down described PBT film being carried out figuration, to handle the back stacked with other film or thin-film laminate, makes the laminate film with first shape, and (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, obtain PBT laminate film with good shape memory and heat-resisting dimensional stability.

The present invention is based on this kind invention and finishes.

Promptly, the feature of the manufacture method of polybutylene terephthalate (PBT) film of the present invention is, the pipe of the fusion polybutylene terephthalate (PBT) resin that utilizes the air cooling plavini to make to extrude from annular die expands because of the injection of air, the extrusion resin temperature is made as the fusing point-15 ℃～described fusing point-5 ℃ of described polybutylene terephthalate (PBT) resin, and extrusion resin pressure is made as 8.3～13.7MPa.

The inherent viscosity of described polybutylene terephthalate (PBT) resin preferred 0.8～1.5.Preferred 0.8～the 1.2mm in gap at mould edge (lip), the preferred 120～250mm of mode diameter.Blow-up ratio preferred 2.0～4.0.By blow-up ratio is made as 2.0～4.0, bubble (bubble) is extended well to length direction and horizontal balance simultaneously.

In the manufacture method of polybutylene terephthalate (PBT) film of the present invention, preferably (1) is by from being located near the first hot blast blowing out device ejection hot blast the described annular die, the neck of described bubble is slowly cooled to described fusing point-40 ℃～described fusing point-25 ℃, (2) by second hot blast blowing out device ejection hot blast from the top of being located at the described first hot blast blowing out device, the bulge of described bubble is slowly cooled to described fusing point-70 ℃～described fusing point-40 ℃, (3) by the 3rd hot blast blowing out device ejection hot blast from the top of being located at the described second hot blast blowing out device, frost line (frostline) zone of described bubble is slowly cooled to described fusing point-130 ℃～described fusing point-90 ℃, (4) utilize the certain interval of being separated by to be arranged on the next door on every side in the bubble zone of described frost line top, described bubble zone is cut off with outside atmosphere, and will upwards blow along the outside in described bubble zone from the hot blast of described first～the 3rd hot blast blowing out device ejection.

For a plurality of hot blast outlets are set on described next door, and the hot blast that blows out from described first～the 3rd hot air apparatus is carried out rectification, the inboard that is preferably in described next door is provided with cowling panel.Because the effect of the hot blast that sprays from the described second hot blast blowing out device, the bulge of described bubble is slowly cooled when being held non-crystal state.Temperature for Tg to Tg+65 ℃ of the glass transition temperature that described bubble zone remained on described polybutylene terephthalate (PBT) resin is preferably on the described next door heating arrangements is set.

In order to prevent the rolling of described bubble, preferably described bubble zone is surrounded with cylindric net.Preferred 25～50 ℃ of the temperature of the hot blast that from described first and second hot blast blowing out device, sprays.The temperature that the glass transition temperature of the preferred described polybutylene terephthalate (PBT) of temperature of the hot blast that sprays from described the 3rd hot blast blowing out device is Tg to Tg+65 ℃.

Utilizing the crystallization degree of the film of air cooling plavini acquisition of the present invention is 35～40%, and the percent thermal shrinkage of length direction and width is below 0.4%.

The air cooling swelling film of gained also can carry out cold extension along single shaft or twin shaft again.The uniformity of thickness and the transparency will further improve like this.Cold extension is preferably under the temperature of Tg to Tg+60 ℃ of glass transition temperature of described polybutylene terephthalate (PBT) resin to be carried out.Utilize the formation of the tubular film that the air cooling plavini carries out and the cold extension of described single shaft or twin shaft preferably to carry out continuously.Carry out cold extension along single shaft or twin shaft after also can being divided into two parts at tubular film with gained.Utilize the two halves of the formation of the tubular film that the air cooling plavini carries out, described tubular film to cut apart and described single shaft or the cold extension of twin shaft are preferably carried out continuously.

The feature of the manufacturing installation of polybutylene terephthalate (PBT) film of the present invention is, possess (a) with fusion polybutylene terephthalate (PBT) resin with tubular extruded annular die, (b) in the polybutylene terephthalate (PBT) pipe of gained, inject air and form the mechanism of bubble, (c) be located near the of described annular die and with the slow first hot blast blowing out device of cooling of the neck of described bubble, (d) be located at the top of the described first hot blast blowing out device and with the slow second hot blast blowing out device of cooling of the bulge of described bubble, (e) be located at the top of the described second hot blast blowing out device and the 3rd hot blast blowing out device that the frost line zone of described bubble is slowly cooled off, (f) be located at the top of described the 3rd hot blast blowing out device and being located at than described frost line more by around the bubble zone of top, described bubble zone is cut off with outside atmosphere, and the next door that the hot blast that will spray from described first～the 3rd hot blast blowing out device upwards blows along the outside in described bubble zone, described next door has a plurality of hot blast outlets.

In the manufacturing installation of the present invention, the inboard that is preferably in described next door is provided with cowling panel.In order to prevent the rolling of described bubble, the inboard that is preferably in described next door is provided with the cylindric net that surrounds described bubble zone.Preferably utilize the bulge slowly cooling under non-crystal state of the hot blast that from the described second hot blast blowing out device, sprays with described bubble.Preferably also has mechanism with the cold extension of air cooling swelling film of gained.

Air cooling expansion mechanism and described cold extension mechanism with described annular die, described air injecting mechanism, the described first hot blast blowing out device, the described second hot blast blowing out device, described the 3rd hot blast blowing out device and described next door preferably dispose continuously along the direct of travel of air cooling swelling film.

Manufacturing installation of the present invention preferably possesses the niproll of the tubular film traction that will utilize described air cooling expansion mechanism to form, and between described air cooling expansion mechanism and described cold extension mechanism, the device that also has the ear end position (marginal position) of the laminar described tubular film that (a) control drawn by described niproll, (b) with described ear end position controlled described tubular film be divided into the cutting mechanism of two halves, described air cooling expansion mechanism, described marginal position controlling organization, described cutting mechanism, described cold extension mechanism is preferably arranged continuously with this order.

The feature of shape memory polybutylene terephthalate (PBT) laminate film of the present invention is, have polybutylene terephthalate (PBT) film that (1) utilize manufacture method of the present invention to obtain, (2) by from paper sheet, other resin film and metal forming at least a other film or the thin-film laminate of making selected, 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 of the present invention, the temperature of getting back to described first shape is below the glass transition temperature of described polybutylene terephthalate (PBT).Get back to more preferably 15～25 ℃ of the temperature of described first shape.

In the preferred example of other of shape memory polybutylene terephthalate (PBT) laminate film of the present invention, the temperature of getting back to described first shape surpasses its fusing point of the glass transition temperature of described polybutylene terephthalate (PBT)～be lower than.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 can be with shape memory polybutylene terephthalate (PBT) laminate film along described wire trace in fact along smooth tearing.1～40% of the preferred described polybutylene terephthalate (PBT) film thickness of the degree of depth of described wire trace.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.

Description of drawings

Fig. 1 is the schematic diagram that an example of the device utilize the polybutylene terephthalate (PBT) film that the expansion-molded method of air cooling of the present invention obtains is made in expression.

Fig. 2 is that expression will be steeped the slowly schematic section of an example of the device of cooling.

Fig. 3 (a) is the vertical view of an example of expression cowling panel.

Fig. 3 (b) is the vertical view of another example of expression cowling panel.

Fig. 3 (c) is the vertical view of another example of expression cowling panel.

Fig. 4 (a) is PBT film partial cross section's diagrammatic side view of an example of the device that extends of twin shaft one by one that expression will utilize the expansion-molded manufactured of air cooling.

Fig. 4 (b) is the diagrammatic top view of the device of Fig. 4 (a).

Fig. 5 (a) is the diagrammatic side view of an example of the device of the expression PBT film cold extension along its length that will utilize the expansion-molded manufactured of air cooling.

Fig. 5 (b) is the diagrammatic side view of another example of the device of the expression PBT film cold extension along its length that will utilize the expansion-molded manufactured of air cooling.

Fig. 5 (c) is the diagrammatic side view of another example of the device of the expression PBT film cold extension along its length that will utilize the expansion-molded manufactured of air cooling.

Fig. 6 is the diagrammatic side view of an example of the device of the expression cold extension of PBT film utilization string row's mode that will utilize the expansion-molded manufactured of air cooling.

Fig. 7 is the sectional view of the layer configuration example of expression shape memory PBT (PBT) thin-film laminate.

Fig. 8 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.

Fig. 9 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.

Figure 10 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.

Figure 11 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.

Figure 12 is other the sectional view of layer configuration example of expression shape memory PBT laminate film.

Figure 13 is the schematic diagram of an example of the expression device of making shape memory PBT laminate film.

Figure 14 is other the schematic diagram of example of the expression device of making shape memory PBT laminate film.

Figure 15 is other the schematic diagram of example of the expression device of making shape memory PBT laminate film.

Figure 16 is other the schematic diagram of example of the expression device of making shape memory PBT laminate film.

Figure 17 is other the schematic diagram of example of the expression device of making shape memory PBT laminate film.

Figure 18 is the schematic diagram of an example of the expression device of making the container have lid.

Figure 19 is the stereogram of the expression container for fast food that will have been broken a seal by the lid that shape memory PBT laminate film of the present invention is made in order to inject hot water.

Figure 20 is that expression will be disconnected 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 21 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 22 is the stereogram of representing the state behind the container Kaifeng that has lid of Figure 21.

Figure 23 is expression food recovers the state of shape with employed shape memory PBT laminate film in the pallet a schematic diagram.

Figure 24 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 25 is illustrated in the device shown in Figure 24, send the partial enlarged drawing of compressed-air actuated state to the top blast of film and pattern roller sliding-contact.

Figure 26 is illustrated in the device shown in Figure 24, and cross-sectional view is amplified in the part of the state of film and pattern roller sliding-contact.

Figure 27 (a) is the front view and the right view of an example of expression nozzle.

Figure 27 (b) is other the front view and the right view of example of expression nozzle.

Figure 27 (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 28 is other the schematic diagram of example that is illustrated in the device that forms the wire trace on the direct of travel of film.

Figure 29 is the stereogram of expression formation with respect to an example of the device of the wire trace of the direct of travel inclination of film.

Figure 30 (a) is illustrated in the device shown in Figure 29, the local amplification plan view of the state of film and the sliding-contact of pattern endless belt.

Figure 30 (b) is the schematic section of seeing from the D direction in Figure 30 (a).

Figure 31 is other the schematic diagram of example of the expression device that forms the wire trace that the direct of travel with respect to film tilts.

Figure 32 is illustrated in the device shown in Figure 31, the local amplification plan view of the state of film and roller formation sliding-contact.

Figure 33 (a) is other the local amplification plan view of example of the expression device that forms the wire trace that the direct of travel with respect to film tilts.

Figure 33 (b) is the schematic diagram of seeing from the E direction in Figure 33 (a).

Figure 34 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 35 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 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 (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 37 (b) is the schematic diagram of seeing from the F direction in Figure 37 (a).

The specific embodiment

[1] manufacture method of polybutylene terephthalate (PBT) laminate film

(I) raw material polybutylene terephthalate (PBT) resin

The polybutylene terephthalate (PBT) (PBT) that becomes raw material is though resin is not particularly limited, and preferably by with 1,4-butanediol and terephthalic acid (TPA) constitute as the homopolymers of constituent.But in the scope of not damaging rerum naturas such as shape memory, heat-shrinkable, 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.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 preferred PBT resin, for example can enumerate the homogeneous PBT resin of selling with trade name " ト レ コ Application " by east beautiful (strain).

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 thermoplastic resin, can enumerate PETG (PET), PEN polyester such as (PEN); Polyphenylene sulfide (PPS); Polyamide (PA); Pi (PI); The inferior acid amides (PAI) of polyamide; Polyether sulfone (PES); Polyether-ether-ketone (PEEK); Merlon; Polyurethane; Fluorine resin; Polyethylene; Polyolefin such as polypropylene; Polyvinyl chloride; Elastomer etc.When containing other thermoplastic resin, if its ratio is counted 100 quality % with PBT resin integral body, then preferred 5～15 quality %, preferred especially 5～10 quality %.So if be not particularly limited, employed in this manual term " polybutylene terephthalate (PBT) resin " should be understood to comprise other these two kinds of implications of composition of thermoplastic resin of PBT and PBT+.

The molecular weight of PBT film is preferably than higher.Molecular weight is high more, and the pipe that then makes the fusion PBT resin of extruding from annular die expands when forming bubble by the injection of air, and the just easy more bulge with bubble remains non-crystal state.Specifically, the IV value (inherent viscosity) preferred 0.8～1.5 of PBT film.

In the PBT resin, can suitably use general thermoplastic resin to reach the known additive that in thermosetting resin, is added according to desired performance, that is, 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.

(II) air cooling is expansion-molded

Fig. 1 represents to utilize the operation of the manufacture method of the PBT film that the expansion-molded method of air cooling of the present invention carries out.By from air injection tube 26, sending into air and be expanded to the film of required width sharp to the tubular film inside of extruding from the annular die 1 that is installed on the extruder 12, be pulled 13 clampings of machine niproll and draw, reeled by wireline reel 14.Annular die 1 has the die head 10 and the weld part 11 of ring-type.Be not particularly limited the mechanism that to enumerate mechanism that air injection tube 26 and air blast are formed by connecting, air injection tube 26 and compressed air pump is formed by connecting etc. for the air injecting mechanism of supplying with the air in tubular film, inject.

When making the PBT film, at first carry out the mixing of PBT resin and required additive etc.By melting temperature and mixing pressure are adjusted, make extrusion resin temperature described later and extrusion resin pressure reach scope of the present invention.For fear of melting temperature reach temperature required more than, in the extruder of single shaft extruder and so on, carry out when mixing, use to have the extruder of athermic spiral structure, or have the extruder of suitable cooling device.

The extrusion resin temperature of PBT resin is made as-15 ℃ of fusing points (if following do not particularly point out then abbreviate " fusing point " as the)～fusing point-5 ℃ of PBT resin, preferably is made as fusing point-10 ℃～fusing point-5 ℃.And the extrusion resin temperature is a temperature of utilizing the Temperature Detector 112 (thermocouple etc.) in the resin stream of weld part 11 of the inlet 111 be located at the outlet 110 that connects extruder 12 and die head 10 to measure.Because the extruded velocity of resin is very fast,, also can be estimated as roughly in the temperature range of fusing point-15 ℃～fusing point-5 ℃ even therefore in the outlet 110 of extruder 12 and the outlet of die head 10.But the structure of weld part 11 is not limited to illustrated structure.For example when the PBT resin is homopolymers, because its fusing point is 220 ℃, so extrusion resin is 205～215 ℃, preferred 210～215 ℃.By the extrusion resin temperature being made as fusing point-15 ℃～fusing point-5 ℃, just can obtain the uniformity and the good PBT film of heat-resisting shrinkage of the higher and thickness of crystallization degree.

Extrusion resin pressure is made as 8.3～13.7MPa (85～140kgf/cm ²).Can't measure the resin pressure in the die head 10 on the formation of device, the pressure of therefore utilization being located at pressure detector 121 mensuration of outlet of extruder 110 is made as extrusion resin pressure.By extrusion resin pressure is made as 8.3～13.7MPa,, also can extrudes and have the resin that can fully form the melt viscosity of bubble even the extrusion resin temperature is fusing point-15 ℃～fusing point-5 ℃.Preferred 9.3～11.8MPa (95～the 120kgf/cm of extrusion resin pressure ²).Extrusion resin pressure can make up the mesh of (screenpack) 120 by the screen pack in the change extruder, or the gap of change circular aperture is adjusted.

Preferred 120～the 250mm of external diameter at the mould edge (die lip) of die head 10, in addition, the preferred 0.8～1.2mm in the gap at mould edge.

The bubble of extruding from annular die 13 not only extends to MD (length direction), and extends to TD (laterally) when the device that is cooled slowly cools off.Among Fig. 2, the bubble cooling device have annular die be located at 1 near the first hot blast blowing out device 20, be located at the top of the first hot blast blowing out device 20 the second hot blast blowing out device 21, be located at the top of the second hot blast blowing out device 21 the 3rd hot blast blowing out device 22, be located at the top of the 3rd hot blast blowing out device next door 23, be located at the inboard in next door 23 heating arrangements 24, be located at inboard (the steeping 3 sides) net 25 cylindraceous in next door 23.And in Fig. 2, the heat-barrier material of the top of annular die 1 is located in 15 expressions, 16 expression guiding rollers.

In the device of above formation, the temperature control of the bubble 3 that forms through the air cooling plavini is depended in the configuration in each hot blast blowing out device 20～22 and next door 23, therefore followingly describes steeping 3 shape and Temperature Distribution.

From the circular aperture 100 of mould 1, extrude the PBT resin or the PBT resin combination of fusion, form bubble 3, but bubble 3 after just having extruded soon becomes thin footpath shape owing to fusion tension force is lower, form so-called neck 31.On neck 31, bubble 3 mainly extends along the MD direction.Then, bubble 3 expands sharp, reaches the bubble diameter of regulation.On this bulge 32, bubble 3 extends simultaneously towards MD direction and TD direction.Bulge 32 roughly above near frost line 34 is arranged, here the PBT resin becomes the cooling curing state.Owing to the next door 23 in the bubble zone 33 of being located at frost line 34 tops and the effect of heating arrangements 24, bubble 3 is further cooled.

If will utilize the expansion-molded method of air cooling of the present invention to obtain the PBT film, need carry out following control to the temperature of steeping each one of 3.

(a) the extrusion resin temperature is controlled to be fusing point-15 ℃～fusing point-5 ℃.

(b) slowly cool to fusing point-40 ℃～fusing point-25 ℃ at neck 31 places.

(c) slowly cool to fusing point-70 ℃～fusing point-40 ℃ at bulge 32 places.

(d) slowly cool to fusing point-130 ℃～fusing point-90 ℃ in the zone of frost line 34.

(e) remain at regional 33 places of bubble more than the Tg of PBT resin below (not containing Tg)～Tg+65 ℃.

Above-mentioned condition (a) for condition (b), when not slowly cooling to fusing point-40 ℃～fusing point-25 ℃ at neck 31 places, just can't realize that fully twin shaft extends in the time of MD and TD direction by bulge 32 below as mentioned above.That is,, just bulge 32 slowly can be cooled off/remains fusing point-70 ℃～fusing point-40 ℃ " condition (c) " by slowly cool to fusing point-40 ℃～fusing point-25 ℃ at neck 31 places.When the PBT resin is homopolymers, preferably neck slowly is cooled to 180 ℃～195 ℃.When bulge 32 not being remained fusing point-70 ℃～fusing point-40 ℃, the fusion tension force that does not just have appropriateness at bulge 32 places can be with the master that extends to of MD, can't filming.When making bulge 32 be lower than fusing point-70 ℃, crystallization can take place, therefore just can't keep non-crystal state.When the PBT resin is homopolymers, preferably bulge 32 is slowly cooled to 150～180 ℃.

In order to satisfy this kind temperature conditions, preferably blow-up ratio (bulb diameter/mode diameter) is made as 2.0～4.0.Especially preferably blow-up ratio is made as 2.0～2.8.

For condition (d), slowly cool to fusing point-130 ℃～fusing point-90 ℃ by bubble temperature with the zone of frost line 34, just can realize steeping 3 twin shaft in the time of MD and TD fully and extend.When the bubble temperature was lower than fusing point-130 ℃ in the zone of frost line 34, the film fold might take place.When the PBT resin was homopolymers, preferably the zone with frost line 34 slowly cooled to 90～130 ℃.

For condition (e), by remaining more than the Tg of PBT resin below (not containing Tg)～Tg+65 ℃ will steeping 3 above the frost line 34, just can prevent the generation of film fold, and can make uniformly the formation stabilisation of thin bubble 3.Preferably will steep zone 33 and remain 90～110 ℃.The temperature that to steep zone 33 when next door 23 and heating arrangements 24 are not set remains on Tg when following, might cause uneven extension, steeps 3 integral body thus and will become unstable.The Tg of PBT resin is generally 22～45 ℃.Tg can JIS K7121 be that benchmark is measured.

Among the present invention, as shown in Figure 2, preferably will steep the periphery in zone 33 and further surround with cylindric net 25.So just can make the further stabilisation of temperature in bubble zone 33, and can prevent to steep 3 rolling.

In order to carry out the temperature control of aforesaid bubble 3, the configuration of the first hot blast blowing out device 20, the second hot blast blowing out device 21, the 3rd hot blast blowing out device 22, next door 23, heating arrangements 24 and cylindric net 25 is as follows.

(i) the first hot blast blowing out device 20

Be located at from the very near position of annular die 1,, make the temperature of neck 31 slowly cool to fusing point-40 ℃～fusing point-25 ℃, preferred 25～50 ℃ of the temperature of this kind hot blast by the ejection hot blast.

The (ii) second hot blast blowing out device 21

Be located at bulge 32 under, by the ejection hot blast, make the temperature of bulge 32 slowly cool to fusing point-70 ℃～fusing point-40 ℃.Preferred 25～50 ℃ of the temperature of this kind hot blast.

(iii) the 3rd hot blast blowing out device 22

Be located at frost line 34 under, by the ejection hot blast, make the temperature in the zone of frost line 34 slowly cool to fusing point-130 ℃～fusing point-90 ℃.The Tg of the preferred PBT resin of the temperature of this kind hot blast is above below (not containing Tg)～Tg+65 ℃.

(iv) next door 23 and heating arrangements 24

Next door 23 is positioned at the top of the 3rd hot blast blowing out device 22, is arranged to surround bubble zone 33 and the hot blast that sprays from first～the 3rd hot blast blowing out device is upwards blown along the outside in bubble zone 33.Heating arrangements 24 is located at the inboard in next door 23.By next door 23 and heating arrangements 24 are set, just bubble zone 33 and outside atmosphere (temperature temperature etc.) can be cut off, avoid its influence, the Tg that remains the PBT resin is above below (not containing Tg)～Tg+65 ℃.

(v) cylindric net 25

Be positioned at the inboard in next door 23, be arranged to surround bubble zone 33.

In above method, the mechanism for being used to supply with the hot blast that sprays respectively from first～the 3rd hot blast blowing out device is not particularly limited, and can enumerate and can carry out temperature controlled air blast etc.The flow of the hot blast that sprays respectively from first～the 3rd hot blast blowing out device can be in the mode of described temperature range according to the bubble temperature in the zone that makes neck 31, bulge 32 and frost line 34 respectively suitably to be regulated.In the time can't obtaining stable slow cooling effect, bubble 3 becomes unstable, so the temperature of hot blast will be controlled to as far as possible and remains unchanged.

Material for next door 23 is not particularly limited, but in order to observe the bubble zone 33 that is surrounded by next door 23, preferred acrylic resins.If can surround bubble zone 33 from the four directions, then the shape for next door 23 just is not particularly limited, and for example can enumerate cylindrical configuration, cuboid structure, preferably drum shape structure.As the heating arrangements 24 of the inboard of being located at next door 23, for example can enumerate bar-shaped or banded electric heater.Bar-shaped electric heater preferably is provided with a plurality of.Thereby also can adopt and lay aluminium foil on the inner face of next door 23 and can block thermal-radiating formation.As required, bottom that also can next door 23 (the 3rd hot blast blowing out device 22 directly over) is provided with the mechanism that the cold wind about room temperature is upwards blown.Like this, not only the temperature adjustment of 23 inboards, next door is more easy, and the air mass flow adjustment of 23 inboards, next door also becomes easy.

As shown in Figure 2, the top that is preferably in next door 23 is provided with hot blast outlet 230.By hot blast outlet 230 is set, just can carry out rectification to hot blast from the ejection of first～the 3rd hot blast blowing out device.Just can prevent the rolling of the bubble 3 that causes by hot blast thus.Hot blast outlet 230 preferably is provided with more than 2, more preferably is provided with 2～4.In the example shown in Fig. 2, the top of the side 231 of next door 23 is provided with hot blast outlet 230, but also can be arranged on top 232 of next door 23.Wherein the number of hot blast outlet 230 and bore can be got the amount of the degree that can not damage the heat insulating ability that utilizes next door 23 acquisitions.

As shown in Figure 2, the inside upper part that is preferably in next door 23 is provided with the cowling panel 28 of ring-type.By cowling panel 28 is set, can improve the ability that the hot blast that sprays is carried out rectification from first～the 3rd hot air apparatus, further improve the rolling that prevents of bubble 3.As shown in Figure 2, preferably cowling panel 28 from extending near the cylindric net 25 near the medial surface in next door 23.For the structure of cowling panel 28 without limits, can enumerate structure that sheet material that the quilt shown in Fig. 2 and Fig. 3 (a) arranges along a direction separates, shown in Fig. 3 (b), be separated into cancellate structure, the punching tabular that is provided with a plurality of circular holes shown in Fig. 3 (c), reticulated structure etc.The percent opening of cowling panel 28 preferred 40～60%.Be not particularly limited for the material that constitutes cowling panel 28, can enumerate aluminium, synthetic resin etc.Though the sheet number that is provided with for cowling panel 28 also is not particularly limited, and a slice is set usually gets final product.

As the fiber that constitutes cylindric net 25, can use metallic fibers such as plastic optical fibres such as natural fiber, nylon, polypropylene, polyester, stainless steel, copper, brass, nickel such as silk (silk), cotton etc.When using netted structure as cylindric net 25, preferred 5～20 orders of its reticular density, preferred especially 8～10 orders.

The system film that utilizes the expansion-molded method of air cooling of PBT resin of the present invention to carry out can realize that other condition can be used the general condition in the expansion fashion by keeping above necessary condition.That is, use the cross head mould, upward or the below extrude tubulose fusion PBT resin, with end pinch roll clamping, to wherein sending into air, when making it to expand into the size of regulation, reel continuously, also can prevent thick partially betwixt with mould rotation or counter-rotating.

Manufacturing method according to the invention, (after extruding soon, neck, bulge, frost line zone, bubble zone) is maintained at required temperature all the time respectively because each one of bubble, so the quality total energy keeps evenly.Thereby just can further realize making at a high speed film.

(III) extension process

Also the PBT film (expansion PBT film) that the expansion-molded method of the air cooling that utilizes above explanation can be obtained (do not containing Tg) more than the Tg of PBT resin～temperature below the Tg+60 ℃ under, further carry out the cold extension of single shaft along its length or laterally or reach along its length laterally carrying out one by one the cold extension of twin shaft.So just can be with the further filming of expansion PBT film, and further improve the uniformity and the transparency of the thickness of film.Preferred cold elongating temperature is 55～65 ℃.The percentage elongation of the cold extension of this kind single shaft reaches at length direction and transversely preferably is made as more than 2 times, more preferably is made as 2～6 times.When carrying out the cold extension of single shaft, be preferably on the length direction and carry out.This kind percentage elongation of the cold extension of twin shaft one by one represented preferably to be made as more than 4 times with the face multiplying power, more preferably is made as 4～16 times.

In general, when the PBT film being surpassed when extending under Tg+60 ℃ the temperature, because crystal orientation is arranged on bearing of trend, so the hot strength on the differently-oriented directivity, spring rate, rigidity etc. increase substantially.But the intensity on the non-oriented direction will descend, when therefore under surpassing Tg+60 ℃ temperature, carrying out one by one the twin shaft extension, and the problem that will exist film to split.In contrast, when more than the Tg of PBT resin, (do not contain Tg)～temperature below the Tg+60 ℃ under during with the cold extension of PBT film, and comparing surpassing the situation of extending under Tg+65 ℃ the temperature, the orientation of the strand on the bearing of trend is less.(do not containing Tg) more than the Tg thus～temperature below the Tg+60 ℃ under, extend even expansion PBT film is carried out one by one twin shaft, film can not split yet.And, by (not containing Tg) more than the Tg～carrying out cold extension under the temperature below the Tg+60 ℃,, can not produce fissility even under the situation of having carried out uniaxial extension yet.In addition, by (not containing Tg) more than the Tg～carrying out cold extension under the temperature below the Tg+60 ℃, crystallization is destroyed and generate small spherocrystal, so the transparency of film will be improved.

PBT film by the expansion-molded acquisition of air cooling is owing to be tubulose, therefore carrying out under the situation of the cold extension of single shaft with rolled-on method (roll method), perhaps utilize rolled-on method and tentering method to carry out under the situation of the cold extension of twin shaft one by one, after the expansion PBT film with tubulose is cut to 2 parts, implementing cold extension.When the expansion PBT film with tubulose is cut to 2 parts, can superimposed be under the state of thin slice, flatly cut with respect to sheet plane from the two ends kink, or horizontal two ends ear cut away with cutting cutter with cutting knife.

Cutting expansion-molded by (a) air cooling, (b) tubulose expansion PBT film reaches the operation that (c) cold extension constitutes, it also can be following operation one by one, promptly after air cooling is expansion-molded, the PBT film that respectively expands that is cut into 2 parts is made coiled film respectively earlier, in with each coiled film uncoiling successively, carry out cold extension, but the string that preferably operation of described (a)～(c) is carried out on a series of production line continuously row (in line) operation.

Fig. 4 (a) reaches (b) to be illustrated in the PBT film by the expansion-molded acquisition of air cooling is cut to 2 parts in advance, behind the formation coiled film, reaches an example that laterally carries out the device of the cold extension of twin shaft one by one along its length earlier.

The expansion PBT film 2 that is rolled out extends under the effect of the warm-up mill 43 between slow driven roller 41 and the fast driven roller 42 on length direction extension 4 in the longitudinal direction.The PBT film 2 that has extended along its length enters stenter 5 (horizontal expansion portion), is heated under the state that the film two ends are kept, and along horizontal expansion, heat-treats.By in cooling tower 27, blowing cooling air and cooling rapidly to the PBT film 2 that has laterally also extended.

The extension of length direction is as shown in concrete among Fig. 5 (a), by between the slow driven roller 41 and aftermost fast driven roller 42 of forefront, dispose a plurality of warm-up mills that rotate freely 43, and expansion PBT film 2 is passed between them, the peripheral speed of suitably setting slow driven roller 41 and fast driven roller 42 recently realizes.The temperature of warm-up mill 43 can reach it according to the temperature that makes expansion PBT film and (not contain Tg) more than the Tg～and the mode of temperature below the Tg+60 ℃ sets.

Fig. 5 (b) and (c) other example of expression length direction extension 4.The example of Fig. 5 (b) expression clamping roll-type, (b) example of expression ripping bar roller (crow bar roll) formula.In any one mode, all a plurality of preparation heating of expansion PBT film 2 usefulness are prepared heating with roller 43, between each slow driven roller 41 that has heated and fast driven roller 42, heat extension thereafter, cool off with roller 44 with a plurality of coolings then.

In the stenter 5, the chain (not shown) with film niproll 51 circulates with ring-type along track (not shown).Stenter 5 is made of this 3 part of preheating part, extension and heat treatment portion.The PBT film 2 of Yan Shening is heated by the hot blast that imports by hot blast entrance hole 53 respectively in preheating part, extension and heat treatment portion along its length.In Fig. 4,52 expression gears, 54 expressions are used for cover that hot blast is blowed equably to PBT film 2.The temperature of the hot blast that sprays in preheating part, extension and heat treatment portion can be set the temperature that makes the PBT film 2 by each one for and be retained as respectively more than the Tg and (do not contain Tg)～temperature below the Tg+60 ℃.The chilling that utilizes cooling tower 27 to carry out makes the PBT film 2 after extending reach the following temperature of glass transition temperature.

When with expansion PBT film 2 only to length direction or when laterally carrying out the cold extension of single shaft, after only expansion PBT film 2 being extended, carry out chilling and get final product with the length direction extension 4 of above explanation or horizontal expansion portion 5.

Be not limited to as shown in Figure 4 the mode that rolls or stenter mode in length direction or the cold extension of single shaft transversely and length direction and the cold extension of twin shaft one by one transversely, also can adopt cylinder method methods such as (tubular).When adopting the cylinder method, the string row operation that operation expansion-molded and (b) cold extension formation is preferably carried out on a series of production line continuously by (a) air cooling.

Fig. 6 represents to be used for to carry out continuously that air cooling is expansion-molded on a series of production line, the example of the string arranging device of the cutting of tubulose expansion PBT film and cold extension.The tubular film 2 that is pulled machine niproll 13 clampings traction is under the state of the thin slice that is folded, flatly split with respect to sheet plane from the two ends kink by cutting knife 18, on length direction extension 4,4, carry out cold extension respectively with respect to the PBT film of cutting apart up and down 2 ', 2 ' that respectively expands.As shown in Figure 6, be preferably in cutting knife 18 marginal position control device (EPC:Edge Position Control Unit) 6 is set before.Like this when cutting with cutting knife 18, just can be on certain position with ear end position (marginal position) master control of expansion PBT film, the PBT film 2 that therefore just tubulose can be expanded is cut apart all the time equably.Marginal position control device 6 shown in Figure 6 has two guiding rollers 61,61, connects connecting axle 62, the sensor 63 of guiding roller 61,61, and according to the instruction from sensor 63 make the guiding roller 61,61 gradient change, thereby the ear end position (marginal position) of expansion PBT film 2 can be controlled certain position all the time.As the marginal position control device, be not limited to illustrated device, also can use known other controlling organization.

On length direction extension 4,4, between the slow driven roller 45,45 and fast driven roller 46,46 of heating, with each expansion PBT film 2 ', 2 ' cold extension through cooling off.Late the temperature of driven roller 45,45 can reach it according to the temperature that makes expansion PBT film and (not contain Tg) more than the Tg～mode of temperature below the Tg+60 ℃ sets.The temperature of speed driven roller 46,46 is set at below the Tg of expansion PBT, is preferably set to the temperature that is lower than Tg.Percentage elongation can recently be regulated by the peripheral speed of suitably setting slow driven roller 45,45 and fast driven roller 46,46.Also can adopt following formation, that is, after length direction extension 4,4, stenter shown in Figure 45 (horizontal expansion portion) is set, thereby realize to horizontal further cold extension.

Heater 19 preferably is set as shown in Figure 6, when keeping level, the film after the cold extension is implemented heat treatment with niproll 17,17.Also can replace heater 19, utilize the roller heating to heat-treat.Heat treatment is carried out below being preferably in above (not containing the Tg)～fusing point-50 of Tg ℃ of PBT.Utilize the heat treatment after the cold extension, the uniformity of the transparency, hot strength, heat-resisting shrinkage and thickness is further improved, and can suppress the generation of fold.By more than Tg+60 ℃～heat-treat below the fusing point-50 ℃, just can make film have the straight line tearability.When need not to give film straight line tearability, (do not containing Tg) more than the Tg～(not containing Tg+60 ℃) below the Tg+60 ℃ heat-treat and get final product.Change heat treatment temperature as described above, can change the straight line tearability of film and the tearing toughness that accompanies with it.

By using string arranging device shown in Figure 6, just can improve cutting expansion-molded by (a) air cooling, (b) tubulose expansion PBT film and reach (c) efficient of a series of operation of cold extension formation.

[2] polybutylene terephthalate (PBT) film

Utilize the PBT film of the expansion-molded manufactured of air cooling of narration in described [1] to compare with expansion-molded film in the past, crystallization Du Genggao, the uniformity of thickness is more good, and percent thermal shrinkage is lower.Specifically, the deviation of the thickness of the film of average film thickness 8～30 μ m is ± 1～3 μ m, and percent thermal shrinkage is below 0.4% on MD (length direction) and TD (width).In this specification, the deviation of so-called thickness is meant, the thickness at the central part of the width of PBT film and both ends is one group with 2 respectively measures the maximum wherein calculated after 6 and the difference of minimum of a value altogether.This value is more little, and then the result is just good more.In addition, so-called percent thermal shrinkage is meant and measures respectively the MD of PBT film when down exposing 10 minutes for 175 ℃ and the value of the shrinkage factor of TD.Thus, just can form less printed layers of uneven phenomenon or metal evaporation layer.In addition, in secondary operations such as heat seal, printing, the variation of film dimensions is less.

As mentioned above, utilize the percent thermal shrinkage of the PBT film of the expansion-molded manufactured of air cooling of narration in described [1] lower, its reason can be thought, because of will slowly cooling off to the zone of frost line from the neck of bubble, and when roughly extending equably along vertical (MD) horizontal (TD) direction, to steep the zone, to remain Tg above below (not containing Tg)～Tg+65 ℃, therefore can not produce distortion (stress) in the bubble that is generated.

Particularly after air cooling is expansion-molded, in described [1] enforcement of narration the average film thickness of cold extension be that the deviation of thickness of the film of 3～30 μ m is 1～2 μ m, the percent thermal shrinkage of cold bearing of trend is below 1%.And on any one direction, all not having fissility, mechanical strength is good.

Utilize the PBT film of the expansion-molded manufactured of air cooling of narration in described [1] to compare crystallization Du Genggao with expansion-molded film in the past.Specifically, the crystallization degree that utilizes determination of x-ray of expansion PBT film of the present invention is 35～40%.Utilize the PBT film of the expansion-molded manufactured of air cooling of narration in described [1] good aspect mechanical strength thus.In contrast, under the extrusion resin temperature more than the fusing point, be inflated the crystallization degree of PBT film of shaping usually below 30%.And utilize the crystallization degree of the PBT of casting shaping to be generally about 8～10%.

The PBT film of having implemented cold extension has many fine linear folds of extending along cold bearing of trend.That is, when the concave-convex surface to the PBT film of having implemented cold extension utilizes AFM (atomic force microscope) when measuring, concavo-convex difference of height is generally 50～500nm, and concavo-convex width (interval between the summit of linear fold) is generally 500～20000nm.But reaching along its length under the situation that width carries out the cold extension of twin shaft one by one, the linear fold that is produced by the cold extension of formerly carrying out can disappear, and only has the linear fold that is caused by the cold extension of carrying out thereafter to remain on the surface of PBT film.Therefore, even carry out one by one the cold extension of twin shaft, the direction of the linear fold that the PBT film is had also is a direction.

The PBT film of having implemented cold extension is because of having aforesaid linear fold, thereby has the effect that makes optical diffraction/scattering.For example when passing PBT film and observe light source such as bulb with linear fold, on the rectangular direction of the direction of linear fold, can observe with the light source be the center and with a light of the roughly the same width of light source.By having the PBT film and the combination of light sources of linear fold, just can make ornamental illuminating lamp etc. thus.The PBT film that will have linear fold is according to the different each other mode of the direction that the makes linear fold laminate film that multi-disc forms of fitting, and is bigger to diffraction of light/dispersion effect.This kind laminate film can be used as the transparent membrane of the transparent electromagnetic wave shielded film that stacked electromagnetic wave shielding (sealed) layer forms on transparent membrane.In addition, having the laminate film self of the PBT film of linear fold can also be as the electromagnetic shielded film utilization.To be the PBT processing film with linear fold that the structure of the honeycomb tectosome that forms of the film adhered multi-disc of wave sheet shape is stronger to diffraction of light/dispersion effect particularly, the transparent electromagnetic wave shielding be also higher.This kind honeycomb tectosome can be used as acoustic material.

[3] shape memory polybutylene terephthalate (PBT) laminate film

Shape memory polybutylene terephthalate (PBT) laminate film of the present invention have layer that (a) be made of the PBT film that utilizes manufacture method of the present invention to obtain, (b) from paper sheet, other resin film and metal forming at least a (being designated hereinafter simply as " other film or thin-film laminate ") selected.

(I) layer constitutes

(1) polybutylene terephthalate (PBT) film

As the use of PBT film is the film that utilizes manufacture method acquisition of narration in described [1].Though the thickness for the PBT film is not particularly limited, in practicality, preferably be made as about 5～50 μ m, more preferably be made as about 8～30 μ m.

(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 in the paper sheet layer is unqualified, also comprises synthetic fibre paper.The thickness of paper sheet layer preferably is made as about 60～110g/m ², more preferably be made as about 75～90g/m ²When the thickness of paper sheet is thinner than about 60g/m ²The time, then the hardness of paper sheet is low excessively, can't give enough stationary states.On the other hand, even the thickness of paper sheet surpasses about 110g/m ²,, therefore can't further improve stationary state because cost is too high.

(b) sealing film

When shape memory PBT laminate film was used for the lid of container for fast food, the upper end flange portion that is arranged on container body carried out thermosealed sealing film.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.

As sealing film, for example can use the laminate film of low molecular weight polyethylene film of the upper end flange portion side of the polyethylene substrate film of paper sheet side and container body.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, 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 in 2002-183197 number that disclosed sealing film is by comprising the material that straight chain shape ethylene and poly resin combination constitute, described straight chain shape ethylene 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 ³, MFR (JIS K6921,190 ℃, 2.16kg load) is 1～100g/10 minute.Like this, even the sealing surface of container body is in polyethylene or the 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.When using the PET film of the different biaxial orientation of the uniaxial orientation or the degree of orientation as the PET film, needing under the situation of fissility 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 " ェ Application Block レ ッ ト PC " (ュ ニ チ カ (strain)).

(b) light-proofness ink lay

When requiring shape memory PBT laminate film to possess light-proofness, light-proofness ink lay or metal foil layer are set., just be 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 as light-proofness printing ink.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, just 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. 7～Figure 10 has enumerated shape memory PBT laminate film used with packaging material as the lid of container for fast food constitutes.Laminate film 7 expressions shown in Figure 7 constitute as the layer that basic comprising has PBT thin layer 2, paper sheet 71, sealing film 72.Between PBT thin layer 2 and paper sheet 71, have by bond layer 74 and the adhesive linkage (I) that the polyethylene layer (I) 73 that is extruded lamination constitutes, the adhesive linkage (II) that is made of bond layer 74 ' and the polyethylene layer (II) 73 ' that is extruded lamination is arranged between paper sheet 71 and sealing film 72.Under the situation of layer configuration example shown in Figure 7, the bed thickness of outside layer that is made of PBT film 2 and adhesive linkage (I) (73 and 74) and the la m that is made of adhesive linkage (II) (73 ' and 74 ') and sealing film 72 is than preferred outside layer/la m=100/35～100/100.The edge-rolling of PBT film 2 and stationary state are brought into play 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. 8 represents to be provided with between paper sheet layer 71 and sealing film 72 for the rigidity that improves shape memory PBT laminate film the example of stiffness films 75.And, in Fig. 8,73 " expression is extruded the polyethylene layer (III) of lamination, 74 " expression bond layer (III).

Fig. 9 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 76.Light-proofness ink lay 76 preferably is printed on PETG (PET) film in advance.In addition, light-proofness ink lay 76 can be arranged on the inboard of PBT film 2, or be arranged on a side's of paper sheet layer 71 the face (for example inboard of paper sheet 71).Laminate film shown in Figure 10 has metal foil layer 77 as the layer of giving light-proofness.

The example that layer when Figure 11 and Figure 12 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 11 has PBT film 2, stiffness films 75, sealing film 72 as basic comprising.Bond layer (for example hot melt adhesive layer) 74 is arranged between PBT film 2 and stiffness films 75, bond layer (for example hot melt adhesive layer) 74 ' is arranged between paper sheet 71 and sealing film 72.Figure 12 represents to be provided with on the medial surface of stiffness films 75 in order to give good light-proofness the example of light-proofness ink lay 76.

Employed lid in the container that places semi-solid food is not because therefore the resealability after requiring to inject hot water unlike the lid that is used for container for fast food often 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, its shape recovery capability might be insufficient.Thus, when manufacturing has PBT film and poly shape memory PBT laminate film, be preferably in described stiffness films is set between PBT film and the polyethylene film.

(II) 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) with the PBT film and described other film or thin-film laminate bonding after, to the laminate film of the gained temperature T below the Tg at described PBT when keeping first shape ₁Under carry out figuration and handle (cold working), (b) with the figuration laminate film of gained in the temperature T that surpasses described Tg ₂Following deformation processing is second shape, (c) by being cooled to the temperature T below the Tg ₃And be fixed as the operation of second shape.

Below, so that first shape is made as the crimping shape, the situation that second shape is made as smooth shape is that example describes.Figure 13 represents to make an example of the device of shape memory PBT laminate film.From the PBT film 2 of raw-material spool 80 uncoilings that are wound with the PBT film through guiding rollers 130, under the effect of gravure roll 131,131 on a side face applied bonding agent (for example PUR) 74, in drying oven 132 with the bond layer drying.Thereafter, adjust roller 133 through excess pressure,, will overlap on the bond layer from other film or thin-film laminate 82 of uncoiling on the spool 81 across the molten polyethylene of from mould 134, extruding 73, simultaneously, pass between chill roll 135 and the rubber rollers 135 ' and (extrude lamination).Temperature T below the Tg at PBT in 136 conveyances of cold working roller ₁Laminate film to gained carries out the figuration processing down.So just can give edge-rolling to the PBT film of laminate film.Utilize heater 138, will give the laminate film (edge-rolling laminate film) 78 of edge-rolling in the temperature T that surpasses Tg ₂Down hastily annealing the time, deformation processing is a flat condition between two niprolls 137,137 ', then by making it to contact the temperature T that is cooled to below the described Tg with chill roll 139 ₃So just can be fixed as smooth shape.Utilize spool that the edge-rolling laminate film is reeled to its inverse hemming direction, form coiled film 83 (shape memory PBT laminate film 7) thereafter.In this specification, when being different from 7 bendings of shape memory PBT laminate film, can keep so-called edge-rolling the stationary state of this state, be meant by shape memory PBT laminate film 7 is exposed to more than the temperature of having given edge-rolling, and second shape that can have been obtained after having given edge-rolling (smooth shape, inverse hemming shape etc.) returns to the character of crimping shape (can make 7 bendings 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 78 after the cooling annealing ₃Must be below described Tg, preferred 15～25 ℃.The PBT film generally has about 20～45 ℃ Tg.

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 ℃) more than 45 ℃～below 65 ℃, on the basis that is 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 137,137 '.In addition, in temperature T ₂Under annealing in process after, preferably be chilled to temperature T ₃Among Figure 13, utilize heater 138,138 to heat, but also can only heater 138 be set in the PBT of edge-rolling laminate film 78 film side from the two sides of edge-rolling laminate film 78.The hot-air that adds that also can use nozzle to come out from heater 138 blows to the PBT of edge-rolling laminate film 78 film.

In the example shown in Figure 13, edge-rolling laminate film 78 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 in order not make edge-rolling disappearance that utilizes the cold working acquisition and the recovery of doing one's utmost to suppress the 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 7 can be remained smooth state, the edge-rolling laminate film 78 during therefore with coiled film 83 (shape memory PBT laminate film 7) 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, making layer is stacked in other film or the thin-film laminate on the PBT film in advance so that shape memory PBT laminate film become as described [3] (I) layer shown in (3) constitute.Other film or thin-film laminate 82 also can utilize any one mode in extruding layer platen press or the dry lamination method to form, but preferably utilize the extruding layer platen press to form.

For with regard to the encirclement method of cold working roller 136, preferably as shown in figure 13, make involving in direction and rolling out direction angulation θ of laminate film with regard to laminate film ₁Be in 45～60 ° scope.So just can give enough edge-rollings to PBT film 2.If will be with angle θ ₁Be made as required value, as long as the position relation of cold working roller 136 and pressure adjustment roller 133 ' is suitably adjusted.Preferred 20～the 80cm of the diameter of cold working roller 136.So just can give enough edge-rollings to PBT film 2.Usually the peripheral speed of cold working roller 136 was made as 30～100m/ minute.

PBT film 2 and other film or thin-film laminate 82 being passed between chill roll 135, the rubber rollers 135 ' when bonding, apply usually to PBT film 2 and carry out in the tension force more than the 4kgf/m width utilizing pressure to adjust roller 133.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 82 bonding.Like this, just can be bonding with other film or thin-film laminate 82 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 7 is further improved.So-called ductility that can elastic telescopic generally is to extend 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 13, though bonding other film or thin-film laminate 82 on the single face of PBT film 2 only also can be given edge-rolling behind bonding other film or thin-film laminate 82 on the two sides of PBT film 2.

Figure 14 represents 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 13.In this example, except PBT film 2 and other film or thin-film laminate 82 are utilized the dry lamination method bonding, identical with example shown in Figure 13.The PBT film 2 that is provided with bond layer is adjusted roller 133 through excess pressure, passes between a pair of warm-up mill 140,140 in overlapping at film or thin-film laminate 82 and bond layer with other.But when needing stronger adhesive strength, preferably utilize extruding layer platen press shown in Figure 13 that PBT film 2 and other film or thin-film laminate 82 is bonding.

Below, first shape as shape memory PBT laminate film is adopted the pallet shape and adopts the example of the situation of smooth shape to describe as second shape.Figure 15 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 13.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 84 usefulness pressure of gained are adjusted roller 133,133 send, when the extrusion die 141 of pallet shape is given in ejection, in described temperature T ₁Under carry out cold working, give the shape that forms according to the profile of extrusion die 141 discontinuously.The figuration laminate film 85 that makes gained by a pair of annealing with between the roller 142,142, by in described temperature T ₂Following annealing and general planarization utilizes cooling device 143,143 to be cooled to described temperature T then ₃With the general planar change the coating of deformation layer laminate film 85 and uncoiling from spool 86 with film 87 stackedization in, use with the take up roll 144 of extrusion die 141 similar shapes and reel, form coiled film.Like this, just can become potentialization of distortion that will form according to the profile of extrusion die 141, not have the laminate film that is out of shape on apparent.In the temperature T of in PBT film 2 ejection extrusion dies 141, carrying out ₁Under cold working carry out getting final product in 10～60 seconds.And, in the example shown in Figure 15, use hypocraterimorphous extrusion die 141, but also can suitably use the extrusion die that will carry out the required form of shape memory.

(second manufacture method)

Second manufacture method of shape memory PBT laminate film comprises: (a) temperature T that (is not containing Tg) more than the Tg～(do not containing fusing point) below the fusing point when keeping first shape by (i) ₄Down the laminate film that comprises the PBT film is carried out that figuration is handled or (ii) when keeping first shape in described temperature T ₄Down the PBT film is carried 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 ₆Following deformation processing is second shape, afterwards, (d) is cooled to the following temperature T of Tg ₇And be fixed as the operation of described second shape.

The Tg of PBT resin is 22～45 ℃ near room temperature, and the operation that be heated to the above temperature of Tg, is cooled to the temperature that is lower than Tg is very easy.And, because fusing point is higher, be about 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, will be to adopt the crimping shape as first shape, adopting the situation of smooth shape as second shape is that example describes.

Figure 16 represents to utilize 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 74 on the one side of PBT film 2 and in drying oven 132 operation with the bond layer drying identical with example shown in Figure 13.As shown in figure 16, the 2 usefulness pressure of the PBT film behind the dry bond layer are adjusted roller 133 send, with the face that do not have adhesive linkage as contact-making surface, in warm-up mill 145 conveyances of using with figuration, in described temperature T ₄Under handle, give edge-rolling thus.Thereafter, with other film or thin-film laminate 82 with the adhesive linkage of PBT film 2 overlapping in, make it to pass warm-up mill 145 and the roller 145 ' that contacts with it between, both are bonding.Contact with chill roll 139 by the edge-rolling laminate film 78 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 83.The coiled film 83 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 7.After having formed coiled film 83, in temperature T ₆Under carry out heat treated, then by being cooled to temperature T ₇And, be formed on the laminate film of general planar in appearance with potentialization of crimping shape of described laminate film.Do not having particular determination aspect the mode that coiled film 83 is heated or cool off, for example can enumerate coiled film 83 is put into groove back with around the heater heating tank or with the method for cooling device cooling.

The heating-up temperature T of warm-up mill 145 ₄Be necessary for the temperature of above (not containing the Tg)～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 139 ₅Be necessary for the following temperature of described Tg, preferred below 40 ℃.Also can not use chill roll 139 in the cooling of edge-rolling laminate film 78, and use the cooling air.The heating-up temperature T of coiled film 83 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 83 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 16,, 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 145, preferably make involving in direction and rolling out direction angulation θ of PBT film 142 shown in Figure 16 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 145 and pressure adjustment roller 133,133 is suitably adjusted.Preferred 60～the 80cm of the diameter of warm-up mill 145.So just can give enough edge-rollings to PBT film 2.Usually the peripheral speed of warm-up mill 145 was made as 30～100m/ minute.

As described in (1) to the explanation of first manufacture method, by PBT film 2 and other film or thin-film laminate 82 are passed between warm-up mill 145 and the touch roll 145 ' when bonding, when applying tension force more than the common 4kgf/m width, 133,133 pairs of PBT films 2 of roller carry out utilizing a pair of pressure to adjust.Identical with first manufacture method, preferably PBT film 2 is applied the tension force of 10～20kfg/m width.

Figure 17 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 13.In this example, by the film of PBT film and other or thin-film laminate is bonding and in advance behind the making layer laminate film, give edge-rolling to this PBT thin layer.Operation till PBT film 2 and other film or thin-film laminate 82 being utilized a pair of warm-up mill 140,140 bonding is identical with example shown in Figure 14.When the laminate film of gained is used warm-up mill 145 conveyances, the temperature T that more than the Tg of PBT, (does not contain Tg)～(do not contain fusing point) below the fusing point ₄Following figuration.So just can give edge-rolling to the PBT film of laminate film.Contact with chill roll 139 by the edge-rolling laminate film 78 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 83.Coiled film 83 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, be cooled to the following temperature T of described Tg then ₇, obtain shape memory PBT laminate film 7.

In the embodiment shown in Figure 17, about temperature T ₄～T ₇Requirement identical with embodiment shown in Figure 16.The involving in direction and roll out direction angulation θ of laminate film 78 ₃Preferably be in 45～60 ° scope.In the example shown in Figure 17, though bonding other film or thin-film laminate 82 on the single face of PBT film 2 only, also can be on PBT film 2 two-sided bonding other film or thin-film laminate 82 given edge-rolling afterwards.

Utilize second manufacture method, also can make as first and form the shape memory PBT laminate film that adopts the pallet shape and adopted smooth shape as second shape.The manufacturing installation of this moment is identical with device shown in Figure 15, therefore utilizes Figure 15 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 84 of gained is adjusted roller 133,133, the temperature T that when the extrusion die 141 of pallet shape is given in ejection, (does not contain Tg) more than the Tg of PBT～(do not contain fusing point) below the fusing point through a pair of pressure ₄Under be implemented heat treated, give the shape that forms according to the profile of extrusion die 141 discontinuously.The figuration laminate film 85 of gained is contacted with hypocrateriform extrusion die or cooling air with the cooling of the back segment of being located at extrusion die 141, be cooled to the following temperature T of described Tg ₅, pass then between a pair of warm-up mill 142,142, more than described Tg, (do not contain Tg)～temperature T ₄Below (do not contain T ₄) temperature T ₆Under carry out heat treated, utilize cooling device 143,143 to be cooled to the following temperature T of described Tg then ₇, make it planarization.To push the temperature T of carrying out when mould 141 presses against on the laminate film 84 ₄Under heat treated carry out getting final product in 10～60 seconds.

(III) shape memory polybutylene terephthalate (PBT) laminate film

The shape memory PBT laminate film that utilizes described first method acquisition is at T ₁Can utilize the shape recovery capability to recover first shape in fact under the above temperature.Also can be even the PBT film is fixed to second shape in described annealing and refrigerating work procedure at T 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 do not relaxed, 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 ₄Can utilize the shape recovery capability to recover first shape in fact under the above temperature.Also can be even the PBT film is fixed to second shape in described heating deformation processing and refrigerating work procedure at T ₄Though it is also uncertain to 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, in temperature T ₅Owing to be glassy zone, therefore distortion is fixed, though pass through temperature T down ₆Under the heating deformation processing with temperature T ₄Under the part of distortion relax 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.

The shape memory PBT laminate film that can recover 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, shape memory PBT laminate film utilization lid material sealing device is carried out stamping-out processing, with the lid of gained immediately heat seal on container.When heat seal, though the seal head of the sealing tegmentum material sealing device of lid is heated to 120～160 ℃ usually, also applied heat this moment on the part beyond the sealing of lid, so lid is at T ₁Or T ₄Processed under the above temperature conditions.Thus, lid just recovers the crimping shape, though be sealed on the container during 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 further improve.

[4] has the manufacture method of the container of shape memory polybutylene terephthalate (PBT) laminate film system lid

Below the manufacture method of container with shape memory PBT laminate film system lid is narrated.Utilize shape memory PBT laminate film 7 that the method for record in described (2) obtains since in its manufacturing process from being made into general planar in appearance, and then be used as coiled film 83 keepings, therefore general planar in appearance when it is rolled out.But at shape recovery temperature lower or keeping long period, be exposed in the megathermal period in summer under the situation such as room temperature, will occur slowly recovering the crimping shape in the keeping process, or being wound on and defectives such as the opposite side of crimping shape through shape memory bends during because of keeping.

Container with shape memory PBT laminate film system lid is to make on container by the shape memory PBT laminate film of having remembered the crimping shape being carried out stamping-out processing and heat seal, if when shape memory PBT laminate film is rolled out not is general planar, just can't heat seal on container, even or can lid also because of the crooked defective work that become.Thus when manufacturing has the container of lid, make uneven shape memory PBT laminate film when rolling out not long ago become the shape of general planar at heat seal.

Figure 18 represents to make an example of the device of the container with shape memory PBT laminate film system lid.To use heater 147,147 from the shape memory PBT laminate film 7 that coiled film 83 rolls out, in the temperature T of the Tg that surpasses PBT ₈Down, between two niprolls 146,146 ', keep smooth in annealing, from making it general planar in appearance.150 pairs of lid material sealing devices that utilize seal head 151 to move up and down become smooth basically shape memory PBT laminate film 7 carry out stamping-out processing, heat seal is on container 170 immediately.And can in container, be blown into inert gas as required.

Wherein, temperature T ₈Under annealing proceed to the degree that edge-rolling that shape memory PBT laminate film is remembered does not disappear.Thus, temperature T ₈Preferred 80～120 ℃, more preferably 90～100 ℃.Shape memory PBT laminate film is heated to temperature T hastily ₈, remaining smooth after annealing 30～60 seconds.Tension force that applied is made as 5～10kgf/m width in order to keep smooth between two niprolls 146,146 '.Usually the gait of march of shape memory PBT laminate film 7 was made as 30～100m/ minute.Among Figure 18, though utilize heater 147,147 to heat from the two sides of shape memory PBT laminate film 7, when shape memory PBT laminate film 7 only when single face has the PBT film, also can only heater 147 be set in this PBT film side.Also can use nozzle to blow the hot-air that adds that from heater 147, comes out to the PBT film of shape memory PBT laminate film 7.

The stamping-out processing of lid and the heat seal on container 170 are owing to be to carry out off and on, therefore deflection (relaxing) and maintenance certain force of strain in shape memory PBT laminate film 7 interval between guiding roller 149 and touch roll 152, what preferably as shown in figure 18, be provided with that easy on and off moves prevents that deflection is with roller 148.And in Figure 18,88 expressions are by the coiled film that the shape memory PBT laminate film 7 behind the lid stamping-out is constituted.

When heat seal, though the seal head 151 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 will recover the crimping shape, though be sealed on the container during keep smooth, will show the crimping shape after peeling off from container.

[5] containers for food use

Utilize the lid of the container of the manufacture method acquisition of narrating in described [4] after peeling off from container, to show the crimping shape of utilizing shape memory to obtain.For example when on the lid that shape memory PBT laminate film is used for container for fast food, just as shown in figure 20, when the joint of holding lid 7 ( Block) portion 160 peels off to mark 161 from container body 170 lid 7, the flap portion (flap) of exposing because of Kaifeng also can be retained as the state of abundant crimping even do not have aluminium lamination always.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 be further improved.When shape memory PBT laminate film is used for the lid of container for fast food, constitute preferably described [3] (I) Fig. 7～formation shown in Figure 10 of (3) middle narration as its layer.

When the shape memory PBT laminate film that will have the PBT film that has formed wire trace described later is used for the lid of container for fast food, as shown in figure 20, by both sides otch 162,162 is set in connector portions 160, just can be with the easily local Kaifeng of lid 7.When an opposite layback of lid 7 was stretched, lid 7 will form peristome 163 from otch 162,162 upper edge smooth tearings on lid 7 when clamping the connector portions 160 of lid 7 with finger.Because of tear the state that the flap portion 164 that forms keeps abundant crimping always.Get final product so directly hot water is injected in peristome 163.

After injecting hot water, when flap portion 164 is returned to original position, because the jagged 164a of portion, the 164a of breaking of paper arranged on the outer rim of the one-sided or both sides of flap portion 164, therefore itself and the portion of the breaking interlock of the 163a of sawtooth portion, the 163a of the paper of peristome 163, flap portion 164 just can not lift.And this moment peristome 163 area not only less than the peristome of in the past comprehensive Kaifeng formula, and because flap portion 164 is in the state that combines with peristome 163, even therefore mistake also can reduce the amount that hot water spills with container body 170 reversings.And in Figure 20,180 expression dried noodles.

Container body 170 for example can utilize synthetic resin such as paper, foamed styrene to make.Under the situation of paper-made vessel main body, it is very easy not only to burn, and has do not produce the advantage that environment is caused dysgenic gas when burning.In addition, under the situation of foamed styrene container made main body, has the good advantage of heat insulating ability.The shape of container body 170 is not limited to illustrated shape, can carry out various changes according to the kind of content.

Figure 21 and Figure 22 represent shape memory PBT laminate film is used to place example on the lid of 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 representative is described [3] (I) Figure 11 of narration and formation shown in Figure 12 in (3) as its layer.As shown in figure 21, under sealing state, the lid 70 minutes that is sealed on the container 170 is smooth.But because lid 7 recovers crimping shape (but being smooth in appearance) on being thermally sealed on container 170 time, therefore after the lid of being made by the shape memory PBT laminate film that does not have paper sheet or aluminium foil 7 is peeled off from container 170, will be as shown in figure 22, because of shape memory crimping consumingly.Container body 170 for example can utilize synthetic resin such as polypropylene, polyethylene to make.The shape of container body 170 is not limited to illustrated embodiment, can carry out various changes according to the kind of content.The lid that this kind has a strong edge-rolling also is suitable for the purposes such as lid of portable bag (Port one シ ョ Application パ ッ Network) usefulness of coffee milk etc.

By with described [3] (II) in narration memory 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 23, the food of gained hold on pallet 153 make things convenient for quick-frozen food 154 after, utilize packaging film 155 packings, make package goods 156.As shown in figure 23, packaged food 156 utilizes microwave oven 157 grades to heat in order to eat, and pass through at said temperature T this moment ₁Or T ₄Carry out the heat treated of appropriate time under the above temperature, can make food recover the pallet shape that forms by extrusion die 141 with pallet 153.When shape memory PBT laminate film being used for food with pallet 153 as described above, following convenience is arranged, promptly, under the state of package goods 156 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 155 of pallet 153, preferably utilize method described later at food, forming many parallel in fact wire traces on the one side at least.Like this, packaging film 155 just can have a straight line tearability on the direction, and this and its orientation is irrelevant, thereby can begin along the wire trace along smooth tearing from position arbitrarily.When edible, just packaging film 155 easily can be broken a seal the part thus.This kind wire trace is not owing to run through film, even so packaging film 155 after forming the wire trace, also very good aspect gas-barrier property.

[6] formation of the wire trace on film

In order to make shape memory PBT laminate film have the straight line tearability, be preferably at least one whole in the middle of PBT film, stiffness films and the sealing film, 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 and the method that the wire trace with a plurality of fine projections forms mechanism's sliding-contact.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 24 is illustrated in an example that forms the device of wire trace on the direct of travel of film 301.Roller (hereinafter referred to as " pattern roller ") 302 that Figure 24 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 303 that can blow air as the film dipper crowding gear.By making from the film 301 process niprolls 312 that are wound with raw-material spool 311 uncoilings of film, with pattern roller 302 sliding-contacts, form the wire trace, the straight line tearability film of gained is reeled by wireline reel 316 through niproll 313, guiding roller 314 and 315.

Pattern roller 302 is fixed on the assigned position in its rotating shaft mode parallel with the width of film 301 as shown in figure 25, and axis direction length is longer than the width of film 301, make the width of film 301 whole with the pattern roller sliding-contact.

By niproll 312 and 313 being arranged on the front and back of pattern roller 302, just can apply tension force to the film 301 of on pattern roller 302, advancing as the tension adjustment roller.In addition, as shown in figure 25, by on the position of film 301 and pattern roller 302 sliding-contacts, utilize nozzle 303 to blow the air of the blast that has regulation from an opposite side of pattern roller 302, just can apply uniform contact force the face of film 301 and pattern roller 302 sliding-contacts (if following do not particularly point out then be called " roller sliding contact surface ").So just can on pellicular front, form the uniform linear trace.By using nozzle 303 that film 301 is pressed against on the pattern roller 302, just can alleviate the contact inhomogeneities that the uneven thickness by the film on the roller sliding contact surface 301 causes.

Preferably make pattern roller 302 with the peripheral speed slower, along the direction rotation opposite with the direct of travel of film 301 than the gait of march of film 301.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 on the surface of pattern roller 302, therefore just can form the wire trace of the suitable length and the degree of depth.The gait of march of film 301 preferably was made as 10～500m/ minute among the present invention.In addition, the peripheral speed of pattern roller 302 (making it along the speed of the direction rotation opposite with the direct of travel of film 301) preferably was made as 1～50m/ minute.

As pattern roller 302, 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 is attached with 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 can suitably be 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 is suitably selected attached to the mode that the degree on the surface of roller main body can reach required degree according to the interval between the formed wire trace.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 302, 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 302, more preferably 3～10cm.

As pattern roller 302, 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 302, 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 26 represents that film 301 forms the state of wire trace with pattern roller 302 sliding-contacts.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 304 of pattern roller 302, but as mentioned above, because the gait of march of film 301 is faster than the peripheral speed of pattern roller 302 reverse rotations, therefore the bight of the particulate 304 of incision is left before the roller sliding contact surface, can form long wire trace.

Blow mechanism as air, also can use the nozzle that shown in Figure 27 (b), has a plurality of blow-off outlets 331, replace the nozzle (with the identical nozzle of nozzle shown in Figure 24～25) that shown in Figure 27 (a), has banded blow-off outlet 331.As Figure 27 (c) shown in, have when covering 332 nozzle when using in addition with the form compressed-air blows of coverage diagram table roll 302, the compressed air that blows out from blow-off outlet 331 was difficult for diffusion before the position that arrives film 301 and pattern roller 302 sliding-contacts, therefore just can make the film 301 on the roller sliding contact surface and the further homogenising of contact force of pattern roller 302.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 film 301 on the roller sliding contact surface and the contact force homogenising of pattern roller 302.The pressure of preferred compressed air stream is 9.8～196kPa (0.1～2kgf/cm ²).In addition, from blow-off outlet 331 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 331 with air blast or nozzle increases to required degree when above, be used to obtain suitable blast and the compressed-air actuated amount of needs increases, therefore not ideal enough.

With regard to regard to encirclement (the volume I the is hung け) method of the film 301 of the pattern roller 302 that is fixed in assigned position, preferably make involving in direction and roll out direction angulation θ and being in 60～170 ° scope of the film 301 shown in Figure 27 (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.If angle θ will be made as required value, the height and position by changing pattern roller 302 etc. is then suitably adjusted the position relation of pattern roller 302 and niproll 312 and 313 and to be got final product.In addition,, the blast that utilizes niproll 312 and 313 to offer the tension force of film 301 and to utilize nozzle 303 to provide is suitably adjusted, just can be obtained the wire trace of the required length and the degree of depth according to encirclement method and external diameter to the film 301 of pattern roller 302.Among the present invention, utilize niproll 312 and 313 to be added in tension force (tension force on the per unit width) on the film, preferably be made as the scope of 0.01～5kgf/cm width.

By making brush replace the use that air blows mechanism, can on the roller sliding contact surface, apply uniform contact force with the face sliding-contact of an opposite side of roller sliding contact surface.The rough lumber of brush is preferably, the material that can move along the direct of travel rightabout with film 301 with the speed slower than the gait of march of film 301 on the sliding contact surface of brush and film 301 (if following do not particularly point out then be called " brush sliding contact surface ").Thus, as brush, preferably as shown in figure 28, use has the rotation roller brush 305 of many rough lumbers with radial configuration around brush axle (rotating shaft), and according to making its rotating shaft mode parallel be fixed on the assigned position with the width of film 301, make axis direction length longer, make the whole and brush sliding-contact of width of film 301 than the width of film 301.

Preferred 5～the 10cm of external diameter of rotation roller brush 305.About the rough lumber 351 of rotation roller brush 305, 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 351 on the brush sliding contact surface of rotation roller brush 305 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 351 is not particularly limited, preferred approximate U font or taper.Though the material for rough lumber 351 also is not particularly limited, the synthetic resin of optimization polypropylene, nylon, acrylic acid, polyethylene etc.

Rotation roller brush 305 is preferably according to making the pressure on the brush sliding contact surface reach 1～490kPa (0.01～5kgf/cm ²) mode and film 301 sliding-contacts.The peripheral speed of rotation roller brush 305 (make it along with the speed of the direct of travel rightabout rotation of film 301) preferably was made as 1～50m/ minute.

In order to satisfy the degree of required straight line tearability, 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 301, pattern roller 302, diamond particle 304, pattern roller, nozzle 303, rotation roller brush 305, utilize tension force that niproll 312 and 313 provide etc. suitably to set the length and the degree of depth of adjusting the wire trace.

(II) situation of the wire trace that formation is tilted on film

Figure 29 represents to form with respect to the direct of travel of film 301 example of the device of the wire trace that tilts.Used identical reference marks for member identical or part with Figure 24.In the device shown in Figure 29, form mechanism as the wire trace and have the pattern endless belt 306 that has connected a plurality of little pattern rollers 321, and have the Ring form brush 307 that on the endless belt, has disposed many rough lumbers 371 as the film dipper crowding gear.Figure 30 (a) is illustrated in the device shown in Figure 29, makes the local amplification plan view of pattern endless belt 306 along the state of the width rotation of film 301, and Figure 30 (b) is the schematic section of seeing from the D direction in Figure 30 (a).

By make pattern endless belt 306 as Figure 30 (a) and (b) along the rotation of the width of film 301, make little pattern roller 321 continuously with film 301 sliding-contacts, just can form wire trace with respect to the direct of travel inclination of film 301.Preferably make the number of the pattern roller 321 that constitutes pattern endless belt 306 more, make the density of pattern roller 321 higher.The axis direction length of little pattern roller 321 and the preferred 5～10cm of external diameter.

The wire trace of incline direction can be by suitably adjusting pattern endless belt 306 with respect to the angle of film direct of travel peripheral speed and the gait of march of film 301 change.Usually the peripheral speed with pattern endless belt 306 was made as 1～100m/ minute.Little pattern roller 321 is rotated in opposite direction with respect to the direct of travel of pattern endless belt 306 on the roller sliding contact surface.Its peripheral speed is identical with the situation of the pattern roller 302 of described (I) middle narration, is 1～50m/ minute.

Ring form brush 307 preferably according to make its rough lumber 371 with film 301 sliding-contacts in the direction that moves and pattern endless belt 306 with film 301 sliding-contacts in the opposite mode of the direction that moves rotate.Will make Ring form brush 307 and pattern endless belt 306 have identical direction of rotation like this.Preferred 4～the 8cm of length of the rough lumber 371 of Ring form brush 307.Situation about rotation roller brush 305 of narration among the condition of density, head end shape and material on the crooked recovery rate of the rough lumber 371 of Ring form brush 307, diameter, the brush sliding contact surface and described (I) is identical.The situation of the rotation roller of narration brush 305 is identical among the pressure of Ring form brush 307 on the brush sliding contact surface and described (I), is 1～490kPa (0.01～5kgf/cm ²).The Ring form brush 307 and the pressure of film 301 sliding-contacts can be regulated by the upper-lower position that rotation height release handle 373 is suitably set Ring form brush 307.Preferred 1～the 50m/ of the peripheral speed of Ring form brush 307 minute.The peripheral speed of Ring form brush 307 can be regulated by the rotary speed of suitably setting motor 374.

Pattern endless belt 306 and Ring form brush 307 preferably make direct of travel length longer than the width of film 301, so that the width of film 301 is whole and pattern endless belt 306 and Ring form brush 307 sliding-contacts.

Figure 31 represents to form other example of the device of the wire trace that the direct of travel with respect to film 301 tilts.Member identical with Figure 24 or part have been used identical reference marks.In the device shown in Figure 31, form mechanism as the wire trace and have a plurality of less pattern roller 322a are installed in side by side the roller formation 308a that forms on the guide rail 381a (supporter), reach a plurality of less pattern roller 322b are installed in the roller formation 308b that forms on the guide rail 381b (supporter) side by side shown in figure 32.

Supporting the back shaft 391a of pattern roller 322a and 322b and 391b can free lifting, and roller formation (train) 308a and 308b can move by the width straight line along guide rail 381a and 381b along film 301 respectively.The guide mechanism that utilization is made of back shaft 391a that can free lifting and 391b and guide rail 381a and 381b, roller formation 308a and 308b can move independently along the width of film 301.Thus, can carry out following circulation repeatedly, promptly, make roller formation 308a and 308b from film 301 one distolateral to another distolateral with film 301 sliding-contacts in move, separate with film 301 and get back to original position moving to other end rear flank, move by control roll formation 308a and 308b's this moment, make any one roller formation all the time with the whole sliding-contact of the width of film 301, can form the wire trace that the direct of travel with respect to film tilts.As guide mechanism, also can not adopt to make back shaft 391a and 391b mode, but adopt the formation that makes guide rail 381a and 381b free lifting with respect to guide rail 381a and not lifting of 381b.

The axis direction length of pattern roller 322a and 322b and external diameter are to get final product about 5～10cm.Gap between the pattern roller of pattern roller 322a and 322b is preferably narrower than the roller width of pattern roller at least, to improve the density of pattern roller.The length separately of roller formation 308a and 308b is longer than the width of film 301.

In the device shown in Figure 31,, be provided with Ring form brush 307a and the 307b identical respectively abreast with respect to roller formation 308a and 308b with the mechanism that device had shown in Figure 29 across film 301 as the film dipper crowding gear.But the supporting member 372,372 that supports Ring form brush 307a and 307b can free lifting.Thus by its lifting of control, make Ring form brush 307a and roller formation 308a while and film 301 sliding-contacts, and make Ring form brush 307b and roller formation 308b while and film 301 sliding-contacts by controlling its lifting, can provide certain contact force all the time by the pair roller sliding contact surface.

Ring form brush 307a and 307b preferably according to make its rough lumber with film 301 sliding-contacts in the direction that moves and roller formation 308a and 308b with film 301 sliding-contacts in the opposite mode of the direction that moves rotate.About the peripheral speed of pressure, Ring form brush 307a and 307b on the brush sliding contact surface of the condition of density, head end shape and material on the crooked recovery rate of the rough lumber of Ring form brush 307a and 307b, diameter, length, the brush sliding contact surface and Ring form brush 307a and 307b, identical with the situation of the Ring form brush that device had 307 shown in Figure 29.

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 308a and 308b sliding-contact and film 301 is suitably adjusted.In addition, pattern roller 322a and 322b rotate in opposite direction with respect to advancing of roller formation 308a and 308b on the roller sliding contact surface.Identical the getting final product of situation of the pattern roller 302 of narration among its peripheral speed and described (I).

Figure 33 (a) and Figure 33 (b) expression forms other example of the device of the wire trace that tilts with respect to the direct of travel of film 301.In this example, axis direction length is provided with before and after longer 2 the pattern roller 323a of the width of film 301 and 323b are on the direct of travel of film 301 abreast.More than 2 times of width of the axis direction length preferred film 301 of pattern roller 323a and 323b.

Supporting the back shaft 392a of pattern roller 323a and 323b and 392b can free lifting, and pattern roller 323a and 323b can move by straight line on the width of film 301 along guide rail 382a and 382b respectively.The guide mechanism that utilization is made of back shaft 392a that can free lifting and 392b and guide rail 382a and 382b, pattern roller 323a and 323b can move independently along the width of film 301.Thus, can carry out following circulation repeatedly, promptly, make pattern roller 323a and 323b with film 301 sliding-contacts in distolateral from film 301 to other end side shifting, separate with film 301 and get back to original position moving to other end rear flank, move by control chart table roll 323a and 323b's this moment, make any one pattern roller all the time with the whole sliding-contact of the width of film 301, can form the wire trace that the direct of travel with respect to film tilts.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 pattern roller 323a and 323b sliding-contact and film 301 is suitably adjusted.

In the device shown in Figure 33,, be provided with the Ring form brush 307a and the 307b of the energy free lifting identical respectively abreast with respect to pattern roller 323a and 323b across film 301 with the mechanism that device had shown in Figure 31 as the film dipper crowding gear.

And in the device shown in Figure 29～Figure 33, though as the film dipper crowding gear, possess Ring form brush, the air that also can possess narration in described (I) blows mechanism.

(III) situation of the wire trace of formation width on film

Figure 34 is illustrated in an example of the device of the wire trace that forms width on the film 301.Used identical reference marks for member identical or part with Figure 29.Device shown in Figure 34 except pattern endless belt 306 is obliquely installed by the direct of travel with respect to film, other identical with the device shown in Figure 29 and Figure 30 (Ring form brush is not shown).The device that has the formation shown in Figure 34 by use, gait of march, pattern endless belt 306 to film 301 are suitably set with respect to the angle of the direct of travel of film 301, the operating conditions such as peripheral speed of pattern endless belt 306, just can form the wire trace on the width of film 301.

Figure 35 is illustrated on the film 301 other example of the device of the wire trace that forms width.In this example, be that symmetry axis is provided with the pattern endless belt 306a that is connected with a plurality of little pattern roller 321a obliquely and is connected with the pattern endless belt 306b of a plurality of little pattern roller 321b relatively symmetrically and with respect to the direct of travel of film with the center line 317 of film 301.As the film dipper crowding gear, preferably will with pattern endless belt 306a and 306b (not shown) be set abreast respectively across film 301 with the identical Ring form brush in the device shown in Figure 29.

The device that has the formation shown in Figure 35 by use, gait of march, pattern endless belt 306a and 306b to film 301 suitably set with respect to the operating conditions such as peripheral speed of angle, pattern endless belt 306a and the 306b of the center line 317 of film 301, can form the wire trace on the width of film 301.

Figure 36 is illustrated in other example of the device that forms the wire trace on the width of film 301.Device shown in Figure 36 except the roller array 308a shown in Figure 32 and 308b are obliquely installed by the width with respect to film 301, other identical with the device shown in Figure 32 (Ring form brush is not shown).The device that has the formation shown in Figure 36 by use, gait of march, roller array 308a and 308b to film 301 suitably set with respect to the operating conditions such as sliding-contact speed of angle, roller array 308a and the 308b of the direct of travel of film 301, just can form the wire trace on the width of film 301.

Figure 37 (a) and Figure 37 (b) are illustrated in other example of the device that forms the wire trace on the width of film 301.The left surface of the device shown in Figure 37 (b) expression Figure 37 (a) (figure that sees from the F direction of Figure 37 (a)).In this example, possess 2 the pattern roller 324a and the 324b of axis direction that the direct of travel that has with respect to film 301 tilted.The axis direction length of pattern roller 324a and 324b preferably is at least more than 2 times of width of film 301.

Supporting the back shaft 393a of pattern roller 324a and 324b and 393b can free lifting, and pattern roller 324a and 324b can move by straight line when the center line 317 with respect to film 301 keeps the angle of regulation along guide rail 383a and 383b respectively.The guide mechanism that utilization is made of back shaft 393a that can free lifting and 393b and guide rail 383a and 383b, pattern roller 324a and 324b can keep at the center line 317 with respect to film 301 moving independently in the angle of regulation.For axis direction length, because pattern roller 324b is longer than pattern roller 324a, so pattern roller 324a and 324b just can interlock when opposite direction is advanced mutually.Thus, can carry out following circulation repeatedly, promptly, make pattern roller 324a and 324b from film 301 one distolateral to another distolateral with film 301 sliding-contacts in move, separate with film 301 and get back to original position moving to other end rear flank, move by control chart table roll 324a and 324b's this moment, make any one pattern roller all the time with the whole sliding-contact of the width of film 301, can form the wire trace of width with respect to the direct of travel of film.

As the film dipper crowding gear, can be shown in Figure 37 (b), the rotation roller brush 305a and the 305b that are supported by the back shaft 352a of can free lifting and can straight line moving and 352b are set respectively, make it to move matchingly with the moving of roller sliding contact surface of pattern roller 383a and 383b and film 301.In addition, longer by a side who makes rotation roller brush 305a and 305b for axis direction length than the opposing party, can rotate roller brush 305a and 305b interlaced when opposite direction is advanced.Like this, just can apply contact force all the time to the roller sliding contact surface of pattern roller 383a and 383b and film 301.Brush the preferred condition of density, head end shape and material on the crooked recovery rate of the rough lumber 351 of 305a and 305b, diameter, length, the brush sliding contact surface about rotating roller, identical with the situation of rotation roller brush 305 of narrating in described (I).

In addition, in the device shown in Figure 34～Figure 37,, also can form the wire trace of inclination with respect to the direct of travel of film 301 by suitably changing operating condition etc.In addition, about the device shown in Figure 34～Figure 37, 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 (I) blows mechanism.

In the film with straight line tearability of the method manufacturing of more than utilizing, narrating, 1～40% of the degree of depth preferred film thickness of described wire trace.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.

[7] minute aperture of film is processed

To form memory PBT laminate film and have the straight line tearability in order to make, also can on any one whole in the middle of PBT film, stiffness films and the sealing film, 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 is lower than about 500/cm ²The time, fissility 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 spy opens disclosed method in 2002-059487 number.For example in utilizing No. the 2071842nd, Japan's special permission during disclosed method, by film being passed be attached with from the teeth outwards a plurality of Mohs' hardness between second roller of first roller of the particle more than 5 (roller identical) and surface smoothing with the pattern roller 302 of explanation in described [7] with sharp-pointed bight, 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, 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 thus.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.

[8] 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.

[9] functional polyalkylene mutual-phenenyl two acid bromide two alcohol ester film

By forming wire trace and/or minute aperture as described below, can give as the more good function of packaging material PBT film of the present invention.

(I) straight line tearability polybutylene terephthalate (PBT) film

Straight line tearability PBT film is the film that has formed many parallel in fact wire traces according to the method for narration in described [6] at least one face of PBT film.Thus, can have a straight line tearability on the direction, and the orientation of this and material film is irrelevant, can begins along the wire trace along smooth tearing from position arbitrarily.When using the packaging bag of straight line tearability PBT thin film fabrication, just can break a seal with the band shape that head end when keeping certain width does not attenuate.In addition, because the wire trace does not run through film, therefore also has good gas-barrier property in the straight line tearability PBT film.

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 can have 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.Evaporation such as metal, pottery forms at the wire trace of film can on any one party of face or non-formation face.The PBT film that utilizes manufacture method of the present invention to obtain is little owing to percent thermal shrinkage, and therefore under the situation that has formed the evaporation layer, this evaporation layer is comparatively stable.

In addition, straight line tearability PBT film can adopt the laminate film with 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 possess aluminium foil in the intermediate layer, evaporation has the pet film of silica, the films such as pet film that evaporation has aluminium oxide.

In addition, when forming laminate film, also can be by the method manufacturing of the PBT film being implemented after the processing that the wire trace is set described later to dissolve or being dissolved across described intermediate layer and with other thin layer with other thin layer.Stackedization undertaken by extruding lamination after between each layer adhesive linkage being set.As adhesive linkage preferably polyethylene layer.

As the purposes of the straight line tearability PBT film that on the direct of travel (length direction) of film, has formed the wire trace, the packaging bag that has bar-shaped dessert to use.The straight line tearability PBT film that has the wire trace of length direction by use can break a seal with the band shape that head end when keeping certain width does not attenuate, 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 that has the wire trace of incline direction by use 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.Has the straight line tearability PBT film of horizontal wire trace by use, just the bar-shaped packaging bag that can increase gradually with low-cost manufacturing demand.

The method of record in can be according to described [7] 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 straight line tearability can further improve, and also can give tearability to the part beyond the wire trace.

(II) porous polybutylene terephthalate (PBT) film

Porous PBT film is the method according to record in described [7], has been formed uniformly a plurality of fine through holes and/or the film of through hole not on the PBT film.Porous PBT film distortion retentivity height can not break during distortion thus, and warping property is good, and has tearability.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 is lower than about 500/cm ²The time, the distortion retentivity is just insufficient.

Porous PBT film has been kept the characteristic of practical aspect, does not lose hear resistance as the excellent characteristic of PBT film, fragrance protectiveness, resistance to water etc., and is very useful as the packaging material with 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 embodiment to further describe the present invention below, but the present invention and be limited to these.

Embodiment 1

Use device shown in Figure 1, utilize the expansion-molded method of air cooling to make the PBT film.With PBT resin (trade name " ト レ コ Application 1200S ", east beautiful (strain) system, fusing point: 220 ℃, inherent viscosity: 1.2) drop into single shaft extruder (screw diameter: 50mm, extrusion capacity: 50kg/hr),, in extruder, modulated molten resin at 210 ℃ of following melting mixings.Next from outlet of extruder, at 210 ℃ extrusion resin temperature and 11.8MPa (120kgf/cm ²) extrusion resin pressure under, molten resin is extruded, and then from die head (mode diameter: 150mm, the gap at mould edge: the 0.9mm) pipe of resin melt extrusion.The pipe that makes the molten resin of extruding expands with 3.6 blow-up ratio, and (1) by the neck that steeps being slowly cooled to 185 ℃ from first hot blast blowing out device ejection hot blast (30 ℃), (2) by spraying hot blast (30 ℃) from the second hot blast blowing out device, the bulge of bubble is slowly cooled to 160 ℃, (3) by spraying hot blast (50 ℃) from the 3rd hot blast blowing out device, the frost line zone is slowly cooled to 125 ℃, (4) will steep the zone remain on 100 ℃ in traction in 20m/ minute, make the PBT film.The cylindric net that surrounds the bubble zone adopts nylon system net, and the cylindrical shape next door of acrylic resin system 2 positions of side at an upper portion thereof is provided with the hot blast outlet, is provided with heater air flow pressure switch rod in the inboard, and being provided with percent opening in inner upper is 60% cowling panel.

Embodiment 2

Except the extrusion resin temperature is made as 205 ℃, extrusion resin pressure is made as 12.7MPa (130kgf/cm ²) in addition, made the PBT film in the same manner with embodiment 1.

Embodiment 3

Except the extrusion resin temperature is made as 215 ℃, extrusion resin pressure is made as 10.8MPa (110kgf/cm ²) in addition, made the PBT film in the same manner with embodiment 1.

Comparative example 1

Except the extrusion resin temperature is made as 230 ℃, extrusion resin pressure is made as 8.8MPa (90kgf/cm ²) in addition, made the PBT film in the same manner with embodiment 1.

Comparative example 2

Except not using cowling panel, made the PBT film in the same manner with comparative example 1.

Rerum natura to the PBT film of gained in embodiment 1～3 and the comparative example 1,2 is measured with following method.The results are shown in the table 1.

Average film thickness: utilize contact thickness meter, the thickness at central part on the width of thin slice and both ends is one group with 2 has respectively measured 6 points altogether, calculate mean value from measured value.

The deviation of thickness: the thickness at central part on the width of PBT film and both ends is one group with 2 has respectively measured 6 points altogether, try to achieve according to wherein the maximum and the difference of minimum of a value.

Tensile break strength: with ASTM D882 is the tensile break strength that benchmark is measured the rectangle test film of wide 10mm.

Percent thermal shrinkage: measured respectively with the PBT film when down exposing 10 minutes for 175 ℃ MD and the shrinkage factor of TD.

Crystallization degree: utilize determination of x-ray.

Table 1

Annotate: (1) east beautiful (strain) trade name " ト レ コ Application "

As shown in table 1, utilize the PBT thin film crystallization degree height of the embodiment 1～3 that manufacture method of the present invention makes, the uniformity and the tensile break strength of thickness are good, and percent thermal shrinkage is low.Among the embodiment 1～3, in the manufacture process of PBT film, bubble does not have rolling, all-the-time stable.In contrast, comparative example 1 is owing to be made as the extrusion resin temperature more than the fusing point of PBT resin, so the crystallization degree is low, and tensile break strength is poor.Comparative example 2 is not owing to use cowling panel, and therefore bubble has rolling, instability in film is made.

Claims (26)

1. shape memory polybutylene terephthalate (PBT) laminate film, it is characterized in that, has (a) polybutylene terephthalate (PBT) film, (b) from paper sheet, that selects in other resin film and the metal forming is at least a, described polybutylene terephthalate (PBT) film is to form by following air cooling plavini, in the described air cooling plavini, in temperature is the scope of the fusing point-15 ℃～described fusing point-5 ℃ of polybutylene terephthalate (PBT) resin, pressure is to extrude the polybutylene terephthalate (PBT) resin of fusion from annular die under the condition of 8.3～13.7MPa, make it to expand by in resulting polybutylene terephthalate (PBT) pipe, injecting air afterwards

Temperature T below the glass transition temperature of described polybutylene terephthalate (PBT) film ₁Be treated to first shape by figuration down, afterwards in the temperature T that surpasses described glass transition temperature ₂Following deformation processing is second shape, then by being cooled to the temperature T below the described glass transition temperature ₃, be fixed to second shape, by being exposed on described temperature T ₁Above temperature is got back to described first shape by 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 ₂Above 45 ℃ and below 65 ℃, 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, it is characterized in that, has (a) polybutylene terephthalate (PBT) film, (b) from paper sheet, that selects in other resin film and the metal forming is at least a, described polybutylene terephthalate (PBT) film is to form by following air cooling plavini, in the described air cooling plavini, in temperature is the scope of the fusing point-15 ℃～described fusing point-5 ℃ of polybutylene terephthalate (PBT) resin, pressure is to extrude the polybutylene terephthalate (PBT) resin of fusion from annular die under the condition of 8.3～13.7MPa, make it to expand by in resulting polybutylene terephthalate (PBT) pipe, injecting air afterwards

At the glass transition temperature that surpasses described polybutylene terephthalate (PBT) film and be lower than the temperature T of fusing point ₄Be treated to first shape by figuration down, be cooled to the following temperature T of described glass transition temperature afterwards ₅And be fixed to described first shape, surpass described glass transition temperature and be lower than described temperature T ₄Temperature T ₆Following deformation processing is second shape, then is cooled to the following temperature T of described glass transition temperature ₇And be fixed to second shape, by being exposed on described temperature T ₄Above temperature is got back to described first shape by 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 each described shape memory polybutylene terephthalate (PBT) laminate film among the claim 1-6, it is characterized in that first is shaped as the crimping shape, second is shaped as smooth shape or inverse hemming shape.

8. according to each described shape memory polybutylene terephthalate (PBT) laminate film among the claim 1-6, it is characterized in that first is shaped as the pallet shape, 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, (A) layer has described polybutylene terephthalate (PBT) film in constituting successively, described paper sheet, stiffness films and sealing film, and has the light-proofness ink lay on the face of the face of described paper sheet one side of described polybutylene terephthalate (PBT) film or described sealing film one side of described stiffness films, perhaps (B) layer has described polybutylene terephthalate (PBT) film in constituting successively, stiffness films and sealing film, and have the light-proofness ink lay on the face of described sealing film one side of described stiffness films.

13. 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 keeps elastic restoring force.

14. shape memory polybutylene terephthalate (PBT) laminate film according to claim 13, it is characterized in that described polybutylene terephthalate (PBT) film is bonding with other film or thin-film laminate under the elongation state that keeps the 1-3% ductility.

15. according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6, it is characterized in that the inherent viscosity that forms the polybutylene terephthalate (PBT) resin of described polybutylene terephthalate (PBT) film is 0.8～1.5.

16. according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6, it is characterized in that, the gap at edge that is used to form the annular die of described polybutylene terephthalate (PBT) film is 0.8～1.2mm, mode diameter is 120～250mm, and blow-up ratio is 2.0～4.0.

17., it is characterized in that described polybutylene terephthalate (PBT) film is to form by following step according to any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～6,

(1) by spraying hot blast near the first hot blast blowing out device of being located at described annular die, to slowly cool to described fusing point-40 ℃～described fusing point-25 ℃ by the neck that in described polybutylene terephthalate (PBT) film tube, injects the bubble that air expands, (2) by second hot blast blowing out device ejection hot blast from the top of being located at the described first hot blast blowing out device, the bulge of described bubble is slowly cooled to described fusing point-70 ℃～described fusing point-40 ℃, (3) by the 3rd hot blast blowing out device ejection hot blast from the top of being located at the described second hot blast blowing out device, the frost line zone of described bubble is slowly cooled to described fusing point-130 ℃～described fusing point-90 ℃, (4) utilize the phase septal space to be arranged on the next door on every side in the bubble zone of described frost line top, described bubble zone is cut off with outside atmosphere, and will upwards blow along the outside in described bubble zone from the hot blast of described first～the 3rd hot blast blowing out device ejection.

18. shape memory polybutylene terephthalate (PBT) laminate film according to claim 17, it is characterized in that, described polybutylene terephthalate (PBT) film is, when a plurality of hot blast outlets are set, cowling panel is set on described next door, the hot blast from described first～the 3rd hot blast blowing out device ejection is carried out rectification form in the inboard in described next door.

19. shape memory polybutylene terephthalate (PBT) laminate film according to claim 17, it is characterized in that, described polybutylene terephthalate (PBT) film is, utilization is from the hot blast of described second hot blast blowing out device ejection, slowly cools off to form when the bulge with described bubble remains non-crystal state.

20. shape memory polybutylene terephthalate (PBT) laminate film according to claim 17, it is characterized in that, described polybutylene terephthalate (PBT) film is, by in described next door heating arrangements being set, the temperature that described bubble zone is remained on Tg to Tg+65 ℃ of the glass transition temperature of described polybutylene terephthalate (PBT) resin forms.

21. shape memory polybutylene terephthalate (PBT) laminate film according to claim 17 is characterized in that, described polybutylene terephthalate (PBT) film is by described bubble zone is surrounded with cylindric net, to prevent that the rolling of described bubble from forming.

22. shape memory polybutylene terephthalate (PBT) laminate film according to claim 17, it is characterized in that, from the temperature of the hot blast of described first and second hot blast blowing out device ejection is 25～50 ℃, is the temperature of Tg to Tg+65 ℃ of the glass transition temperature of described polybutylene terephthalate (PBT) resin from the temperature of the hot blast of described the 3rd hot blast blowing out device ejection.

23. 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, carries out further by the air cooling swelling film to gained that the cold extension of single shaft or twin shaft forms.

24. shape memory polybutylene terephthalate (PBT) laminate film according to claim 23 is characterized in that the temperature of described cold extension is the temperature that the glass transition temperature of described polybutylene terephthalate (PBT) resin is Tg to Tg+60 ℃.

25. packaging material is characterized in that, are made by any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～24.

26. a cap for container body is characterized in that, is made by any described shape memory polybutylene terephthalate (PBT) laminate film in the claim 1～24.

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