JP6030878B2 - Method for manufacturing piezoelectric body - Google Patents

Description

  The present invention relates to a method for manufacturing a piezoelectric body using polylactic acid.

It is known that polylactic acid is used as a polymer piezoelectric material by stretching (Patent Documents 1 and 2). In addition, a bimorph structure or a multimorph structure is formed using such a polymer piezoelectric material, and the piezoelectric characteristics are further enhanced, so that it can be used as a vibrating body such as a microphone, pickup, buzzer, speaker, optical switch, fan, or piezoelectric actuator. It is known to be used (Patent Documents 3 to 5).
In order to form a bimorph structure or multimorph structure as described above, it is necessary to cut polylactic acid films and laminate carefully cut films so that the piezoelectric properties of each polylactic acid film do not cancel each other. Met.
On the other hand, in the field of tilted alignment optical sheets and films, such as polarizing films, retardation films, etc., which are not related to the piezoelectric body, in order to be able to manufacture with roll-to-roll with the alignment axis aligned from the viewpoint of optical characteristics, Techniques have been proposed for stretching in an oblique direction with respect to the film forming direction (Patent Documents 6 to 8).

JP 05-152638 A JP 2005-213376 A JP 59-115580 A JP 59-2222977 A Japanese Utility Model Publication No. 58-076783 JP 2008-023775 A JP 2009-119774 A JP 2005-284024 A

The present inventors cut and laminated polylactic acid films stretched in a direction perpendicular to the film forming direction to create a multimorph structure, and formed and laminated a conductive layer on each polylactic acid film under the same conditions. Even when many of the completed piezoelectric bodies were evaluated, it was found that there was a great variation in the performance.
Therefore, an object of the present invention is to provide a method for manufacturing a piezoelectric body with small variations in performance when the piezoelectric body is formed by alternately laminating a polylactic acid film and a conductive layer.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have surprisingly found that when a film stretched obliquely with respect to the film-forming direction is used, there is little variation when used as a piezoelectric body, and average The inventors have found that a piezoelectric body having a high performance can be obtained, and have reached the present invention.

Thus, according to the present invention, the following methods (1) to (8) for manufacturing a piezoelectric body are provided.
(1) In an unstretched film made of either poly L-lactic acid or poly D-lactic acid, the angle between the main orientation axis and the main orientation axis is 40 to 50 degrees with respect to the film production direction. Stretching in an oblique direction to form an oriented polylactic acid film, forming a conductive layer on one surface of the oriented polylactic acid film to form a laminate A, and laminate A as an oriented polylactic acid film layer And a step of laminating and press-bonding so that the conductive layers and the conductive layers are alternately arranged.
(2) The method for producing a piezoelectric body according to (1), wherein the total number of oriented polylactic acid films is 4 or more.
(3) The method for producing a piezoelectric body according to (1), wherein the oriented polylactic acid film has a thickness of 15 μm or less.
(4) The method for producing a piezoelectric body according to (1), wherein the heat shrinkage rate at 110 ° C. in the film forming direction and the width direction of the oriented polylactic acid film is in the range of 3% or less.
(5) The method for manufacturing a piezoelectric body according to (1), wherein the thickness unevenness in a direction (width direction) orthogonal to the film forming direction of the oriented polylactic acid film is 30% or less.
(6) When adjacent oriented polylactic acid films are both poly-L-lactic acid or poly-D-lactic acid, the other oriented poly-L-lactic acid and poly-D-lactic acid so that their main orientation axes are perpendicular to each other. In some cases, the method for producing a piezoelectric body according to the above (1), in which the main orientation axes are laminated in the same direction.
(7) The method for producing a piezoelectric body according to (6), wherein all the oriented polylactic acid films are all poly L-lactic acid or poly D-lactic acid.
(8) The method for manufacturing a piezoelectric body according to (1), wherein a plurality of rolls of the laminated body A are prepared, and the rolls are stacked, wound, and pressure-bonded.

In addition, according to the present invention, the following piezoelectric bodies (9) to (17) can also be provided.
(9) An oriented polylactic acid film in which the main orientation axis composed of either poly-L-lactic acid or poly-D-lactic acid is oblique with respect to the film forming direction, and formed on one surface of the oriented polylactic acid film A piezoelectric body obtained by laminating a laminate A composed of a conductive layer so that an oriented polylactic acid film layer and a conductive layer are alternately arranged and press-bonded.
(10) The piezoelectric body according to (9), wherein the total number of oriented polylactic acid films is 4 or more.
(11) The piezoelectric body according to (9), wherein the oriented polylactic acid film has a thickness of 15 μm or less.
(12) The piezoelectric body according to (9), wherein the thermal shrinkage rate at 110 ° C. in the film forming direction and the width direction of the oriented polylactic acid film is in the range of 3% or less.
(13) The piezoelectric body according to (9), wherein the thickness unevenness in a direction (width direction) orthogonal to the film forming direction of the oriented polylactic acid film is 30% or less.
(14) When the adjacent oriented polylactic acid films are both poly L-lactic acid or poly D-lactic acid, the other is made of poly L-lactic acid and poly D-lactic acid so that their main orientation axes are perpendicular to each other. In some cases, the piezoelectric body according to the above (9), which is laminated so that the main orientation axes thereof are in the same direction.
(15) The piezoelectric body according to (14), wherein all the oriented polylactic acid films are all poly L-lactic acid or poly D-lactic acid.

  According to the present invention, it is possible to efficiently manufacture a piezoelectric body having small variations when used as a piezoelectric body.

It is explanatory drawing of the laminated body A which provided the conductive layer in the oriented film in this invention. The upper side is a laminate A provided with a resin layer and a conductive layer for the right margin, and the lower side is a laminate A provided with a resin layer and a conductive layer for the left margin. 2 is an explanatory diagram of a laminate in the present invention, and the top diagram in FIG. 2 shows a laminate A provided with a resin layer and a conductive layer for the right margin in FIG. 1, and a resin layer for the left margin in FIG. 2 and the laminate A provided with conductive layers are alternately arranged. The middle diagram in FIG. 2 is a diagram of a laminate B obtained by pressure-bonding them, and the lowermost diagram in FIG. FIG. 4 is a diagram in which a conductive paste is provided at both ends of a laminate B. It is the figure which showed the evaluation method of the piezoelectric characteristic of the piezoelectric material in this invention.

<Method for manufacturing piezoelectric body>
In the method for producing a piezoelectric body of the present invention, an unstretched film made of either poly-L-lactic acid or poly-D-lactic acid is stretched so that the main orientation axis is oblique with respect to the film forming direction. A process for forming a polylactic acid film,
Forming a conductive layer on one surface of the oriented polylactic acid film to form a laminate A, and laminating the laminate A so that the oriented polylactic acid film layer and the conductive layer alternate, and pressing the laminate. Have.

Hereinafter, the present invention will be described in detail.
<Laminated structure of piezoelectric body>
The laminated structure of the piezoelectric body obtained by the manufacturing method of the present invention will be described with reference to FIGS. 1 and 2 are schematic views showing an example of the laminated structure of the piezoelectric body of the present invention. In FIG. 1, reference numeral 1 denotes a resin layer for the right margin and an oriented polylactic acid film layer (1), and reference numeral 2 denotes a resin layer for the left margin and an oriented polylactic acid film layer adjacent to the oriented polylactic acid film layer (1). (2) is shown respectively. In the piezoelectric body of the present invention, a plurality of oriented polylactic acid film layers (1) and (2) are alternately laminated as described above. FIG. 2 shows a case where the number of oriented polylactic acid film layers (1) is three and the number of oriented polylactic acid film layers (2) is six, for a total of six.
Reference numeral 3 denotes a conductive layer M. In the present invention, a conductive layer M (3) is provided between the oriented polylactic acid film layers (1) and (2). In addition, the conductive layer M (3) is preferably provided on at least one surface of the piezoelectric body, and the conductive layer M (3) may be provided on the other surface.

  Then, as shown in FIG. 2, by alternately short-circuiting the conductive layer (3) with the conductive paste (6), it is possible to apply an opposite charge to the adjacent conductive layer (3). To. Therefore, the adjacent oriented film layers (1) and (2) are laminated so that the piezoelectric characteristics do not cancel each other when opposite charges are applied. Therefore, when the adjacent oriented polylactic acid films are both poly-L-lactic acid or poly-D-lactic acid, they are poly-L-lactic acid and poly-D-lactic acid so that their main orientation axes are perpendicular to each other. In some cases, the layers are laminated so that their main orientation axes are in the same direction. In addition, the fact that the main orientation axes of adjacent oriented polylactic acid films in the present invention are orthogonal means an angle of approximately 90 degrees, and the closer to 90 degrees, the more effectively the piezoelectric characteristics are expressed. From such a viewpoint, when the adjacent oriented polylactic acid films are both poly L-lactic acid or poly D-lactic acid, the acute angle formed by the main orientation axis of the preferred adjacent oriented polylactic acid film is 80 degrees or more. It is preferable that it is 85 degrees or more, more preferably 88 degrees or more. In the present invention, the main orientation axes of adjacent oriented polylactic acid films in the same direction mean an angle of almost 0 degrees, and the closer to 0 degrees, the more effectively the piezoelectric characteristics are expressed. . From such a viewpoint, when the adjacent oriented polylactic acid films are poly L-lactic acid and poly D-lactic acid, the acute angle formed by the main orientation axis of the preferred adjacent oriented polylactic acid film is 10 degrees or less. It is preferably 5 degrees or less, more preferably 2 degrees or less.

<Polylactic acid>
The poly L-lactic acid in the present invention is substantially composed of only L-lactic acid units (hereinafter may be abbreviated as PLLA), and the co-polymerization of L-lactic acid and other monomers. Although it is a coalescence etc., it is especially preferable that it is poly L-lactic acid substantially comprised only by L-lactic acid unit.

The poly-D-lactic acid in the present invention is composed of poly-D-lactic acid (hereinafter sometimes abbreviated as PDLA) substantially composed only of D-lactic acid units, D-lactic acid and other monomers. Although it is a copolymer etc., it is especially preferable that it is poly D-lactic acid substantially comprised only from a D-lactic acid unit.
Here, “main” means that 60% by mass or more of polylactic acid (poly L-lactic acid in layer L and poly D-lactic acid in layer D) is 60% by mass or more with respect to the mass of the resin constituting each layer, preferably 75. It indicates that it is at least mass%, more preferably at least 90 mass%, particularly preferably at least 95 mass%. Further, “substantially” indicates that the amount of L- (D-) lactic acid units in poly L- (D-) lactic acid is 90 mol% or more.

  The amount of L- (D-) lactic acid units in poly L- (D-) lactic acid is preferably 90 from the viewpoints of crystallinity, enhancing the improvement of piezoelectric properties, and film heat resistance. It is -100 mol%, More preferably, it is 95-100 mol%, More preferably, it is 98-100 mol%. That is, the content of units other than L- (D-) lactic acid units is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.

Such polylactic acid preferably has crystallinity, and it becomes easy to obtain the orientation / crystal mode as described above, and the effect of improving the piezoelectric characteristics can be enhanced. The melting point is preferably 150 ° C. or higher and 190 ° C. or lower, and more preferably 160 ° C. or higher and 190 ° C. or lower. With such an embodiment, the film has excellent heat resistance.
The polylactic acid in the present invention preferably has a weight average molecular weight (Mw) in the range of 80,000 to 250,000, and more preferably 100,000 to 250,000 or less. Particularly preferred is a range of 120,000 to 200,000. When the weight average molecular weight Mw is in the above numerical range, the rigidity of the film is excellent and the thickness unevenness of the film becomes good.

(Copolymerization component)
The poly L-lactic acid and poly D-lactic acid used in the present invention can contain a copolymer component other than L-lactic acid and D-lactic acid, as desired, within a range not impairing the object of the present invention. At this time, it is preferable to contain in the range which does not impair the crystallinity of polylactic acid largely. Such copolymerization component is not particularly limited. For example, hydroxycarboxylic acids such as glycolic acid, caprolactone, butyrolactone, propiolactone, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-propanediol, 1,5-propanediol, hexanediol, octanediol, decanediol, dodecanediol, aliphatic diols having 2 to 30 carbon atoms, succinic acid, maleic acid, adipic acid, 2 carbon atoms To 30 or more monomers selected from aromatic diols such as aliphatic dicarboxylic acid, terephthalic acid, isophthalic acid, hydroxybenzoic acid, hydroquinone, and aromatic dicarboxylic acid.

(Polylactic acid production method)
The method for producing poly L-lactic acid and poly D-lactic acid is not particularly limited, and conventionally known methods can be suitably used. For example, a method of directly dehydrating and condensing L-lactic acid or D-lactic acid, a method of solid-phase polymerizing L- or D-lactic acid oligomers, once dehydrating and cyclizing L- or D-lactic acid into lactide, and then melt-opening The method of superposing | polymerizing etc. is illustrated.
Among them, polylactic acid obtained by a direct dehydration condensation method or a melt ring-opening polymerization method of lactides is preferable from the viewpoint of quality and production efficiency, and among them, a melt ring-opening polymerization method of lactides is particularly preferably selected.

The catalyst used in these production methods is not particularly limited as long as polylactic acid can be polymerized so as to have the predetermined characteristics described above, and a known catalyst can be used as appropriate.
The obtained poly L-lactic acid and poly D-lactic acid may be removed by a conventionally known method or the catalytic activity of the polymerization catalyst is deactivated or deactivated using a deactivator. It is preferable for the melt stability and wet heat stability of the film.

  When using a deactivator, the amount used is 0.3 to 20 equivalents, more preferably 0.5 to 15 equivalents, and even more preferably 0.5 to 10 equivalents per equivalent of metal element of the specific metal-containing catalyst. Particularly preferably, it may be 0.6 to 7 equivalents. If the amount of the deactivator used is too small, the activity of the catalyst metal cannot be lowered sufficiently, and if used excessively, the deactivator may cause decomposition of the resin, which is not preferable.

<Oriented polylactic acid film>
One of the characteristics of the present invention is that the oriented polylactic acid film layer to be used has a main orientation axis in an oblique direction with respect to the film forming direction. In order to have the main orientation axis in such an oblique direction, the film may be stretched in the oblique direction as described in Patent Documents 6 to 8 described above. In order to set the acute angle formed by the main alignment axes of the adjacent aligned polylactic acid films to 0 degrees or 90 degrees, the main alignment axis of the aligned polylactic acid film layer is 45 with respect to the film forming direction. It is preferable that Then, the closer the angle formed by the film forming direction and the main alignment axis is to 45 degrees, the closer the acute angle formed by the main alignment axes of adjacent aligned polylactic acid film layers can be to 0 degrees or 90 degrees. From such a viewpoint, the angle formed by the film forming direction and the main orientation axis is preferably in the range of 40 to 50 degrees, more preferably 42 to 48 degrees.
In addition, the main orientation axis in this invention is a direction with the highest refractive index of the in-plane direction measured using the ellipsometer (model M-220; JASCO).

By the way, the reason why the variation in the piezoelectric body can be suppressed by setting the main orientation axis to be oblique with respect to the film forming direction in this way is not clear, but it is performed by roll-to-roll until it is laminated on the piezoelectric body. It is difficult to cause an angle shift when laminating, and a large orientation difference is required between the main orientation axis and a direction perpendicular to the main orientation axis in order to develop piezoelectric characteristics. Although it differs greatly in the film-forming direction and the width direction, since the main orientation axis is inclined with respect to the film-forming direction, the film-forming direction and the width direction can be simply stacked or turned upside down without changing the film-forming direction and the width direction. It is considered that the effect of the difference in the characteristics is mitigated because the lamination is sufficient.
From such a viewpoint, it is preferable that the manufacturing method of the present invention prepares a plurality of rolls of the laminate A, rolls them up, and crimps them.

  Hereinafter, the manufacturing method of the oriented polylactic acid film in this invention is demonstrated. The oriented polylactic acid film in the present invention is formed by, for example, extruding a polylactic acid resin composed of either poly L-lactic acid or poly D-lactic acid in a molten state to form an unstretched film. The film is stretched at least twice to obtain an oriented polylactic acid film. In addition, about manufacture of an oriented film layer, although the method to manufacture the oriented film layer L is demonstrated, also about the oriented film layer D, it manufactures similarly as the resin D which uses poly D-lactic acid as the main component. be able to.

(Extrusion process)
First, poly L-lactic acid (in the case of layer L. In the case of layer D, it is referred to as poly D-lactic acid) containing a carboxyl group-capping agent, a lubricant, and other additives, which will be described later, if desired. Resin L (when poly L-lactic acid is used. When poly D-lactic acid is used, resin D. The same applies hereinafter) is melted in an extruder and extruded from a die onto a cooling drum. In addition, in order to suppress decomposition at the time of melting, the resin supplied to the extruder is preferably subjected to a drying process before being supplied to the extruder so that the water content is about 100 ppm or less.

  The resin temperature in the extruder is a temperature at which the resin has sufficient fluidity, that is, when the melting point of the resin L is Tm, it is carried out in the range of (Tm + 20) to (Tm + 50) (° C.), but the resin does not decompose. It is preferable to perform melt extrusion at a temperature, and such a temperature is preferably 200 to 260 ° C, more preferably 205 to 240 ° C, and particularly preferably 210 to 235 ° C. Within the above temperature range, flow spots are unlikely to occur.

(Casting process)
After extruding from the die, the film is cast on a cooling drum to obtain an unstretched film. At that time, it is preferable that the electrostatic charge is applied from the electrode by an electrostatic contact method so that it is sufficiently brought into close contact with the cooling drum and cooled and solidified. At this time, the electrode to which an electrostatic charge is applied preferably has a wire shape or a knife shape. The surface material of the electrode is preferably platinum, and can prevent impurities sublimated from the film from adhering to the electrode surface. Further, it is possible to prevent adhesion of impurities by blowing a high-temperature air flow on or near the electrode, keeping the temperature of the electrode at 170 to 350 ° C., and installing an exhaust nozzle above the electrode.

(Stretching process)
The unstretched film obtained above is stretched obliquely in a direction of 45 degrees with respect to the film forming direction. In order to obtain such an obliquely stretched film, the unstretched film is stretched by heating to a temperature at which the unstretched film can be stretched, for example, a glass transition temperature (Tg) or higher (Tg + 80) ° C. of the resin L. In addition, the film forming direction in the present invention is a direction in which the film travels, and when the direction of stretching after stretching is considered as the film forming direction when it changes before and after stretching as in Patent Document 8 described above. Good.

  The draw ratio in the oblique direction is preferably 3 to 10 times, more preferably 3.5 to 8 times. By making the draw ratio within the above numerical range, the effect of improving the piezoelectric characteristics can be enhanced. When the draw ratio is high, the mechanical properties of the film tend to be inferior, while when it is low, the effect of improving the piezoelectric properties tends to be low. From such a viewpoint, the draw ratio is more preferably 4 to 7, and particularly preferably 4.5 to 6.

(Heat treatment process)
The oriented polylactic acid film obtained above is preferably heat-treated. The heat treatment temperature may be higher than the above-mentioned stretching temperature and lower than the melting point (Tm) of the resin, preferably the glass transition temperature (Tg + 15) ° C. or more and (Tm−10) ° C. or less, more preferably (Tg + 20). ) ° C. or higher (Tm−20) ° C., particularly preferably (Tg + 30) ° C. or higher (Tm−35) ° C. When the heat treatment temperature is in the above range, the main alignment axis can be easily aligned and the mechanical properties can be excellent while improving the thickness unevenness and surface flatness. The heat treatment time is preferably 1 to 120 seconds, more preferably 2 to 60 seconds.
Furthermore, in the present invention, it is possible to adjust the thermal dimensional stability by performing a relaxation treatment in the heat treatment step.

(Corona treatment, primer treatment)
The oriented polylactic acid film layer thus obtained can be subjected to surface activation treatment such as plasma treatment, amine treatment or corona treatment by a conventionally known method if desired.
Among these, from the viewpoint of improving the adhesion with the conductive layer M and enhancing the durability of the laminated film, it is preferable to perform corona treatment on at least one side, preferably both sides, of the oriented film layer. As conditions for such corona treatment, for example, when the electrode distance is 5 mm, the voltage is preferably 1 to 20 kV, more preferably 5 to 15 kV, preferably 1 to 60 seconds, more preferably 5 to 30 seconds, particularly Preferably it is 10 to 25 seconds. Further, such treatment can be performed in the atmosphere.

Similarly, from the viewpoint of improving the adhesion with the conductive layer M, at least one surface, preferably both surfaces, of the oriented film layer can be subjected to primer treatment to form an adhesive layer. In this case, the thickness of the adhesive layer is preferably 1000 nm or less. When the thickness of the adhesive layer is too thick, the resonance characteristics are inferior. As described above, from the viewpoint of adhesiveness, the thickness of the adhesive layer may be appropriately selected so that appropriate adhesiveness can be imparted. However, from the viewpoint of resonance characteristics, the thinner one is preferable, preferably Is 500 nm or less, more preferably 200 nm or less. In the present invention, from the viewpoint of resonance characteristics, a particularly preferred embodiment is an embodiment that does not have an adhesive layer.
Such primer treatment can be performed by a so-called in-line coating method in the process of producing a film, or by a so-called offline coating method after producing the film.

(density)
In the present invention, the density of the oriented polylactic acid film layer is preferably 1.22-1.27 g / cm ³ . When the density is in the above numerical range, the effect of improving the resonance characteristics can be enhanced. When the density is low, the effect of improving the piezoelectric characteristics tends to be low. On the other hand, when the density is high, the effect of improving the resonance characteristics is high, but the mechanical characteristics of the film tend to be inferior. From such a viewpoint, the density is more preferably 1.225 to 1.26 g / cm ³ , and still more preferably 1.23 to 1.25 g / cm ³ .

(Thickness of oriented polylactic acid film)
The thickness of the oriented polylactic acid film in the present invention is not particularly limited as long as it has a thickness that exhibits resonance characteristics in consideration of the tendency that rigidity is too high and resonance characteristics are not exhibited because it is too thick. The thinner one is preferable from the viewpoint of resonance characteristics. In particular, when increasing the number of layers, it is preferable to reduce the thickness of each layer so that the thickness of the entire laminated film does not become too large. From such a viewpoint, the thickness of one layer of the oriented polylactic acid film layer is preferably 15 μm or less, more preferably 12 μm or less, particularly preferably 10 μm or less. Can be high. On the other hand, from the viewpoint of handleability and rigidity, a thicker is preferable, for example, 2 μm or more is preferable, and 3 μm or more is more preferable.

(Heat shrinkage of oriented polylactic acid film layer)
The heat shrinkage rate at 110 ° C. in the film forming direction and the width direction of the oriented polylactic acid film in the present invention is 3% or less, and further 2.5%, from the viewpoint of suppressing the promotion of variation due to the difference in physical properties when laminated. It is preferable to be in the following range. Moreover, it is so preferable that the thermal aberration of a film forming direction and the width direction is small, for example, 2% or less, More preferably, it is 1.5% or less. In order to reduce such a heat shrinkage rate, it can be adjusted by stretching in an oblique direction and increasing the temperature of the heat setting process described above or performing a relaxation process.

(Thickness unevenness of oriented polylactic acid film)
When the thickness is viewed in a direction (width direction) orthogonal to the film-forming direction of the oriented polylactic acid film in the present invention, the value obtained by dividing the difference between the maximum value and the minimum value by the average thickness is 30% or less. Is preferred. When a film is usually formed and wound, it is called oscillation and the film is wound while shifting the position of the film in the width direction. This is because if the position in the width direction is not shifted, the thickness unevenness of the film will continue to overlap, resulting in a film roll with a very poor roll shape, which will be a problem in later steps. However, in the present invention, the angle of the main alignment axis is preferably constant, and the oscillation is preferably as small as possible. From such a viewpoint, the value obtained by dividing the difference between the maximum value and the minimum value of the thickness when viewed over a range of 50 cm in the width direction of the film by the average thickness is preferably 30% or less, and further 20% or less. It is preferable that It is effective to increase the orientation of such thickness spots by increasing the draw ratio or to promote crystallization by increasing the temperature of the heat setting treatment described above. At this time, if the heat setting temperature is raised too much, the orientation is relaxed or the crystals are melted.

(Components that may be added to the oriented polylactic acid film layer)
(Carboxyl group blocking agent)
In the polylactic acid in the present invention, the amount of carboxyl groups is preferably 10 equivalents / 10 ⁶ g or less from the viewpoint of stability during film casting, hydrolysis inhibition, and weight average molecular weight reduction inhibition. From such a viewpoint, The amount of carboxyl groups is more preferably 5 equivalents / 10 ⁶ g or less, and particularly preferably 2 equivalents / 10 ⁶ g or less. In order to set it as such an aspect, it is preferable to mix | blend a carboxyl group sealing agent. Carboxyl group sealant seals terminal carboxyl groups of polyesters such as polylactic acid, as well as carboxyl groups generated by decomposition reactions of polyester and various additives, and carboxyl groups of low molecular compounds such as lactic acid and formic acid. The resin can be stabilized, and there is an advantage that the resin temperature at the time of film formation can be raised to a temperature sufficient to suppress flow spots.

As such a carboxyl group-capping agent, it is preferable to use at least one compound selected from a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, and an isocyanate compound, and among them, a carbodiimide compound is preferable.
As for the usage-amount of a carboxyl group sealing agent, in resin which comprises each layer, 0.01-10 mass parts is preferable per 100 mass parts of polylactic acid, and 0.03-5 mass parts is further more preferable. In the present invention, a sealing reaction catalyst may be further used.

(Lubricant)
In the present invention, a lubricant may be contained in these films for the purpose of improving the winding and running properties of each oriented film layer and laminated film.
Examples of such lubricants include silica produced by a dry method, silica produced by a wet method, zeolite, calcium carbonate, calcium phosphate, kaolin, kaolinite, clay, talc, titanium oxide, alumina, zirconia, aluminum hydroxide, Preferable examples include inorganic particles such as calcium oxide, graphite, carbon black, zinc oxide, silicon carbide, and tin oxide, and organic fine particles such as crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles, and crosslinked silicone resin particles. .
As the lubricant, fine particles having an average particle diameter of 0.001 to 5.0 μm are preferable, and one kind can be used, or two or more kinds can be used in combination. Moreover, a lubricant can be mix | blended in 0.01-0.5 mass% with respect to the mass of each layer of the layer L or the layer D. FIG.

(Resin component)
The oriented polylactic acid film layer in the present invention can contain a resin component having a melting point higher than that of polylactic acid for the purpose of imparting heat resistance.
Such a resin component preferably has a melting point higher by 3 ° C. or more than polylactic acid, and can improve the heat resistance improvement effect. From such a viewpoint, the melting point of the resin component is more preferably 5 ° C. or more higher than that of polylactic acid, and particularly preferably 10 ° C. or more.
Preferred examples of the resin component include polyethylene naphthalate, polyethylene terephthalate, stereocomplex phase polylactic acid, polyetherimide, polyphenylene ether, poly (meth) acrylamide, and polystyrene.

  The content of the resin component is preferably 10 to 50% by mass based on the mass of each layer. When the content is in the above numerical range, excellent heat resistance can be imparted while maintaining excellent resonance characteristics. When the content is too small, the effect of improving heat resistance tends to be low. From such a viewpoint, the content of the resin component is more preferably 20% by mass or more, and particularly preferably 30% by mass or more. On the other hand, when the content is too large, the piezoelectricity of each layer tends to be low, and the effect of improving the resonance characteristics tends to be low. From such a viewpoint, the content of the resin component is more preferably 45% by mass or less, and particularly preferably 40% by mass or less.

  The method of containing the resin component is not particularly limited. For example, a mixture of pellets of polylactic acid constituting the oriented film layer and pellets of the resin component are obtained in advance, and the mixture is put into an extruder. Thus, the polylactic acid and the resin component can be melt-kneaded in the extruder.

(Other additives)
In addition, the layer L and / or the layer D are provided with an antioxidant, an antistatic agent, a colorant, a pigment, a fluorescent whitening agent, a plasticizer, a cross-linking agent, an ultraviolet absorber, and the like, as long as they do not contradict the spirit of the present invention. These resins can be added as necessary.

<Conductive layer>
The type of the conductive layer M in the present invention is not particularly limited as long as the piezoelectric body of the present invention has conductivity that can exhibit piezoelectric characteristics when a voltage is applied, but the piezoelectric layer is more preferably piezoelectric. From the viewpoint of exhibiting characteristics and resonance characteristics, a layer made of a metal or metal oxide is preferable.

  Such metal or metal oxide is not particularly limited, but is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten. Preferably, at least one metal selected from the group described above or an oxide of at least one metal selected from the above group is preferably used. Further, the metal oxide may further contain an oxide of a metal shown in the above group or another metal shown in the above group, if necessary. For example, indium oxide containing tin oxide and tin oxide containing antimony are preferably used.

The thickness of the conductive layer M is not particularly limited, but the surface resistance value is 1 × 10 ⁴ Ω / □ or less, preferably 5 × 10 ³ Ω / □ or less, more preferably 1 × 10 ³ Ω / □ or less. Such a thickness may be selected. For example, the thickness is preferably 10 nm or more. Furthermore, it is preferable that it is 15-35 nm from a viewpoint of electroconductivity and the ease of layer formation, More preferably, it is 20-30 nm. If the thickness is too thin, the surface resistance value tends to be high, and it becomes difficult to form a continuous film. On the other hand, if it is too thick, the quality is excessive, and it is difficult to form the piezoelectric body, and the strength between the layers of the piezoelectric body tends to be weakened.

  The piezoelectric body manufacturing method of the present invention is a laminate in which a conductive layer is formed on one surface of an alignment film obtained by the manufacturing method described later, and the alignment film and the conductive film are in a relationship of the main alignment direction described later. Laminate layers alternately.

  It does not specifically limit as a formation method of the conductive layer M, A conventionally well-known method is employable. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified, and a vapor deposition method or a sputtering method is adopted from the viewpoint that a conductive layer having excellent conductivity can be obtained uniformly and easily. It is preferable to do. In addition, after forming a metal layer, it can crystallize by giving an annealing process within the range of 100-150 degreeC as needed. For this reason, it is preferable that the layer L and the layer D have heat resistance of 100 ° C. or higher, more preferably 110 ° C. or higher. Moreover, although the conductive layer M may be formed on both surfaces of the oriented film layer, it is preferable to form the conductive layer M only on one surface from the viewpoint of adhesion.

<Other layers>
In the present invention, as long as it has a laminated structure like the above-described piezoelectric body, it may have other layers within a range not impairing the object of the present invention. For example, an aromatic polyester layer such as polyethylene terephthalate or polyethylene naphthalate for increasing the rigidity of the laminated film can be provided on the surface of the laminated film. On the other hand, from the viewpoint of resonance characteristics, such a layer is preferably thin and particularly preferably not.

<Method for manufacturing piezoelectric body>
In the production method of the present invention, the oriented polylactic acid film layer having the conductive layer M obtained as described above is laminated and pressure-bonded so as to have the above-described laminated structure, thereby producing a laminate.
It is preferable that the temperature conditions for such pressure bonding are (Tg-5) to (Tsm + 20) ° C. Here, Tg indicates the highest glass transition temperature among the glass transition temperature of the resin L constituting the oriented film layer L used for forming the laminated film and the glass transition temperature of the resin D constituting the oriented film layer D. Tsm indicates the lowest sub-peak temperature among the sub-peak temperature of the oriented film layer L and the sub-peak temperature of the oriented film layer D used for forming the laminated film. In addition, subpeak temperature is temperature resulting from the heat setting temperature in a film manufacturing process. By adopting the above temperature condition, a laminated film having excellent resonance characteristics can be obtained. At the same time, the adhesion of each layer of the laminated film is excellent. If the temperature is too low, the adhesion tends to be inferior. On the other hand, if the temperature is too high, the orientation is lost and the resonance characteristics tend to be inferior. From such a viewpoint, more preferable temperature conditions are Tg to Tsm + 15, and particularly preferably Tg + 10 to Tsm + 10.

Moreover, it is preferable that pressure conditions shall be 1-100 Mpa. Thereby, it is possible to obtain a laminated film excellent in adhesion while having excellent resonance characteristics. If the pressure is too low, the adhesion tends to be inferior, whereas if the pressure is too high, the resonance characteristics tend to be inferior. From such a viewpoint, the more preferable pressure condition is 2 to 80 MPa, and particularly preferably 2 to 50 MPa.
It is preferable to perform thermal lamination for 10 to 600 seconds under the above temperature and pressure conditions. Thereby, it is possible to obtain a laminated film excellent in adhesion while having excellent resonance characteristics. If the time is too short, the adhesion tends to be inferior, while if too long, the resonance characteristics tend to be inferior. From such a viewpoint, a more preferable time condition is 30 to 300 seconds, and particularly preferably 60 to 180 seconds.

<Piezoelectric body>
The piezoelectric body obtained by the production method of the present invention is a laminate of the oriented polylactic acid film layer (1) and the conductive layer M, and the oriented polylactic acid film layer (2) and the conductive layer M, and has high piezoelectric characteristics. In view of the above, the total number of oriented polylactic acid film layers is preferably 4 or more, more preferably 8 or more, and particularly preferably 10 or more. On the other hand, the upper limit of the total number is 300 or less from the viewpoint of preventing the thickness of the entire piezoelectric laminate from becoming excessively strong while giving the oriented polylactic acid film layer a thickness that has a certain degree of handleability. It is preferable that it is 200 or less.

Further, as described above, when the adjacent oriented polylactic acid films are both poly L-lactic acid or poly D-lactic acid so that the piezoelectric properties do not cancel each other, the main orientation axes thereof are orthogonal to each other. On the other hand, in the case of poly L-lactic acid and poly D-lactic acid, it is preferable to laminate them so that their main orientation axes are in the same direction.
Among them, all the oriented polylactic acid film layers forming the piezoelectric body in the present invention are preferably composed of either poly L-lactic acid or poly D-lactic acid. In the method of alternately laminating film layers made of poly-L-lactic acid and film layers made of poly-D-lactic acid, the raw materials used are different. Although it is difficult, as long as it is either poly L-lactic acid or poly D-lactic acid, it is only necessary to form a film of the same raw material under the same conditions, and the control can be performed more easily.

  When the adjacent oriented polylactic acid film layers are both poly L-lactic acid or poly D-lactic acid, a conductive layer is formed on one surface of the oriented polylactic acid film layer, and the oriented polylactic acid film layer. It is preferable to prepare a layer having a conductive layer formed on the other surface and laminate them alternately. In addition, when the adjacent oriented polylactic acid film layers are poly L-lactic acid and poly D-lactic acid, each prepared by forming a conductive layer on the same surface of the oriented polylactic acid film layer is prepared, and these are alternately arranged. It is preferable to laminate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive limitation at all by this. In addition, each value in an Example was calculated | required according to the following method.

(1) Piezoelectric properties As shown in FIG. 2, a conductive adhesive (made by Fujikura Kasei, Dotite D550) is applied to both short sides of the obtained piezoelectric laminate to form an electrode (symbol 6), and the piezoelectric A sex structure was created. Thus, in each aluminum vapor deposition layer, the conductive adhesive and the aluminum vapor deposition layer are not short-circuited on the side having a margin, and the conductive adhesive and the aluminum vapor deposition layer are short-circuited on the side having no margin. It becomes composition.
An aluminum foil is attached to each electrode of this piezoelectric laminate, and as shown in FIG. 3, it is attached to a piezoelectric characteristic measuring apparatus 12 (manufactured by Agilent Technologies, trade name: Precision Impedance Analyzer 4294A), and resonance of admittance by the two-terminal method. Measurements were made. At this time, as shown in FIG. 3, the piezoelectric laminate was placed on the cylinder 11 so as to reduce the contact area with the desk surface so as not to affect the resonance. The admittance resonance was measured by a method of measuring a piezoelectric resonance waveform with the equivalent circuit pattern E, and the piezoelectric ratio (unit: pC / N) was calculated from the various parameters obtained. Higher piezoelectricity means better piezoelectric performance.
In addition, the said measurement produced 10 samples and performed about each, and made those averages the piezoelectricity. Further, the difference between the maximum value and the minimum value among the ten measured values divided by the minimum value was calculated as the variation (%) in piezoelectricity.

(2) Peeling of laminated film The end of the laminated film was squeezed to make a notch, each layer was peeled off, the oriented film layer L and layer D were peeled off, and used for evaluating physical properties of each layer.

(3) Density The film sample peeled from the laminated film was measured according to JIS standard C2151.

(4) Main orientation axis Using an ellipsometer (model M-220; JASCO), the obtained film was subjected to transmitted light measurement with the incident angle of 550 nm monochromatic light varied, and the sample stage on which the film was fixed was By rotating in a plane perpendicular to the optical axis about the axis, the direction with the highest refractive index in the in-plane direction was determined, and that direction was defined as the main alignment axis. The angles formed by the main orientation axis and the film forming direction were determined and are shown in Table 1.

(5) Glass transition temperature (Tg), sub-peak temperature (Tsm), melting point (Tm)
About the oriented film layer obtained as a laminated film before forming a laminated film, about 10 mg of a sample is enclosed in an aluminum pan for measurement and attached to a differential calorimeter (trade name “DSC2920” manufactured by TA instruments), 25 The film was heated from 210 ° C. to 210 ° C. at a rate of 10 ° C./min, and the sub-peak temperature (Tsm: ° C.) and melting point (Tm: ° C.) of the film were measured. Next, after continuously holding at 210 ° C. for 3 minutes, it is taken out, immediately transferred onto ice and rapidly cooled, this pan is again attached to the differential calorimeter, and the temperature is raised from 25 ° C. at a rate of 10 ° C./min. The glass transition temperature (Tg: ° C.) and melting point (Tm: ° C.) of the resin constituting the film were measured.

(6) Conductivity (surface resistance value)
It measured based on JISK7194 using Mitsubishi Chemical Corporation make and brand name: Lorester MCP-T600. The measurement was performed by taking three measurement sample pieces from one film and carrying out the measurement at five arbitrary locations, and taking the average value as the surface resistance value (unit: Ω / □).

[Reference Example 1] Synthesis of poly L-lactic acid (PLLA) by melt ring-opening polymerization of lactide Vertical type equipped with full zone blades equipped with vacuum piping and nitrogen gas piping, catalyst, L-lactide solution addition piping, and alcohol initiator addition piping The stirring tank (40 L) was purged with nitrogen. Thereafter, 30 kg of L-lactide, 0.90 kg of stearyl alcohol (0.030 mol / kg), and 6.14 g of tin octylate (5.05 × 10 ⁻⁴ mol / 1 kg) were charged in an atmosphere with a nitrogen pressure of 106.4 kPa. The temperature was raised to 150 ° C. When the contents were dissolved, stirring was started and the internal temperature was further raised to 190 ° C. Since the reaction started when the internal temperature exceeded 180 ° C., the internal temperature was maintained from 185 ° C. to 190 ° C. while cooling and the reaction was continued for 1 hour. The reaction was further carried out at a nitrogen pressure of 106.4 kPa and an internal temperature of 200 ° C. to 210 ° C. for 1 hour while stirring, and then stirring was stopped and a phosphorus-based catalyst deactivator was added.
After removing the bubbles by standing still for 20 minutes, the internal pressure was increased from 2 to 3 atm with nitrogen pressure, the prepolymer was pushed out to a chip cutter, and a prepolymer having a weight average molecular weight of 130,000 and a molecular weight dispersion of 1.8 was obtained. Pelletized.
Further, the pellets were dissolved by an extruder, charged into a non-axial vertical reactor at 15 kg / hr, reduced in pressure to 10.13 kPa to reduce the remaining lactide, and chipped again. The obtained poly L-lactic acid (PLLA) has a glass transition temperature (Tg) of 55 ° C., a melting point (Tm) of 175 ° C., a weight average molecular weight of 120,000, a molecular weight dispersion of 1.8, and a lactide content of 0.005% by mass. there were.

[Reference Example 2] Synthesis of poly D-lactic acid (PDLA) by melt ring-opening polymerization of lactide Glass transition temperature (Tg) in the same manner as above except that D-lactide was used instead of L-lactide. Poly-D-lactic acid (PDLA) having a temperature of 55 ° C., a melting point (Tm) of 175 ° C., a weight average molecular weight of 120,000, a molecular weight dispersion of 1.8, and a lactide content of 0.005% by mass was obtained.

[Example 1]
(Production of oriented poly L-lactic acid monolayer film 1)
The PLLA obtained in Reference Example 1 was sufficiently dried using a dryer, then charged into an extruder, melted at 220 ° C, and the molten resin was extruded from a die held at 220 ° C to form a single layer. The sheet was formed into a sheet, and the sheet was cooled and solidified with a cooling drum having a surface temperature of 25 ° C. to obtain an unstretched film. The obtained unstretched film was led to a tenter heated to 75 ° C. by a variable simultaneous biaxial stretching machine manufactured by Andritz, and the stretching direction was 45 ° with respect to the film forming direction (thus, with respect to the width direction). The clip on the left side in the direction of travel so as to be in the direction of 45 °), the speed of the clip on the right side is increased, the film is stretched 4.5 times in the 45 ° direction, and then the ends of the stretched film are clipped. While maintaining the temperature at 110 ° C. in a tenter for 30 seconds, uniformly cooled, cooled to room temperature, and 7 μm thick oriented poly L-lactic acid monolayer film 1 having a main axis at 45 ° ( 45 ° PLLA oriented film) was obtained. The obtained film was 700 mm in width, wound up to 100 m, and further slit to a width of 70 mm.

(Vapor deposition)
Single-sided corona treatment was performed on the oriented poly L-lactic acid monolayer film 1 having a width of 100 mm produced as described above using Kasuga's high frequency power source CG-102 type under the conditions of a voltage of 10 kV and a treatment time of 20 seconds. At this time, the film applied to the surface not in contact with the cooling drum during film formation is the oriented film 45L-A, and the film applied to the side in contact with the cooling drum is the oriented film 45L-D. Is a surface on which the conductive layer M is formed. Next, in the width direction of the corona-treated surface, the oriented film 45L-A is masked with a region having a width of 10 mm on the right side, and the oriented film 45L-D is masked with a region having a width of 10 mm on the left side as a margin. The remaining region (6 cm wide region) was subjected to aluminum deposition with a thickness such that the surface resistance value was 10 Ω / □. The conductive layer had a thickness of 50 nm. Then, the orientation film 45L-A and the orientation film 45L-D are overlapped so that the respective margins are arranged on the opposite side as shown in FIG. Wound around (total 20 layers). The laminated rolls were cut open and bonded by heat lamination at 110 ° C. and a pressure of 40 MPa over 3 minutes. Thereafter, the film was cut out in a size of 3 cm in the film forming direction and 7 cm in the width direction to produce a piezoelectric body, which was assembled and the piezoelectric characteristics were measured as described in the above (1) Piezoelectric characteristics. Table 1 shows the characteristics of the obtained piezoelectric body.

[Example 2]
Instead of the oriented poly L-lactic acid monolayer film 1, the same as in Example 1 was used except that the oriented poly L-lactic acid monolayer film 2 having a thickness of 7 μm with the draw ratio changed from 4.5 times to 5 times was used. The operation was repeated. Table 1 shows the characteristics of the obtained piezoelectric body.

[Example 3]
Instead of the oriented poly L-lactic acid monolayer film 1, the same operation as in Example 1 was used except that the oriented poly L-lactic acid monolayer film 3 having a thickness of 7 μm with the heat setting temperature changed from 110 ° C. to 100 ° C. was used. Was repeated. Table 1 shows the characteristics of the obtained piezoelectric body.

[Example 4]
The PDLA obtained in Reference Example 2 was sufficiently dried using a dryer, then charged into an extruder, melted at 220 ° C, and the molten resin was extruded from a die held at 220 ° C to form a single layer. The sheet was formed into a sheet, and the sheet was cooled and solidified with a cooling drum having a surface temperature of 25 ° C. to obtain an unstretched film. The obtained unstretched film was led to a tenter heated to 75 ° C. by a variable simultaneous biaxial stretching machine manufactured by Andritz, and the stretching direction was 45 ° with respect to the film forming direction (thus, with respect to the width direction). The clip on the left side in the direction of travel so as to be in the direction of 45 °), the speed of the clip on the right side is increased, the film is stretched 4.5 times in the 45 ° direction, and then the ends of the stretched film are clipped. While maintaining the temperature in the tenter for 30 seconds under a temperature condition of 110 ° C., uniformly cooled to room temperature, and 7 μm thick oriented poly D-lactic acid monolayer film 1 having a main axis at 45 ° ( 45 ° PDLA alignment film) was obtained. The obtained film was 700 mm in width, wound up to 100 m, and further slit to a width of 70 mm.

(Vapor deposition)
Single-sided corona treatment was performed on the oriented poly L-lactic acid monolayer film 1 having a width of 100 mm produced as described above using Kasuga's high frequency power source CG-102 type under the conditions of a voltage of 10 kV and a treatment time of 20 seconds. At this time, the film applied to the surface not in contact with the cooling drum at the time of film formation is the oriented film 45D-A, and the film applied to the side in contact with the cooling drum is the oriented film 45D-D. Is a surface on which the conductive layer M is formed. Next, in the width direction of the corona-treated surface, the alignment film 45D-A is masked with a region having a width of 10 mm on the right side, and the alignment film 45D-D is masked with a region having a width of 10 mm on the left side as a margin. The remaining region (6 cm wide region) was subjected to aluminum deposition with a thickness such that the surface resistance value was 10 Ω / □. The conductive layer had a thickness of 50 nm. Then, the orientation film 45D-A and the orientation film 45D-D are overlaid so that the respective margins are arranged on the opposite side as shown in FIG. The piezoelectric body was produced by repeating the same operation as in Example 1 by winding (total 20 layers). The obtained piezoelectric body was evaluated in the same manner as in Example 1. Table 1 shows the characteristics of the obtained piezoelectric body.

[Example 5]
Instead of the oriented poly L-lactic acid single layer film 1, the same operation as in Example 1 was repeated except that the oriented poly L-lactic acid single layer film 4 having a thickness changed from 7 μm to 10 μm was used. Table 1 shows the characteristics of the obtained piezoelectric body.

[Example 6]
The same operation as in Example 1 was repeated except that the number of windings around the core was changed from 10 (total 20 layers) to 20 (total 40 layers). Table 1 shows the characteristics of the obtained piezoelectric body.

[Example 7]
The same operation as in Example 1 was repeated except that the number of windings around the core was changed from 10 (total 20 layers) to 5 (total 10 layers). Table 1 shows the characteristics of the obtained piezoelectric body.

[Example 8]
The same operation as in Example 1 was repeated except that the oriented film 45D-A in Example 5 was used instead of the oriented film 45L-D in Example 1. Table 1 shows the characteristics of the obtained piezoelectric body.

[Example 9]
In Example 8, 5% by mass of the core shell structure (Paraloid ^TM BPM-500) manufactured by Rohm & Haas Japan Co., Ltd. was added to each oriented film, and the pressure during thermal lamination was changed to 20 MPa. The same operation as in Example 8 was repeated except that. Table 1 shows the characteristics of the obtained piezoelectric body.

[Comparative Example 1]
The PLLA obtained in Reference Example 1 was sufficiently dried using a dryer, then charged into an extruder, melted at 210 ° C., and the molten resin was extruded from a die and formed into a single-layer sheet, The sheet was cooled and solidified with a cooling drum having a surface temperature of 20 ° C. to obtain an unstretched film. The obtained unstretched film was led to a roll group heated to 75 ° C., stretched 1.1 times in the longitudinal direction, and cooled by a roll group at 25 ° C. Subsequently, both ends of the longitudinally stretched film were guided to a tenter while being held with clips, and stretched 4.5 times in the transverse direction in an atmosphere heated to 80 ° C. Thereafter, heat treatment is performed in a tenter at a temperature of 110 ° C. for 30 seconds, uniformly cooled to room temperature, and a 7 μm-thick biaxially oriented poly L-lactic acid monolayer film 5 having a principal axis at 0 ° in the width direction ( A PLLA oriented film L1) was obtained. The surface on the side not in contact with the cooling drum at the time of film formation was subjected to corona treatment under the conditions of a voltage of 10 kV and a treatment time of 20 seconds using a high-frequency power source CG-102 manufactured by Kasuga.
The obtained oriented film L1 was cut out at 7 cm × 3 cm so that 45 ° and 135 ° were in the length direction with respect to the film forming direction, and were used as oriented films L1-45 and L1-135, respectively.
Next, a 1 cm region (1 cm × 3 cm region) from one short side is masked as a margin to leave a portion not deposited, and the surface resistance value is 10 Ω / □ in the remaining region (6 cm × 3 cm region). The aluminum was deposited with such a thickness as follows. The conductive layer had a thickness of 50 nm. Moreover, the margin positions were created on the short sides on the opposite sides of the alignment film L1-45 and the alignment film L1-135. About the obtained vapor deposition film, each 10 sheets, a total of 20 sheets, were laminated | stacked, the pressure of 40 Mpa was applied for 3 minutes at 110 degreeC, and it bonded together by the thermal lamination. After the electrode step, the same operation as in Example 1 was repeated. Table 1 shows the characteristics of the obtained piezoelectric body.

[Comparative Example 2]
The PDLA obtained in Reference Example 2 was sufficiently dried using a dryer, then charged into an extruder, melted at 210 ° C., and the molten resin was extruded from a die and formed into a single-layer sheet, The sheet was cooled and solidified with a cooling drum having a surface temperature of 20 ° C. to obtain an unstretched film. The obtained unstretched film was led to a roll group heated to 75 ° C., stretched 1.1 times in the longitudinal direction, and cooled by a roll group at 25 ° C. Subsequently, both ends of the longitudinally stretched film were guided to a tenter while being held with clips, and stretched 4.5 times in the transverse direction in an atmosphere heated to 80 ° C. Thereafter, heat treatment is performed in a tenter at a temperature of 110 ° C. for 30 seconds, uniformly cooled to room temperature, and a biaxially oriented poly-D-lactic acid monolayer film 2 having a main axis at 0 ° in the width direction having a thickness of 7 μm ( A PDLA oriented film D1) was obtained. The surface on the side not in contact with the cooling drum at the time of film formation was subjected to corona treatment under the conditions of a voltage of 10 kV and a treatment time of 20 seconds using a high-frequency power source CG-102 manufactured by Kasuga.
The obtained oriented film L1 was cut out at 7 cm × 3 cm so that 45 ° was in the length direction with respect to the film forming direction, to obtain an oriented film D1-45.
And operation similar to the comparative example 1 was repeated except having used the oriented film D1-45 instead of each oriented film L1-135 of the comparative example 1. FIG. Table 1 shows the characteristics of the obtained piezoelectric body.

  According to the present invention, a piezoelectric body with small variations and excellent piezoelectric characteristics can be provided, and can be used as a vibrating body such as a microphone, a pickup, a buzzer, a speaker, an optical switch, a fan, or a piezoelectric actuator.

1 Resin layer for right margin 2 Resin layer for left margin 3 Conductive layer 4 Laminate A
5 Laminate B
6 Silver paste 7 Piezoelectric property measuring device 8 Conductor 9 Clip 10 Aluminum foil 11 Cylinder

Claims (8)

An unstretched film made of either poly-L-lactic acid or poly-D-lactic acid is inclined in an oblique direction in which the main orientation axis is in the range of 40 to 50 degrees with respect to the film-forming direction. Stretching to make an oriented polylactic acid film,
A step of forming a conductive layer on one surface of the oriented polylactic acid film to form a laminate A, and a step of laminating and pressing the laminate A so that the oriented polylactic acid film layers and the conductive layers are alternately arranged A method for manufacturing a piezoelectric body comprising:   The method for manufacturing a piezoelectric body according to claim 1, wherein the total number of layers of the oriented polylactic acid film is 4 or more.   The method for producing a piezoelectric body according to claim 1, wherein the oriented polylactic acid film has a thickness of 15 μm or less.   2. The method for producing a piezoelectric body according to claim 1, wherein the thermal contraction rate at 110 ° C. in the film forming direction and the width direction of the oriented polylactic acid film is in a range of 3% or less.   The method for producing a piezoelectric body according to claim 1, wherein the thickness unevenness in a direction (width direction) orthogonal to the film forming direction of the oriented polylactic acid film is 30% or less.   When the adjacent oriented polylactic acid films are both poly L-lactic acid or poly D-lactic acid, the main orientation axes thereof are perpendicular to each other, and the other is poly L-lactic acid and poly D-lactic acid. The method for manufacturing a piezoelectric body according to claim 1, wherein lamination is performed so that their main orientation axes are in the same direction.   The method for producing a piezoelectric body according to claim 6, wherein all the oriented polylactic acid films are poly-L-lactic acid or poly-D-lactic acid.   The method for manufacturing a piezoelectric body according to claim 1, wherein a plurality of rolls of the laminated body A are prepared, and the rolls are stacked, wound, and pressure-bonded.