TWI771452B - Piezoelectric material and composition for piezoelectric material - Google Patents
Piezoelectric material and composition for piezoelectric material Download PDFInfo
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Abstract
[課題]本發明係的目的係提供一種具有優異的柔軟性及伸縮性的壓電材料,以及用於獲得該壓電材料的壓電材料組成物。[解決手段]本發明的一種壓電材料,其係包含:偏氟乙烯/三氟乙烯共聚物;以及丙烯酸系彈性體,其係具有來自式(I)所表示之丙烯酸系單體的構造單元,且重量平均分子量為100萬以上;(式中的R係,可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代之具有1至10個碳原子的烷基;具有至少一個碳原子可被氧原子取代之碳原子數為3~6的脂環式烴基之碳原子數為3~12的烴基;亞烷基部份的碳原子數為1~4,且亞烷基部份的一個-CH2 -可被-O-取代之苯基亞烷基;或者,以-((CH2 )m -O-)n -X表示的基[式中的m及n係各自表示2或3的數字,X係表示氫原子或甲基])。[Problem] The object of the present invention is to provide a piezoelectric material having excellent flexibility and stretchability, and a piezoelectric material composition for obtaining the piezoelectric material. [Solution] A piezoelectric material of the present invention includes: a vinylidene fluoride/trifluoroethylene copolymer; and an acrylic elastomer having a structural unit derived from an acrylic monomer represented by formula (I) , and the weight average molecular weight is more than 1 million; (R in the formula is an alkyl group with 1 to 10 carbon atoms which can be substituted by a hydroxyl group, an alkyl group with 1 or 2 carbon atoms and/or an alkoxy group with 1 to 6 carbon atoms; An alicyclic hydrocarbon group with 3 to 6 carbon atoms in which one carbon atom can be replaced by an oxygen atom; a hydrocarbon group with 3 to 12 carbon atoms; the alkylene moiety has 1 to 4 carbon atoms, and the alkylene group has 1 to 4 carbon atoms. A part of -CH 2 - may be substituted by -O- phenylalkylene; or, a group represented by -((CH 2 ) m -O-) n -X [m and n in the formula are each A number representing 2 or 3, and X represents a hydrogen atom or a methyl group]).
Description
本發明係關於壓電材料及壓電材料用組成物。The present invention relates to piezoelectric materials and compositions for piezoelectric materials.
作為強介電性高分子之包含偏氟乙烯(VDF)與三氟乙烯共聚物(TrFE)的共聚物,將偏氟乙烯/三氟乙烯共聚物(P(VDF/TrFE)作為具有優異壓電特性與自發極化(殘留極化)之壓電材料,係廣為人知的。此壓電材料,被用於例如壓電傳感器‧換能器、紅外線熱釋電傳感器等各種壓電元件。As a ferroelectric polymer including vinylidene fluoride (VDF) and trifluoroethylene copolymer (TrFE) copolymer, vinylidene fluoride/trifluoroethylene copolymer (P(VDF/TrFE) Piezoelectric materials with characteristics and spontaneous polarization (residual polarization) are widely known. Such piezoelectric materials are used in various piezoelectric elements such as piezoelectric sensors, transducers, and infrared pyroelectric sensors.
於專利文獻1中,揭示一種壓電膜,其係在特定的莫耳比下,由將偏氟乙烯與三氟乙烯共聚合而獲得之共聚物所製成。Patent Document 1 discloses a piezoelectric film made of a copolymer obtained by copolymerizing vinylidene fluoride and trifluoroethylene at a specific molar ratio.
[先前技術文獻] [專利文獻] [專利文獻1]國際公開第2016/159354號[Prior Art Document] [Patent Document] [Patent Document 1] International Publication No. 2016/159354
[發明概要] [發明所欲解決的課題] 近年來,已經嘗試在包括可穿戴設備的領域中使用壓電材料。針對在此領域所使用之壓電材料而言,尋求著相較於習知更優異的柔軟性及伸縮性。因此,本發明人們著眼於包含偏氟乙烯與三氟乙烯之共聚物的壓電材料,並針對提供在可穿戴設備等領域中所需之具有高柔韌性與可拉伸性的材料進行探討。舉例來說,在如同專利文獻1所記載之壓電膜中,從柔軟性及伸縮性的觀點來看,尋求著更進一步的改善。[Summary of the Invention] [Problem to be Solved by the Invention] In recent years, attempts have been made to use piezoelectric materials in fields including wearable devices. For piezoelectric materials used in this field, more excellent flexibility and stretchability than conventional ones are sought. Therefore, the inventors of the present invention have focused on piezoelectric materials comprising copolymers of vinylidene fluoride and trifluoroethylene, and have studied to provide materials with high flexibility and stretchability required in the fields of wearable devices and the like. For example, in the piezoelectric film as described in Patent Document 1, further improvements are sought from the viewpoints of flexibility and stretchability.
因此,本發明的目的之一,係提供具有優異柔軟性、伸縮性之壓電材料及用於獲得該壓電材料的壓電材料用組成物。Therefore, one of the objects of the present invention is to provide a piezoelectric material having excellent flexibility and stretchability, and a piezoelectric material composition for obtaining the piezoelectric material.
[用以解決課題之手段] [1]本發明的壓電材料,其係包含: 偏氟乙烯/三氟乙烯共聚物;以及丙烯酸系彈性體,其係具有來自式(I)所表示之丙烯酸系單體的構造單元,且重量平均分子量為100萬以上; 式(I) : [化1](式中的R係,可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代之具有1至10個碳原子的烷基;具有至少一個碳原子可被氧原子取代之碳原子數為3~6的脂環式烴基之碳原子數為3~12的烴基;亞烷基部份的碳原子數為1~4,且亞烷基部份的一個-CH2 -可被-O-取代之苯基亞烷基;或者,以-((CH2 )m -O-)n -X表示的基[式中的m及n係各自表示2或3的數字,X係表示氫原子或甲基])。 在本說明書中,亦將偏氟乙烯/三氟乙烯共聚物簡稱為PVT。又,在偏氟乙烯/三氟乙烯的聚合比為80mol%/20mol%時,亦將其簡稱為PVT80/20。[MEANS TO SOLVE THE PROBLEM] [1] The piezoelectric material of the present invention, comprising: a vinylidene fluoride/trifluoroethylene copolymer; and an acrylic elastomer having acrylic acid derived from formula (I) The structural unit of the monomer, and the weight average molecular weight is 1 million or more; Formula (I): [Chemical 1] (R in the formula is an alkyl group with 1 to 10 carbon atoms which can be substituted by a hydroxyl group, an alkyl group with 1 or 2 carbon atoms and/or an alkoxy group with 1 to 6 carbon atoms; An alicyclic hydrocarbon group with 3 to 6 carbon atoms in which one carbon atom can be replaced by an oxygen atom; a hydrocarbon group with 3 to 12 carbon atoms; the alkylene moiety has 1 to 4 carbon atoms, and the alkylene group has 1 to 4 carbon atoms. A part of -CH 2 - may be substituted by -O- phenylalkylene; or, a group represented by -((CH 2 ) m -O-) n -X [m and n in the formula are each A number representing 2 or 3, and X represents a hydrogen atom or a methyl group]). In this specification, the vinylidene fluoride/trifluoroethylene copolymer is also abbreviated as PVT. In addition, when the polymerization ratio of vinylidene fluoride/trifluoroethylene is 80 mol %/20 mol %, it is also abbreviated as PVT80/20.
本發明還包含以下較佳態樣。 [2]如[1]所述之壓電材料,其中,基於壓電材料整體,偏氟乙烯/三氟乙烯共聚物的量係98~70質量%,基於壓電材料整體,丙烯酸系彈性體的量係2~30質量%。The present invention also includes the following preferred aspects. [2] The piezoelectric material according to [1], wherein the amount of the vinylidene fluoride/trifluoroethylene copolymer is 98 to 70% by mass based on the entire piezoelectric material, and the acrylic elastomer is based on the entire piezoelectric material The amount of 2~30% by mass.
[3]如[1]或[2]所述之壓電材料,其中,偏氟乙烯/三氟乙烯共聚物的黏度平均分子量係10萬/mol以上。[3] The piezoelectric material according to [1] or [2], wherein the vinylidene fluoride/trifluoroethylene copolymer has a viscosity-average molecular weight of 100,000/mol or more.
[4]如[1]~[3]中任一者所述之壓電材料,其中,在偏氟乙烯/三氟乙烯共聚物中,基於全部構造的量,來自偏氟乙烯構造單元的量係55~90mol%。[4] The piezoelectric material according to any one of [1] to [3], wherein, in the vinylidene fluoride/trifluoroethylene copolymer, the amount derived from the vinylidene fluoride structural unit is based on the amount of all the structures Department of 55~90mol%.
[5]如[1]~[4]中任一者所述之壓電材料,其中,楊氏率(Young's modulus)係3.1GPa以下。[5] The piezoelectric material according to any one of [1] to [4], wherein a Young's modulus is 3.1 GPa or less.
本發明的壓電材料用組成物,其係包含: 偏氟乙烯/三氟乙烯共聚物;以及丙烯酸系彈性體,其係具有來自式(I)所表示之丙烯酸系單體的構造單元,且重量平均分子量為100萬以上; 式(I) : [化2](式中的R係,可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代之具有1至10個碳原子的烷基;具有至少一個碳原子可被氧原子取代之碳原子數為3~6的脂環式烴基之碳原子數為3~12的烴基;亞烷基部份的碳原子數為1~4,且亞烷基部份的一個-CH2 -可被-O-取代之苯基亞烷基;或者,以-((CH2 )m -O-)n -X表示的基[式中的m係表示2或3的數,n係表示1~3的數,X係表示氫原子或甲基])。The composition for piezoelectric materials of the present invention comprises: a vinylidene fluoride/trifluoroethylene copolymer; and an acrylic elastomer having a structural unit derived from the acrylic monomer represented by the formula (I), and The weight average molecular weight is more than 1 million; Formula (I): [Chemical 2] (R in the formula is an alkyl group with 1 to 10 carbon atoms which can be substituted by a hydroxyl group, an alkyl group with 1 or 2 carbon atoms and/or an alkoxy group with 1 to 6 carbon atoms; An alicyclic hydrocarbon group with 3 to 6 carbon atoms in which one carbon atom can be replaced by an oxygen atom; a hydrocarbon group with 3 to 12 carbon atoms; the alkylene moiety has 1 to 4 carbon atoms, and the alkylene group has 1 to 4 carbon atoms. One part of -CH 2 - may be substituted by -O- phenylalkylene; or, a group represented by -((CH 2 ) m -O-) n -X [where m represents 2 or A number of 3, n represents a number from 1 to 3, and X represents a hydrogen atom or a methyl group]).
[發明之效果] 因為本發明的壓電材料具有優異的柔軟性、伸縮性,故能夠適用於可穿戴設備等領域。[Effect of the Invention] Since the piezoelectric material of the present invention has excellent flexibility and stretchability, it can be applied to fields such as wearable devices.
[用以實施發明之形態] 以下,針對本發明實施形態的一例進行詳細說明。又,本發明的範圍並不限於此處所說明的實施形態,能夠在不脫離本發明意旨的範圍內進行各種變更。又,「~」所示之數值範圍係包含其上限及下限。[Mode for Carrying out the Invention] Hereinafter, an example of an embodiment of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the scope of the present invention. In addition, the numerical range shown by "~" includes the upper limit and the lower limit.
本發明的壓電材料係含有偏氟乙烯/三氟乙烯共聚物及特定的丙烯酸系彈性體。基於壓電材料全體的量,被含於本發明壓電材料之偏氟乙烯/三氟乙烯共聚物的量較佳係98~70質量%。若偏氟乙烯/三氟乙烯共聚物的量在上述上限值以下,則容易提高柔軟性及伸縮性。又,若偏氟乙烯/三氟乙烯共聚物的量在上述下限值以上,則壓電材料的自發極化不容易下降,容易提高壓電特性。The piezoelectric material of the present invention contains a vinylidene fluoride/trifluoroethylene copolymer and a specific acrylic elastomer. The amount of the vinylidene fluoride/trifluoroethylene copolymer contained in the piezoelectric material of the present invention is preferably 98 to 70% by mass based on the amount of the entire piezoelectric material. When the amount of the vinylidene fluoride/trifluoroethylene copolymer is equal to or less than the above upper limit value, flexibility and stretchability are easily improved. In addition, when the amount of the vinylidene fluoride/trifluoroethylene copolymer is equal to or greater than the above lower limit value, the spontaneous polarization of the piezoelectric material is not easily reduced, and the piezoelectric properties are easily improved.
本發明的壓電材料亦包含,含有偏氟乙烯/三氟乙烯共聚物及特定的丙烯酸系彈性體以外之材料(以下稱為其他材料)的態樣。就其他材料而言,雖然可舉出例如偏氟乙烯/三氟乙烯共聚物及特定的丙烯酸系彈性體以外的共聚物、彈性體、氧化防止劑、紫外線吸收劑等的添加劑;熱傳導性填料;導限性填料等,但並不限於此。The piezoelectric material of the present invention also includes an aspect containing a vinylidene fluoride/trifluoroethylene copolymer and a material other than a specific acrylic elastomer (hereinafter referred to as other material). For other materials, for example, vinylidene fluoride/trifluoroethylene copolymers and copolymers other than specific acrylic elastomers, additives such as elastomers, oxidation inhibitors, and ultraviolet absorbers; thermally conductive fillers; Conductive fillers, etc., but not limited to this.
基於壓電材料全體的量,被含於本發明壓電材料之丙烯酸系彈性體的量較佳係2~30質量%。若丙烯酸系彈性體的量在上述下限值以上,則容易提高柔軟性及伸縮性。又,若丙烯酸系彈性體的量在上述上限值以下,則能夠使壓電材料中偏氟乙烯/三氟乙烯共聚物的量相對地變大,容易提高壓電特性。The amount of the acrylic elastomer contained in the piezoelectric material of the present invention is preferably 2 to 30% by mass based on the amount of the entire piezoelectric material. When the amount of the acrylic elastomer is at least the above lower limit value, flexibility and stretchability are likely to be improved. In addition, when the amount of the acrylic elastomer is below the above upper limit value, the amount of the vinylidene fluoride/trifluoroethylene copolymer in the piezoelectric material can be relatively increased, and the piezoelectric properties can be easily improved.
基於被含於本發明壓電材料之偏氟乙烯/三氟乙烯共聚物及丙烯酸系彈性體的合計重量,被含於本發明壓電材料之偏氟乙烯/三氟乙烯共聚物的量較佳係88~96質量%。若偏氟乙烯/三氟乙烯共聚物的量在上述下限值以上,則壓電材料的自發極化不容易下降,容易提高壓電特性。又,若偏氟乙烯/三氟乙烯共聚物的量在上述上限值以下,則容易提高柔軟性及伸縮性。The amount of the vinylidene fluoride/trifluoroethylene copolymer contained in the piezoelectric material of the present invention is preferably based on the total weight of the vinylidene fluoride/trifluoroethylene copolymer and the acrylic elastomer contained in the piezoelectric material of the present invention The system is 88~96% by mass. When the amount of the vinylidene fluoride/trifluoroethylene copolymer is equal to or greater than the above lower limit value, the spontaneous polarization of the piezoelectric material is not easily reduced, and the piezoelectric properties are easily improved. Further, when the amount of the vinylidene fluoride/trifluoroethylene copolymer is equal to or less than the above-mentioned upper limit value, the flexibility and stretchability are easily improved.
本發明的壓電材料用組成物,其係包含:偏氟乙烯/三氟乙烯共聚物;以及丙烯酸系彈性體,其係具有來自式(I)所表示之丙烯酸系單體的構造單元,且重量平均分子量為100萬以上; 式(I) : [化3](式中的R係,可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代之具有1至10個碳原子的烷基;具有至少一個碳原子可被氧原子取代之碳原子數為3~6的脂環式烴基之碳原子數為3~12的烴基;亞烷基部份的碳原子數為1~4,且亞烷基部份的一個-CH2 -可被-O-取代之苯基亞烷基;或者,以-((CH2 )m -O-)n -X表示的基[式中的m及n係各自表示2或3的數字,X係表示氫原子或甲基])。The composition for piezoelectric materials of the present invention comprises: a vinylidene fluoride/trifluoroethylene copolymer; and an acrylic elastomer having a structural unit derived from the acrylic monomer represented by the formula (I), and The weight-average molecular weight is more than 1 million; Formula (I): [Chem. 3] (R in the formula is an alkyl group with 1 to 10 carbon atoms which can be substituted by a hydroxyl group, an alkyl group with 1 or 2 carbon atoms and/or an alkoxy group with 1 to 6 carbon atoms; An alicyclic hydrocarbon group with 3 to 6 carbon atoms in which one carbon atom can be replaced by an oxygen atom; a hydrocarbon group with 3 to 12 carbon atoms; the alkylene moiety has 1 to 4 carbon atoms, and the alkylene group has 1 to 4 carbon atoms. A part of -CH 2 - may be substituted by -O- phenylalkylene; or, a group represented by -((CH 2 ) m -O-) n -X [m and n in the formula are each A number representing 2 or 3, and X represents a hydrogen atom or a methyl group]).
(丙烯酸系彈性體) 被含於本發明壓電材料的丙烯酸系彈性體係包含,來自式(I)所示之丙烯酸系單體的構造單元: [化4](式中的R係,可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代之具有1至10個碳原子的烷基;具有至少一個碳原子可被氧原子取代之碳原子數為3~6的脂環式烴基之碳原子數為3~12的烴基;亞烷基部份的碳原子數為1~4,且亞烷基部份的一個-CH2 -可被-O-取代之苯基亞烷基;或者,以-((CH2 )m -O-)n -X表示的基[式中的m及n係各自表示2或3的數字,X係表示氫原子或甲基])。 換言之,本發明壓電材料所包含之丙烯酸系彈性體,係將上述式(I)所示之丙烯酸系單體作為構造單元而含有的聚合物(Polymer)。因為被含於本發明壓電材料之丙烯酸系彈性體的重量平均分子量,係較高之100萬以上,故各分子鏈具有較長的分子鏈。若具有如此之長分子鏈的高分子成為集合體,則具有彈性體的特性。(Acrylic Elastomer) The acrylic elastomer contained in the piezoelectric material of the present invention contains a structural unit derived from the acrylic monomer represented by the formula (I): [Chem. 4] (R in the formula is an alkyl group with 1 to 10 carbon atoms which can be substituted by a hydroxyl group, an alkyl group with 1 or 2 carbon atoms and/or an alkoxy group with 1 to 6 carbon atoms; An alicyclic hydrocarbon group with 3 to 6 carbon atoms in which one carbon atom can be replaced by an oxygen atom; a hydrocarbon group with 3 to 12 carbon atoms; the alkylene moiety has 1 to 4 carbon atoms, and the alkylene group has 1 to 4 carbon atoms. A part of -CH 2 - may be substituted by -O- phenylalkylene; or, a group represented by -((CH 2 ) m -O-) n -X [m and n in the formula are each A number representing 2 or 3, and X represents a hydrogen atom or a methyl group]). In other words, the acrylic elastomer contained in the piezoelectric material of the present invention is a polymer (polymer) containing the acrylic monomer represented by the above formula (I) as a structural unit. Since the weight average molecular weight of the acrylic elastomer contained in the piezoelectric material of the present invention is higher than 1 million, each molecular chain has a longer molecular chain. When a polymer having such a long molecular chain is aggregated, it has the properties of an elastomer.
藉由於壓電材料含有上述丙烯酸系彈性體,不會使壓電材料的電特性顯著下降,且能夠提高壓電材料的柔軟性、伸縮性。雖然此原因仍未明確,但若添加柔軟性高的彈性體且提高壓電材料的柔軟性及伸縮性,亦有壓電材料之壓電特性下降的情形。在本發明中,藉由使用具有特定構造且具有較高重量平均分子量之丙烯酸系彈性體,因為聚合物鏈的交纏性佳,故被認為其係兼具柔軟性、伸縮性及壓電特性,且能夠將電特性的下降抑制在最小限度,例如將殘留極化的下降抑制在最小限度。又,雖然被含於本發明壓電材料之丙烯酸系彈性體,其係重量平均分子量為100萬以上的聚合物鏈互相交纏,而被認為具有彈性體的特性,但亦可為例如具有交聯有重量平均分子量為100萬以上之聚合物鏈之構造的彈性體。Since the piezoelectric material contains the above-mentioned acrylic elastomer, the flexibility and stretchability of the piezoelectric material can be improved without significantly degrading the electrical properties of the piezoelectric material. Although the reason for this is still unclear, if a highly flexible elastomer is added to improve the flexibility and stretchability of the piezoelectric material, the piezoelectric properties of the piezoelectric material may decrease. In the present invention, by using an acrylic elastomer having a specific structure and a relatively high weight average molecular weight, it is considered that it has both flexibility, stretchability and piezoelectric properties because of good entanglement of polymer chains. , and can minimize the decline in electrical properties, for example, minimize the decline in residual polarization. In addition, although the acrylic elastomer contained in the piezoelectric material of the present invention is considered to have the characteristics of an elastomer because polymer chains having a weight average molecular weight of 1,000,000 or more are intertwined with each other, for example, it may have the properties of an elastomer. Elastomer with a structure in which polymer chains with a weight average molecular weight of 1 million or more are linked.
上述式(I)中的R係 (R1)可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代之具有1至10個碳原子的烷基; (R2)具有至少一個碳原子可被氧原子取代之碳原子數為3~6的脂環式烴基之碳原子數為3~12的烴基; (R3)亞烷基部份的碳原子數為1~4,且亞烷基部份的一個-CH2 -可被-O-取代之苯基亞烷基;或 (R4)以-((CH2 )m -O-)n -X表示的基[式中的m及n係各自表示2或3的數字,X係表示氫原子或甲基]。The R system (R1) in the above formula (I) may be substituted by a hydroxyl group, an alkyl group having 1 or 2 carbon atoms, and/or an alkoxy group having 1 to 6 carbon atoms, which has 1 to 10 carbon atoms. Alkyl; (R2) a hydrocarbon group with a carbon number of 3 to 12, an alicyclic hydrocarbon group having at least one carbon atom that can be substituted by an oxygen atom; (R3) a carbon atom in an alkylene moiety The number of atoms is 1~4, and one -CH 2 - of the alkylene part can be substituted by -O- phenylalkylene; or (R4) with -((CH 2 ) m -O-) n - The group represented by X [in the formula, m and n each represent a number of 2 or 3, and X represents a hydrogen atom or a methyl group].
關於(R1)可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代之具有1至10個碳原子的烷基,從低變形特性的觀點來看,烷基的碳原子數較佳係1~6,更佳係1~4。在本說明書中,烷基亦可為直鏈狀或分支狀的任一者。就烷基的例子而言,可舉出例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、新戊基、1,1-二甲基丙基、異戊基、正己基、異己基、正辛基等。此等碳原子數為1~10的烷基亦可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代。Regarding (R1) an alkyl group having 1 to 10 carbon atoms which may be substituted by a hydroxyl group, an alkyl group having 1 or 2 carbon atoms, and/or an alkoxy group having 1 to 6 carbon atoms From a viewpoint, the number of carbon atoms of the alkyl group is preferably 1-6, more preferably 1-4. In the present specification, the alkyl group may be either linear or branched. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, Neopentyl, 1,1-dimethylpropyl, isopentyl, n-hexyl, isohexyl, n-octyl, etc. These alkyl groups having 1 to 10 carbon atoms may be substituted by hydroxyl groups, alkyl groups having 1 or 2 carbon atoms, and/or alkoxy groups having 1 to 6 carbon atoms.
就被羥基取代之碳原子數為1~10的烷基的例子而言,可舉出例如羥甲基、羥乙基、羥基正丙基、羥基異丙基、羥基正丁基、羥基異丁基、羥基叔丁基等。Examples of the alkyl group having 1 to 10 carbon atoms substituted with hydroxy include hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, and hydroxyisobutyl. base, hydroxy tert-butyl, etc.
被碳原子數為1或2的烷基取代之碳原子數為1~10的烷基,係以碳原子數1~10的烷基作為主鏈,且該烷基之至少一個氫原子被碳原子數為1或2的烷基(甲基或乙基)取代的基。只要成為主鏈之烷基部份的碳原子數為1~10,烷基整體的碳原子數亦可超過10。就如此之烷基的例子而言,可舉出例如2-乙基己基等。又,在烷基整體的碳原子數未超過10之基的情況下,該基係亦被包含在碳原子數1~10之分枝狀烷基的定義中的基。An alkyl group having 1 to 10 carbon atoms substituted by an alkyl group having 1 or 2 carbon atoms is an alkyl group having 1 to 10 carbon atoms as the main chain, and at least one hydrogen atom of the alkyl group is replaced by a carbon atom. A group substituted with an alkyl group (methyl or ethyl) having 1 or 2 atoms. As long as the number of carbon atoms in the alkyl portion of the main chain is 1 to 10, the number of carbon atoms in the entire alkyl group may exceed 10. As an example of such an alkyl group, a 2-ethylhexyl group etc. are mentioned, for example. Moreover, when the carbon number of the whole alkyl group does not exceed 10 groups, this group is a group which is also included in the definition of a C1-C10 branched alkyl group.
碳原子數為1~6的烷氧基中烷基的碳原子數,較佳係1~4,更佳係1~2。烷氧基中的烷基亦可為直鏈狀或分支狀任一者。The number of carbon atoms of the alkyl group in the alkoxy group having 1 to 6 carbon atoms is preferably 1 to 4, more preferably 1 to 2. The alkyl group in the alkoxy group may be linear or branched.
被碳原子數為1~6的烷氧基取代之碳原子數為1~10的烷基,較佳係被碳原子數為1~6的烷氧基取代之碳原子數為1~6的烷基。就相關基的例子而言,可舉出例如甲氧基乙基、乙氧基乙基、甲氧基丁基。An alkyl group having 1 to 10 carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms alkyl. As an example of a related group, a methoxyethyl group, an ethoxyethyl group, and a methoxybutyl group are mentioned, for example.
就被羥基及碳原子數為1~6的烷氧基取代之碳原子數為1~10的烷基而言,可例如為具有碳原子數為1~6的羥基烷氧基及碳原子數為1~6的烷基,具體而言,可舉出例如羥基甲氧基乙基,羥基乙氧基乙基,羥基丙氧基丙基等。For the alkyl group having 1 to 10 carbon atoms substituted by a hydroxyl group and an alkoxy group having 1 to 6 carbon atoms, for example, a hydroxyalkoxy group having 1 to 6 carbon atoms and a carbon number can be used. It is an alkyl group of 1-6, for example, a hydroxymethoxyethyl group, a hydroxyethoxyethyl group, a hydroxypropoxypropyl group etc. are mentioned specifically,.
在上述烷基中,從容易獲得的觀點來看,較佳係可被羥基及/或碳原子數為1~2的烷氧基取代之碳原子數為1~6的烷基,更佳係可被羥基及/或碳原子數為1~2的烷氧基取代之碳原子數為1~4的烷基,特佳係可被羥基及/或碳原子數為1~2的烷氧基取代之碳原子數為1~2的烷基。Among the above-mentioned alkyl groups, from the viewpoint of easy availability, an alkyl group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group and/or an alkoxy group having 1 to 2 carbon atoms is preferable, and more preferable is an alkyl group having 1 to 6 carbon atoms. An alkyl group with 1 to 4 carbon atoms that can be substituted by a hydroxyl group and/or an alkoxy group with 1 to 2 carbon atoms, particularly preferably an alkoxy group that can be substituted by a hydroxyl group and/or an alkoxy group with 1 to 2 carbon atoms A substituted alkyl group having 1 to 2 carbon atoms.
關於(R2)具有至少一個碳原子可被氧原子取代之碳原子數為3~6的脂環式烴基之碳原子數為3~12的烴基,就碳原子數為3~6的脂環式烴基而言,可舉出例如環己烷。With respect to (R2) a hydrocarbon group having 3 to 12 carbon atoms and a alicyclic hydrocarbon group having 3 to 6 carbon atoms in which at least one carbon atom can be replaced by an oxygen atom, the alicyclic hydrocarbon group having 3 to 6 carbon atoms As a hydrocarbon group, cyclohexane is mentioned, for example.
就至少一個碳原子被氧原子取代之碳原子數為3~6的脂環式烴基而言,可舉出例如,碳原子數為3的脂環式烴基的1個碳原子被氧原子取代之環氧基、碳原子數為4的脂環式烴基的1個碳原子被氧原子取代之氧雜環丁烷基環(Oxetanyl Ring)、碳原子數為5的脂環式烴基的2個碳原子被氧原子取代之二氧戊環、碳原子數為6的脂環式烴基的2個碳原子被氧原子取代之二噁烷環等。又,此等環上之氫原子亦可被碳原子數為1或2的烷基取代。又,含有碳原子數為3~6的脂環式烴基之碳原子數為3~12的烴基,較佳係具有,碳原子數為1~4且一個-CH2 -可被-O-取代的亞烷基部份與上述碳原子數為3~6的脂環式烴基部份之基。此時,雖然取代基的位置並未特別限定,但位於亞烷基部份與環構造之連接部份之氫原子,較佳係被甲基或乙基取代。又,在包含脂環式烴基的2個碳原子被取代成氧原子之構造時,在位於2個氧原子之間的碳原子中,至少1個氫原子較佳係被碳原子數為1或2的烷基取代。就如此之基而言,具體來說,可舉出,3-乙基-3-氧雜環丁烷基丙烯酸甲酯、(2-甲基-2-乙基-1,3-二氧戊環-4-基)丙烯酸甲酯、環狀三羥甲基丙烷縮甲醛(Cyclic trimethylolpropane formal acrylate)等。As for the alicyclic hydrocarbon group having 3 to 6 carbon atoms in which at least one carbon atom is substituted by an oxygen atom, for example, one carbon atom of an alicyclic hydrocarbon group having 3 carbon atoms is substituted by an oxygen atom. Epoxy group, Oxetanyl Ring in which one carbon atom of an alicyclic hydrocarbon group having 4 carbon atoms is substituted by an oxygen atom, and two carbon atoms in an alicyclic hydrocarbon group having 5 carbon atoms Dioxolane rings in which atoms are substituted by oxygen atoms, dioxane rings in which two carbon atoms of an alicyclic hydrocarbon group having 6 carbon atoms are substituted by oxygen atoms, and the like. In addition, the hydrogen atoms on these rings may be substituted with an alkyl group having 1 or 2 carbon atoms. Also, the hydrocarbon group having 3 to 12 carbon atoms and the alicyclic hydrocarbon group containing 3 to 6 carbon atoms preferably has 1 to 4 carbon atoms and one -CH 2 - may be substituted by -O- The alkylene moiety of and the above-mentioned alicyclic hydrocarbon moiety having 3 to 6 carbon atoms. At this time, although the position of the substituent is not particularly limited, the hydrogen atom at the connecting portion between the alkylene moiety and the ring structure is preferably substituted with a methyl group or an ethyl group. Furthermore, in the structure in which two carbon atoms of an alicyclic hydrocarbon group are substituted with oxygen atoms, among the carbon atoms located between the two oxygen atoms, at least one hydrogen atom is preferably replaced by a carbon atom having one or more carbon atoms. 2 alkyl substitution. Specific examples of such groups include methyl 3-ethyl-3-oxetanyl acrylate, (2-methyl-2-ethyl-1,3-dioxolane) Cyclic-4-yl) methyl acrylate, Cyclic trimethylolpropane formal acrylate, etc.
關於(R3)亞烷基部份的碳原子數為1~4,且亞烷基部份的一個-CH2 -可被-O-取代之苯基亞烷基,相關的基較佳係以-(CH2 )k -C6 H5 所表示的基,或是以-(CH2 )k -C6 H5 所表示的基[k為2或3]。Regarding (R3) the number of carbon atoms in the alkylene part is 1 to 4, and one -CH 2 - of the alkylene part can be substituted by -O- phenylalkylene, the relevant group is preferably a A group represented by -(CH 2 ) k -C 6 H 5 or a group represented by -(CH 2 ) k -C 6 H 5 [k is 2 or 3].
就以(R4)之-((CH2 )m -O-)n -X所表示的基[式中的m及n係各自表示2或3的數字,X係表示氫原子或甲基]而言,較佳可舉出甲氧基乙基。With respect to the group represented by -((CH 2 ) m -O-) n -X of (R4) [m and n in the formula each represent a number of 2 or 3, and X represents a hydrogen atom or a methyl group] and Preferable examples include methoxyethyl.
從容易提高壓電材料的電特性、柔軟性、伸縮性及耐變形性的觀點來看,上述式(I)中的R較佳係,可被羥基、碳原子數為1或2的烷基及/或碳原子數為1~6的烷氧基取代之碳原子數為1~10的烷基,更佳係可被碳原子數為1或2的烷基取代之碳原子數為2~8的烷基。From the viewpoint of easily improving the electrical properties, flexibility, stretchability, and deformation resistance of the piezoelectric material, R in the above formula (I) is preferably a system that can be replaced by a hydroxyl group, an alkyl group having 1 or 2 carbon atoms And/or an alkyl group with 1 to 10 carbon atoms substituted by an alkoxy group with 1 to 6 carbon atoms, preferably an alkyl group with 1 to 2 carbon atoms substituted with 2 to 2 carbon atoms 8 alkyl groups.
被含於本發明壓電材料的丙烯酸系彈性體,可僅具有上述式(I)所表示之1種的構造單元,亦可具有上述式(I)所表示之2種以上的構造單元。又,被含於本發明壓電材料的丙烯酸系彈性體,可在不損及本發明壓電材料特性的範圍內,包含至少1種來自其他單體的構造單元。換言之,被含於本發明壓電材料的丙烯酸系彈性體,係可為上述式(I)所表示之構造單元的1種丙烯酸系單體的單聚物,亦可為上述式(I)所表示之構造單元的2種以上之丙烯酸系單體的共聚物,亦可為上述式(I)所表示之構造單元的1種丙烯酸系單體與至少1種其他單體的共聚物。The acrylic elastomer contained in the piezoelectric material of the present invention may have only one structural unit represented by the above formula (I), or may have two or more structural units represented by the above formula (I). In addition, the acrylic elastomer contained in the piezoelectric material of the present invention may contain at least one structural unit derived from another monomer within a range that does not impair the properties of the piezoelectric material of the present invention. In other words, the acrylic elastomer contained in the piezoelectric material of the present invention may be a monomer of one acrylic monomer having a structural unit represented by the above formula (I), or may be a monomer represented by the above formula (I). The copolymer of two or more acrylic monomers of the structural unit represented may be a copolymer of one acrylic monomer and at least one other monomer of the structural unit represented by the above formula (I).
就能夠與上述式(I)所表示之構造單元的1種丙烯酸系單體共聚合之其他單體而言,可舉出例如含有羧基的單體、具有式(I)所表示之構造單元的丙烯酸系單體以外的羧酸烷基酯系單體、含有醯胺基的單體、含有芳基的單體、苯乙烯系單體、含有氮原子的單體、脂肪酸乙烯基酯類單體、甜菜鹼單體等。Other monomers which can be copolymerized with one kind of acrylic monomer of the structural unit represented by the above formula (I) include, for example, a carboxyl group-containing monomer and a monomer having a structural unit represented by the formula (I). Carboxylic acid alkyl ester-based monomers other than acrylic monomers, amide group-containing monomers, aryl group-containing monomers, styrene-based monomers, nitrogen atom-containing monomers, fatty acid vinyl ester-based monomers , betaine monomer, etc.
就含有羧基的單體而言,可舉出例如(甲基)丙烯酸、馬來酸、富馬酸、檸康酸、中康酸、衣康酸、巴豆酸等。As a carboxyl group-containing monomer, (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, crotonic acid, etc. are mentioned, for example.
就具有式(I)所表示之構造單元的丙烯酸系單體以外的羧酸烷基酯系單體而言,可舉出例如十二烷基(甲基)丙烯酸酯、硬脂基(甲基)丙烯酸酯等烷基的碳原子數為11~20的烷基丙烯酸酯;衣康酸甲酯、衣康酸乙酯等之烷基的碳原子數為1~4的衣康酸烷基酯等。Examples of alkyl carboxylate monomers other than acrylic monomers having a structural unit represented by formula (I) include dodecyl (meth)acrylate, stearyl (methyl) ) Alkyl acrylates with alkyl groups such as acrylates having 11 to 20 carbon atoms; alkyl itaconate with 1 to 4 carbon atoms in the alkyl groups such as methyl itaconic acid, ethyl itaconic acid, etc. Wait.
就含有醯胺基的單體而言,可舉出例如,N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-叔丁基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺,N,N-二乙基(甲基)丙烯醯胺等之烷基的碳原子數為1~8之烷基(甲基)丙烯醯胺等。Examples of the amide group-containing monomer include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl(meth)acrylamide. Amine, N-isopropyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl (Meth) acrylamide etc. C1-C8 alkyl (meth) acrylamide etc. of the alkyl group.
就含有芳基的單體而言,可舉出例如(甲基)丙烯酸芐酯等之芳基的碳原子數為6~12的芳基(甲基)丙烯酸酯。Examples of the aryl group-containing monomer include aryl (meth)acrylates having 6 to 12 carbon atoms in the aryl group, such as benzyl (meth)acrylate.
就苯乙烯系單體而言,可舉出例如苯乙烯、α-甲基苯乙烯等。As a styrene-type monomer, styrene, (alpha)-methylstyrene etc. are mentioned, for example.
就含有氮原子的單體而言,可舉出例如N-乙烯基吡咯烷酮,N-乙烯基己內醯胺等。As a nitrogen atom-containing monomer, N-vinylpyrrolidone, N-vinylcaprolactam, etc. are mentioned, for example.
就脂肪酸乙烯基酯類單體而言,可舉出例如乙酸乙烯酯、丙酸乙烯酯等。As a fatty acid vinyl ester type monomer, vinyl acetate, vinyl propionate, etc. are mentioned, for example.
就甜菜鹼單體而言,可舉出例如N-丙烯醯氧基甲基-N,N-二甲基銨甲基-α-磺基甜菜鹼、N-甲基丙烯醯氧基甲基-N,N-二甲基銨甲基-α-磺基甜菜鹼、N-丙烯醯氧基甲基-N,N-二甲基銨乙基-α-磺基甜菜鹼、N-甲基丙烯醯氧基甲基-N,N-二甲基銨乙基-α-磺基甜菜鹼、N-丙烯醯氧基甲基-N,N-二甲基銨丙基-α-磺基甜菜鹼、N-甲基丙烯醯氧基甲基-N,N-二甲基銨丙基-α-磺基甜菜鹼、N-丙烯醯氧基甲基-N,N-二甲基銨丁基-α-磺基甜菜鹼、N-甲基丙烯醯氧基甲基-N,N-二甲基銨丁基-α-磺基甜菜鹼、N-丙烯醯氧基乙基-N,N-二甲基銨甲基-α-磺基甜菜鹼、N-甲基丙烯醯氧基乙基-N,N-二甲基銨甲基-α-磺基甜菜鹼、N-丙烯醯氧基乙基-N,N-二甲基銨乙基-α-磺基甜菜鹼、N-甲基丙烯醯氧基乙基-N,N-二甲基銨乙基-α-磺基甜菜鹼、N-丙烯醯氧基乙基-N,N-二甲基銨丙基-α-磺基甜菜鹼、N-甲基丙烯醯氧基乙基-N,N-二甲基銨丙基-α-磺基甜菜鹼、N-丙烯醯氧基乙基-N,N-二甲基銨丁基-α-磺基甜菜鹼、N-甲基丙烯醯氧基乙基-N,N-二甲基銨丁基-α-磺基甜菜鹼、N-丙烯醯氧基丙基-N,N-二甲基銨甲基-α-磺基甜菜鹼、N-甲基丙烯醯氧基丙基-N,N-二甲基銨甲基-α-磺基甜菜鹼、N-丙烯醯氧丙基-N,N-二甲基銨乙基-α-磺基甜菜鹼、N-丙烯醯氧基丙基-N,N-二甲基銨乙基-α-磺基甜菜鹼、N-丙烯醯氧基丙基-N,N-二甲基銨丙基-α-磺基甜菜鹼、N-甲基丙烯醯氧基丙基-N,N-二甲基銨丙基-α-磺基甜菜鹼、N-丙烯醯氧基丙基-N,N-二甲基銨丁基-α-磺基甜菜鹼、N-甲基丙烯醯氧基丙基-N,N-二甲基銨丁基-α-磺基甜菜鹼、N-丙烯醯氧基丁基-N,N-二甲基銨甲基-α-磺基甜菜鹼、N-甲基丙烯醯氧基丁基-N,N-二甲基銨甲基-α-磺基甜菜鹼、N-丙烯醯氧基丁基-N,N-二甲基銨乙基-α-磺基甜菜鹼、N-甲基丙烯醯氧基丁基-N,N-二甲基銨乙基-α-磺基甜菜鹼、N-丙烯醯氧基丁基-N,N-二甲基銨丙基-α-磺基甜菜鹼、N-甲基丙烯醯氧基丁基-N,N-二甲基銨丙基-α-磺基甜菜鹼、N-丙烯醯氧基丁基-N,N-二甲基銨丁基-α-磺基甜菜鹼、N-甲基丙烯醯氧基丁基-N,N-二甲基銨丁基-α-磺基甜菜鹼等的N-(甲基)丙烯醯氧基烷基-N,N-二甲基銨烷基-α-磺基甜菜鹼等之磺基甜菜鹼單體等。As a betaine monomer, for example, N-acryloyloxymethyl-N,N-dimethylammonium methyl-α-sulfobetaine, N-methacryloyloxymethyl- N,N-Dimethylammoniummethyl-α-sulfobetaine, N-acryloyloxymethyl-N,N-dimethylammoniumethyl-α-sulfobetaine, N-methylpropene Ethyloxymethyl-N,N-dimethylammoniumethyl-α-sulfobetaine, N-propenyloxymethyl-N,N-dimethylammoniumpropyl-α-sulfobetaine , N-methacryloyloxymethyl-N,N-dimethylammoniopropyl-α-sulfobetaine, N-acryloyloxymethyl-N,N-dimethylammoniobutyl- α-Sulfobetaine, N-methacryloyloxymethyl-N,N-dimethylammoniumbutyl-α-sulfobetaine, N-acryloyloxyethyl-N,N-di Methylammonium methyl-α-sulfobetaine, N-methacryloyloxyethyl-N,N-dimethylammonium methyl-α-sulfobetaine, N-acryloyloxyethyl -N,N-dimethylammoniumethyl-α-sulfobetaine, N-methacryloyloxyethyl-N,N-dimethylammoniumethyl-α-sulfobetaine, N- Acryloyloxyethyl-N,N-dimethylammoniopropyl-α-sulfobetaine, N-methacryloyloxyethyl-N,N-dimethylammoniopropyl-α-sulfonic acid Betaine, N-acryloyloxyethyl-N,N-dimethylammoniumbutyl-α-sulfobetaine, N-methacryloyloxyethyl-N,N-dimethylammonium Butyl-α-sulfobetaine, N-acryloyloxypropyl-N,N-dimethylammonium methyl-α-sulfobetaine, N-methacryloyloxypropyl-N, N-dimethylammonium methyl-α-sulfobetaine, N-acryloyloxypropyl-N,N-dimethylammoniumethyl-α-sulfobetaine, N-acryloyloxypropyl -N,N-dimethylammoniumethyl-α-sulfobetaine, N-acryloyloxypropyl-N,N-dimethylammoniumpropyl-α-sulfobetaine, N-methyl Acryloyloxypropyl-N,N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxypropyl-N,N-dimethylammoniumbutyl-α-sulfobetaine Base, N-methacryloyloxypropyl-N,N-dimethylammoniumbutyl-α-sulfobetaine, N-acryloyloxybutyl-N,N-dimethylammoniummethyl -α-sulfobetaine, N-methacryloyloxybutyl-N,N-dimethylammonium methyl-α-sulfobetaine, N-acryloyloxybutyl-N,N- Dimethylammoniumethyl-α-sulfobetaine, N-methacryloyloxybutyl-N,N-dimethylammoniumethyl-α-sulfobetaine, N-acryloyloxybutyl Base-N,N-dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxybutyl-N,N-dimethylammoniumpropyl-α-sulfobetaine, N - Acryloyloxybutyl-N,N-dimethylammoniobutyl-α-sulfobetaine, N-methacryloyloxybutyl-N,N-dimethylammoniobutyl-α- N-(meth)acryloyloxyalkyl-N,N-dimethylammonium alkyl-α-sulfonic acid such as sulfobetaine Sultaines such as sulfobetaine monomers, etc.
從容易獲得具有充分壓電特性之丙烯酸系彈性體的觀點來看,在製造丙烯酸系彈性體時的單體成分中,式(I)所表示之丙烯酸系單體的含有率,較佳係90質量%以上,更佳係93質量%以上,特佳係95質量%以上;且可與單體成分中式(I)所表示之丙烯酸系單體共聚合之單體的含有率,較佳係10質量%以下,更佳係7質量%以下,特佳係5質量%以下。又,從充分地發現使用式(I)所表示之丙烯酸系單體而獲得之效果的觀點來看,在製造丙烯酸系彈性體時的單體成分中,式(I)所表示之丙烯酸系單體的含有率較佳係99質量%以下,更佳係98質量%以下,特佳係97質量%以下;且可與單體成分中式(I)所表示之丙烯酸系單體共聚合之單體的含有率,較佳係1質量%以上,更佳係2質量%以上,特佳係3質量%以上。From the viewpoint of easily obtaining an acrylic elastomer having sufficient piezoelectric properties, the content of the acrylic monomer represented by the formula (I) in the monomer components for producing the acrylic elastomer is preferably 90 mass % or more, more preferably 93 mass % or more, particularly preferably 95 mass % or more; and the content rate of the monomer copolymerizable with the acrylic monomer represented by formula (I) in the monomer component, preferably 10 mass % or less, more preferably 7 mass % or less, and particularly preferably 5 mass % or less. Furthermore, from the viewpoint of sufficiently discovering the effects obtained by using the acrylic monomer represented by the formula (I), among the monomer components in the production of the acrylic elastomer, the acrylic monomer represented by the formula (I) The content of the monomer is preferably 99% by mass or less, more preferably 98% by mass or less, and particularly preferably 97% by mass or less; and a monomer that can be copolymerized with the acrylic monomer represented by the formula (I) in the monomer component The content rate of MgO is preferably 1 mass % or more, more preferably 2 mass % or more, and particularly preferably 3 mass % or more.
又,亦可在不阻礙本發明目的之範圍內,於單體成分中,適當地包含交聯性單體。如上述般,本發明壓電材料所含有之丙烯酸系彈性體係包含來自具有上述式(I)所表示之丙烯酸系單體的構造單元的聚合物。交聯性單體係:(1)其作為構造單元而被包含在具有來自上述式(I)所表示之丙烯酸系單體的構造單元的聚合物的主鏈,且其使含有以上述式(I)所表示之丙烯酸系單體作為構造單元之聚合物們進行鍵結(交聯);及/或(2)其不被包含在將上述式(I)所表示之丙烯酸系單體作為構造單元而含有之聚合物的主鏈,且其與將上述式(I)所表示之丙烯酸系單體作為構造單元而含有之聚合物的側鏈鍵結,並使將上述式(I)所表示之丙烯酸系單體作為構造單元而含有之聚合物們鍵結(交聯)。在(1)及(2)任一者的形態中,因為丙烯酸系彈性體係包含來自交聯性單體的構造單元,使上述式(I)所表示之丙烯酸系單體作為構造單元而含有之複數聚合物鍵結,能夠形成一個分子量更大的聚合物。Moreover, in the range which does not inhibit the objective of this invention, a crosslinkable monomer may be contained suitably in a monomer component. As described above, the acrylic elastic system contained in the piezoelectric material of the present invention includes a polymer derived from a structural unit having an acrylic monomer represented by the above formula (I). A crosslinkable monomer system: (1) It is contained as a structural unit in the main chain of a polymer having a structural unit derived from the acrylic monomer represented by the above formula (I), and it is contained in the above formula ( 1) The polymers having the acrylic monomer represented by the above formula (I) as the structural unit are bonded (crosslinked); and/or (2) they are not included in the polymers having the acrylic monomer represented by the above formula (I) as the structural unit unit and the main chain of the polymer containing the acrylic monomer represented by the above formula (I) is bonded to the side chain of the polymer containing the acrylic monomer represented by the above formula (I) as a structural unit, and the above formula (I) The polymers contained in the acrylic monomer as structural units are bonded (crosslinked). In the aspect of any one of (1) and (2), since the acrylic elastic system includes a structural unit derived from a crosslinkable monomer, the acrylic monomer represented by the above formula (I) is contained as a structural unit. Plural polymer bonds can form a polymer with a larger molecular weight.
就交聯性單體而言,雖然能夠舉出下述化合物之多官能基單體,例如,亞甲基雙丙烯醯胺、亞甲基雙甲基丙烯醯胺等之亞烷基的碳原子數為1~4之亞烷基雙(甲基)丙烯醯胺之具有2個以上(甲基)丙烯醯基的(甲基)丙烯醯胺化合物,較佳係具有2個(甲基)丙烯醯基的(甲基)丙烯醯胺化合物;乙烯二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯等之具有2個以上(甲基)丙烯醯基的(甲基)丙烯酸酯化合物,較佳係具有2個或3個(甲基)丙烯醯基的(甲基)丙烯酸酯化合物;二烯丙胺、三烯丙胺等之具有2個以上碳-碳雙鍵之胺化合物,較佳係具有2個或3個碳-碳雙鍵之胺化合物;二乙烯基苯,二烯丙基苯等之具有2個以上碳-碳雙鍵之芳香族化合物,較佳係具有2個或3個碳-碳雙鍵之芳香族化合物等;但本發明並不僅限於相關示例所列舉之化合物。此等交聯性單體係可各自單獨使用,亦可併用2種以上。As for the crosslinkable monomers, the polyfunctional monomers of the following compounds can be mentioned, for example, carbon atoms of alkylene groups such as methylenebisacrylamide and methylenebismethacrylamide. A (meth)acrylamide compound having two or more (meth)acrylamide groups, preferably having two (meth)propylene groups, of 1 to 4 alkylene bis(meth)acrylamides Acryloyl (meth)acrylamido compounds; ethylene di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate Acrylates, triethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol Alcohol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate ) acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, etc. having two or more (meth)acryloyl groups (meth)acrylate compound, preferably a (meth)acrylate compound with 2 or 3 (meth)acryloyl groups; diallylamine, triallylamine, etc. have 2 or more carbon-carbon Amine compounds with double bonds, preferably amine compounds with 2 or 3 carbon-carbon double bonds; aromatic compounds with more than 2 carbon-carbon double bonds such as divinylbenzene, diallylbenzene, etc., Preferred are aromatic compounds having 2 or 3 carbon-carbon double bonds; however, the present invention is not limited to the compounds listed in the relevant examples. These crosslinkable mono-systems may be used alone or in combination of two or more.
被含於本發明壓電材料之丙烯酸系彈性體的重量平均分子量係100萬以上,較佳係110萬以上,更佳係120萬以上,特佳係130萬以上,最佳係140萬以上。若丙烯酸系彈性體的重量平均分子量小於100萬,則因為聚合物鏈的交纏稀疏,在最後所獲得之壓電材料的變形變大,會損害壓電材料的柔軟性及伸縮性。若丙烯酸系彈性體的重量平均分子量在上述下限值以上,則容易伸縮。又,從製造容易性的觀點來看,丙烯酸系彈性體的重量平均分子量較佳係400萬以下,更佳係300萬以下,特佳係200萬以下。The weight average molecular weight of the acrylic elastomer contained in the piezoelectric material of the present invention is 1 million or more, preferably 1.1 million or more, more preferably 1.2 million or more, particularly preferably 1.3 million or more, and most preferably 1.4 million or more. If the weight-average molecular weight of the acrylic elastomer is less than 1 million, since the entanglement of polymer chains is sparse, the deformation of the piezoelectric material obtained at the end becomes large, and the flexibility and stretchability of the piezoelectric material are impaired. When the weight average molecular weight of an acrylic elastomer is more than the said lower limit, it will expand and contract easily. In addition, from the viewpoint of ease of manufacture, the weight average molecular weight of the acrylic elastomer is preferably 4 million or less, more preferably 3 million or less, and particularly preferably 2 million or less.
丙烯酸系彈性體的重量平均分子量係能夠使用凝膠滲透色譜法(Gel permeation chromatography)進行測定。測定條件等詳細內容係如同實施例所載。The weight average molecular weight of the acrylic elastomer can be measured using gel permeation chromatography (Gel permeation chromatography). Details such as measurement conditions are as described in Examples.
(丙烯酸系彈性體的製法) 被含於本發明壓電材料之丙烯酸系彈性體係能夠藉由使單體成分聚合而獲得。(Production method of acrylic elastomer) The acrylic elastomer contained in the piezoelectric material of the present invention can be obtained by polymerizing monomer components.
就使單體成分聚合的方法而言,雖然可舉出塊狀聚合法、溶液聚合法、乳化聚合法、懸濁聚合法等,但本發明不僅限於所示例之方法。在此等聚合法中,從容易獲得在低施加電壓下變位量大之丙烯酸系彈性體的觀點來看,較佳係塊狀聚合法及溶液聚合法。又,從容易獲得重量平均分子量在100萬以上之丙烯酸系彈性體的觀點來看,較佳係塊狀聚合法。被含於本發明壓電材料之丙烯酸系彈性體,不僅係如習知之丙烯酸橡膠般,藉由使原料的單體成分藉由懸濁聚合法聚合,且較佳係藉由塊狀聚合法進行聚合而獲得之物。在使用塊狀聚合法的情況下,能夠容易地調製伸長性優異且施加低電壓時顯示大的變位量、並且重量平均分子量在100萬以上的丙烯酸系彈性體。The method for polymerizing the monomer components includes a block polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like, but the present invention is not limited to the exemplified methods. Among these polymerization methods, the bulk polymerization method and the solution polymerization method are preferable from the viewpoint of easily obtaining an acrylic elastomer having a large amount of displacement at a low applied voltage. Also, from the viewpoint of easily obtaining an acrylic elastomer having a weight average molecular weight of 1,000,000 or more, a block polymerization method is preferred. The acrylic elastomer contained in the piezoelectric material of the present invention is not only a conventional acrylic rubber, but also by polymerizing the monomer components of the raw material by a suspension polymerization method, and preferably by a bulk polymerization method. obtained by polymerization. When the bulk polymerization method is used, it is possible to easily prepare an acrylic elastomer which is excellent in elongation, exhibits a large amount of displacement when a low voltage is applied, and has a weight average molecular weight of 1 million or more.
在使用溶液聚合法將單體成分聚合時,可使用溶媒。就溶媒而言,較佳係非水系有機溶媒。就非水系有機溶媒而言,雖然可舉出例如,己烷、庚烷、辛烷、異辛烷、癸烷、液體石蠟等烴系有機溶媒;二甲醚、***、四氫呋喃等醚系有機溶媒;丙酮、甲基乙基酮等酮系有機溶媒;乙酸甲酯、乙酸乙酯、乙酸丁酯等酯系有機溶媒;二氯甲烷、氯仿、四氯化碳等氯化物系有機溶媒;二甲基甲醯胺;二乙基甲醯胺;二甲基亞碸;二噁烷等,但本發明不僅限於所示例之溶媒。此等有機溶媒係可各自單獨使用,亦可併用2種以上。雖然溶媒的量係因為該溶媒種類的不同,故不能一概而論地限定,但通常,較佳係每100質量部的單體,使用100~1000質量部左右的溶媒。When polymerizing the monomer components by the solution polymerization method, a solvent can be used. As a solvent, a non-aqueous organic solvent is preferable. Examples of non-aqueous organic solvents include hydrocarbon-based organic solvents such as hexane, heptane, octane, isooctane, decane, and liquid paraffin; ether-based organic solvents such as dimethyl ether, diethyl ether, and tetrahydrofuran. ; ketone-based organic solvents such as acetone and methyl ethyl ketone; ester-based organic solvents such as methyl acetate, ethyl acetate, and butyl acetate; chloride-based organic solvents such as dichloromethane, chloroform, and carbon tetrachloride; dimethyl acetate diethylformamide; dimethylsulfoxide; dioxane, etc., but the present invention is not limited to the exemplified solvents. These organic solvents may be used independently, respectively, or may use 2 or more types together. Although the amount of the solvent cannot be generally limited depending on the type of the solvent, in general, it is preferable to use about 100 to 1,000 parts by mass of the solvent per 100 parts by mass of the monomer.
在使單體成分聚合時,可使用聚合起始劑。就聚合起始劑而言,可舉出例如光聚合起始劑、熱聚合起始劑等。在此等聚合起始劑中,從不使(甲基)丙烯酸系彈性體殘留熱履歷的觀點來看,較佳係光聚合起始劑。When polymerizing the monomer components, a polymerization initiator can be used. As a polymerization initiator, a photopolymerization initiator, a thermal polymerization initiator, etc. are mentioned, for example. Among these polymerization initiators, a photopolymerization initiator is preferable from the viewpoint of not leaving the thermal history of the (meth)acrylic-based elastomer.
就光聚合起始劑而言,雖然可舉出例如,2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2'-雙(鄰氯苯基)-4,4',5,5'-四苯基-1,1'-聯咪唑、2,4,6-三(三氯甲基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(對甲氧基苯基乙烯基)-1,3,5-三嗪、二苯基碘鎓四氟硼酸鹽、二苯基碘鎓六氟磷酸鹽、4,4'-二叔丁基二苯基碘鎓四氟硼酸鹽、4-二乙基氨基苯基重氮六氟磷酸鹽、苯偶姻、2-羥基-2-甲基-1-苯基丙-2-酮、二苯甲酮、噻噸酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、三苯基丁基硼酸四乙基銨、二苯基-4-苯硫基苯基鋶六氟磷酸鹽、2,2-二甲氧基-1,2-二苯基乙-1-酮、苯基乙醛酸甲酯、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、1,2-辛二酮、1-[4-(苯硫基)-2-(鄰苯甲醯基肟)] 、雙(η5-2,4-環戊二烯-1-基)雙[2,6-二氟-3-(1H-吡咯-1-基)苯基鈦]等光自由基聚合起始劑;2,4,6-三(三氯甲基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(對甲氧基苯基乙烯基)-1,3,5-三嗪、二苯基碘鎓四氟硼酸鹽、4,4'-二叔丁基二苯基碘鎓四氟硼酸鹽、4-二乙基氨基苯重氮六氟磷酸鹽、二苯基-4-苯硫基苯基鋶六氟磷酸鹽等光陽離子開環聚合起始劑,但本發明並不僅限於相關示例所列舉之化合物。此等光聚合起始劑係可各自單獨使用,亦可併用2種以上。As the photopolymerization initiator, for example, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4 ',5,5'-tetraphenyl-1,1'-biimidazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(p-methoxyphenylvinyl)-1,3,5-triazine, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, 4,4' -Di-tert-butyldiphenyliodonium tetrafluoroborate, 4-diethylaminophenyldiazonium hexafluorophosphate, benzoin, 2-hydroxy-2-methyl-1-phenylpropane-2 - Ketone, benzophenone, thioxanthone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, tetraethylammonium triphenylbutylborate, diphenyl-4-phenylsulfide Phenyl perylene hexafluorophosphate, 2,2-dimethoxy-1,2-diphenylethan-1-one, methyl phenylglyoxylate, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinopropan-1-one, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 1,2-octanedione, 1- [4-(phenylthio)-2-(o-benzoyl oxime)], bis(η5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-( 1H-pyrrol-1-yl) phenyl titanium] and other photo-radical polymerization initiators; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2,4-bis( Trichloromethyl)-6-(p-methoxyphenylvinyl)-1,3,5-triazine, diphenyliodonium tetrafluoroborate, 4,4'-di-tert-butyldiphenyl Photocationic ring-opening polymerization initiators such as iodonium tetrafluoroborate, 4-diethylaminobenzenediazonium hexafluorophosphate, diphenyl-4-phenylthiophenyl hexafluorophosphate, etc., but the present invention It is not limited to the compounds listed in the relevant examples. These photopolymerization initiators may be used alone or in combination of two or more.
就熱聚合起始劑而言,雖然可舉出例如二甲基-2,2'-偶氮二(2-甲基丙酸)、2,2'-偶氮二異丁腈(AIBN)、2,2'-偶氮二異丁酸二甲酯、偶氮二甲基戊腈等的偶氮系聚合起始劑;過氧化苯甲醯、過硫酸鉀、過硫酸銨等的過氧化物聚合起始劑,但本發明並不僅限於相關示例所列舉之化合物。此等聚合起始劑係可各自單獨使用,亦可併用2種以上。Although the thermal polymerization initiators include, for example, dimethyl-2,2'-azobis(2-methylpropionic acid), 2,2'-azobisisobutyronitrile (AIBN), Azo-based polymerization initiators such as dimethyl 2,2'-azobisisobutyrate, azodimethylvaleronitrile, etc.; peroxides such as benzyl peroxide, potassium persulfate, ammonium persulfate, etc. A polymerization initiator, but the present invention is not limited to the compounds listed in the relevant examples. These polymerization initiators may be used independently, respectively, or may use 2 or more types together.
雖然聚合起始劑的量係因為該聚合起始劑種類的不同,故不能一概而論地限定,但通常,較佳係每100質量部的單體,使用0.01~20質量部左右的聚合起始劑。Although the amount of the polymerization initiator is different depending on the type of the polymerization initiator, it cannot be generally limited, but in general, it is preferable to use about 0.01 to 20 mass parts of the polymerization initiator per 100 mass parts of the monomers. .
在使單體成分聚合時,可使用用於調整獲得之丙烯酸系彈性體分子量的鏈轉移劑。就鏈轉移劑而言,雖然可舉出例如,月桂基硫醇、十二烷基硫醇、硫代甘油等之具有硫醇基的化合物;次磷酸鈉、亞硫酸氫鈉等無機鹽,但本發明並不僅限於相關示例所列舉之化合物。此等鏈轉移劑係可各自單獨使用,亦可併用2種以上。雖然鏈轉移劑的量係因為該鏈轉移劑種類的不同,故不能一概而論地限定,但通常,較佳係每100質量部的單體,使用0.01~10質量部左右的鏈轉移劑。When polymerizing the monomer component, a chain transfer agent for adjusting the molecular weight of the obtained acrylic elastomer can be used. The chain transfer agent includes, for example, compounds having a thiol group such as lauryl mercaptan, dodecyl mercaptan, and thioglycerol; and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The present invention is not limited to the compounds exemplified in the relevant examples. These chain transfer agents may be used alone or in combination of two or more. Although the amount of the chain transfer agent cannot be generally limited depending on the type of the chain transfer agent, it is generally preferable to use about 0.01 to 10 parts by mass of the chain transfer agent per 100 parts by mass of the monomer.
就使單體成分聚合時的氛圍而言,並未特別限定,可在大氣中,或亦可在氮氣、氬氣等惰性氣體氛圍中。The atmosphere at the time of polymerizing the monomer components is not particularly limited, and it may be in the air or in an inert gas atmosphere such as nitrogen and argon.
就使單體成分聚合時的溫度而言,並未特別限定,通常較佳係在5~100℃左右的溫度。就使單體成分聚合時所需要的時間而言,雖然因為聚合條件的不同,不能一概而論地限定,故可為任意的,但通常係在1~20小時左右。Although it does not specifically limit about the temperature at the time of superposing|polymerizing a monomer component, Usually, the temperature of about 5-100 degreeC is preferable. The time required to polymerize the monomer components is not generally limited due to differences in the polymerization conditions, and may be arbitrary, but is usually about 1 to 20 hours.
在殘存之單體成分的量成為20質量%以下時,可任意地停止聚合反應。又,殘存之單體成分的量係能夠使用例如凝膠滲透色譜法(Gel permeation chromatography)進行測定。When the amount of the remaining monomer components becomes 20 mass % or less, the polymerization reaction can be stopped arbitrarily. In addition, the amount of the remaining monomer component can be measured using, for example, gel permeation chromatography (Gel permeation chromatography).
如以上般藉由使單體成分聚合,能夠獲得被含於本發明壓電材料之丙烯酸系彈性體。By polymerizing the monomer components as described above, the acrylic elastomer contained in the piezoelectric material of the present invention can be obtained.
(偏氟乙烯/三氟乙烯共聚物) 被含於本發明壓電材料之偏氟乙烯/三氟乙烯共聚物,係包含來自偏氟乙烯構造單元以及來自三氟乙烯構造單元之共聚物。從容易獲得具有優異耐熱性、耐變形性之壓電材料的觀點來看,基於全部構造單元的量,來自偏氟乙烯/三氟乙烯共聚物中的偏氟乙烯之構造單元的量較佳係55mol%以上,更佳係70mol%以上,再更佳係75mol%以上,特佳係80mol%以上,最佳係85mol%以上。又,從獲得良好壓電特性的壓電材料之觀點來看,基於全部構造單元的量,來自上述偏氟乙烯之構造單元的量較佳係90mol%以下,更佳係86mol%以下。(Vinylidene fluoride/trifluoroethylene copolymer) The vinylidene fluoride/trifluoroethylene copolymer contained in the piezoelectric material of the present invention includes a copolymer derived from a vinylidene fluoride structuring unit and a trifluoroethylene structuring unit. From the viewpoint of easily obtaining a piezoelectric material having excellent heat resistance and deformation resistance, the amount of the structural units derived from vinylidene fluoride in the vinylidene fluoride/trifluoroethylene copolymer is preferably based on the amount of all the structural units More than 55mol%, more preferably more than 70mol%, still more preferably more than 75mol%, especially preferably more than 80mol%, and most preferably more than 85mol%. Also, from the viewpoint of obtaining a piezoelectric material having good piezoelectric properties, the amount of the structural units derived from vinylidene fluoride is preferably 90 mol % or less, more preferably 86 mol % or less, based on the total structural unit amount.
從獲得良好壓電特性的壓電材料之觀點來看,基於全部構造單元的量,來自偏氟乙烯/三氟乙烯共聚物中的三氟乙烯之構造單元的量較佳係10mol%以上,更佳係14mol%以上。又,從獲得良好耐熱性的壓電材料之觀點來看,基於全部構造單元的量,來自上述三氟乙烯之構造單元的量較佳係45mol%以下,更佳係30mol%以下,再更佳係25mol%以下,特佳係20mol%以下。From the viewpoint of obtaining a piezoelectric material with good piezoelectric properties, the amount of the structural units derived from trifluoroethylene in the vinylidene fluoride/trifluoroethylene copolymer is preferably 10 mol % or more based on the amount of all the structural units, and more The best system is more than 14mol%. In addition, from the viewpoint of obtaining a piezoelectric material having good heat resistance, the amount of the above-mentioned structural units derived from trifluoroethylene is preferably 45 mol % or less, more preferably 30 mol % or less, and still more preferably based on the amount of all structural units. Department of 25mol% or less, especially preferably 20mol% or less.
本發明的壓電材料可含有1種的偏氟乙烯/三氟乙烯共聚物,亦可含有2種以上的偏氟乙烯/三氟乙烯共聚物。The piezoelectric material of the present invention may contain one type of vinylidene fluoride/trifluoroethylene copolymer, or may contain two or more types of vinylidene fluoride/trifluoroethylene copolymer.
雖然被含於本發明壓電材料之偏氟乙烯/三氟乙烯共聚物的黏度平均分子量並未特別限定,但從容易獲得難以產生嚴重斷裂變形而損壞之壓電材料的觀點來看,黏度平均分子量較佳係10萬/mol以上,更佳係30萬/mol以上,再更佳係50萬/mol以上,特佳係550萬/mol以上,最佳係60萬/mol以上。黏度平均分子量的上限並未特別限制,例如在200萬/mol以下左右。黏度平均分子量能夠使用習知的方法測定。在本發明之一較佳態樣中,壓電材料包含上述下限值以上(較佳係30萬/mol以上)之黏度平均分子量的偏氟乙烯/三氟乙烯共聚物,此被認為是能夠與具有相對高的重量平均分子量之丙烯酸系彈性體,產生更良好的聚合物鏈交纏,結果,能夠獲得具有優異的柔軟性、伸縮性,且具有優異的耐變形性之壓電材料。如此之壓電材料能夠特別適用於例如可穿戴設備等領域。Although the viscosity-average molecular weight of the vinylidene fluoride/trifluoroethylene copolymer contained in the piezoelectric material of the present invention is not particularly limited, from the viewpoint of easily obtaining a piezoelectric material that is hardly damaged by severe fracture deformation, the viscosity-average molecular weight is not particularly limited. The molecular weight is preferably more than 100,000/mol, more preferably more than 300,000/mol, still more preferably more than 500,000/mol, particularly preferably more than 5.5 million/mol, and most preferably more than 600,000/mol. The upper limit of the viscosity-average molecular weight is not particularly limited, and is, for example, about 2 million/mol or less. The viscosity-average molecular weight can be measured using a known method. In a preferred aspect of the present invention, the piezoelectric material includes a vinylidene fluoride/trifluoroethylene copolymer having a viscosity average molecular weight of not less than the lower limit (preferably not less than 300,000/mol), which is considered to be capable of With the acrylic elastomer having a relatively high weight average molecular weight, better polymer chain entanglement occurs, and as a result, a piezoelectric material having excellent flexibility, stretchability, and excellent deformation resistance can be obtained. Such piezoelectric materials can be particularly suitable for fields such as wearable devices.
在不損及本發明效果的範圍內,在被含於本發明壓電材料之偏氟乙烯/三氟乙烯共聚物中,除了包含來自偏氟乙烯的構造單元以及來自三氟乙烯的構造單元以外,亦可包含來自能夠與偏氟乙烯/三氟乙烯共聚合之其他單體的構造單元。就其他單體的例子而言,可舉出上述關於丙烯酸系彈性體之能夠與丙烯酸系單體共聚合之其他單體。從容易獲得優異耐熱性及壓電特性之壓電材料的觀點來看,在偏氟乙烯/三氟乙烯共聚物中,來自偏氟乙烯的構造單元以及來自三氟乙烯的構造單元之含有率較佳係90質量%以上,更佳係93質量%以上,特佳係95質量%以上;且來自能夠與偏氟乙烯/三氟乙烯共聚合之其他單體的構造單元之含有率較佳係10質量%以下,更佳係7質量%以下,特佳係5質量%以下。又,從容易發揮其他單體之效果的觀點來看,偏氟乙烯/三氟乙烯共聚物中,來自偏氟乙烯的構造單元以及來自三氟乙烯的構造單元之含有率較佳係99質量%以下,更佳係98質量%以下,特佳係97質量%以下;且來自能夠與偏氟乙烯/三氟乙烯共聚合之其他單體的構造單元之含有率較佳係1質量%以上,更佳係2質量%以上,特佳係3質量%以上。The vinylidene fluoride/trifluoroethylene copolymer contained in the piezoelectric material of the present invention includes a structural unit derived from vinylidene fluoride and a structural unit derived from trifluoroethylene within the range that does not impair the effects of the present invention. , and may also contain structural units derived from other monomers that can be copolymerized with vinylidene fluoride/trifluoroethylene. As an example of another monomer, the other monomer which can be copolymerized with an acrylic monomer about the above-mentioned acrylic elastomer can be mentioned. From the viewpoint of easily obtaining a piezoelectric material excellent in heat resistance and piezoelectric properties, in the vinylidene fluoride/trifluoroethylene copolymer, the content ratios of structural units derived from vinylidene fluoride and structural units derived from trifluoroethylene are relatively high. Preferably it is 90 mass% or more, more preferably 93 mass% or more, and particularly preferably 95 mass% or more; and the content of structural units derived from other monomers that can be copolymerized with vinylidene fluoride/trifluoroethylene is preferably 10 mass % or less, more preferably 7 mass % or less, and particularly preferably 5 mass % or less. In addition, in the vinylidene fluoride/trifluoroethylene copolymer, the content ratio of structural units derived from vinylidene fluoride and structural units derived from trifluoroethylene is preferably 99% by mass, from the viewpoint of easily exerting the effects of other monomers. Hereinafter, it is more preferably 98 mass % or less, particularly preferably 97 mass % or less; and the content of structural units derived from other monomers that can be copolymerized with vinylidene fluoride/trifluoroethylene is preferably 1 mass % or more, more preferably 2 mass % or more of the best system, and 3 mass % or more of the extra-best system.
就被含於本發明壓電材料之偏氟乙烯/三氟乙烯共聚物而言,能夠可用例如專利文獻1所示之組成及分子量而成之物,亦可使用市售之物。就市售之偏氟乙烯/三氟乙烯共聚物的例子而言,可舉出例如PIEZOTECH公司製的「FC20」、「FC25」、「FC30」。As the vinylidene fluoride/trifluoroethylene copolymer contained in the piezoelectric material of the present invention, for example, those having the composition and molecular weight shown in Patent Document 1 can be used, or commercially available ones can also be used. Examples of commercially available vinylidene fluoride/trifluoroethylene copolymers include "FC20", "FC25", and "FC30" manufactured by PIEZOTECH, for example.
(壓電材料用組成物及壓電材料) 雖然本發明之壓電材料的製造方法並未特別限定,例如能夠在塗佈含有偏氟乙烯/三氟乙烯共聚物、前述特定的丙烯酸系彈性體及溶媒之溶液並乾燥後,藉由進行熱處理,並使偏氟乙烯/三氟乙烯共聚物結晶化而產生壓電特性,來製造壓電材料。又,乾燥與熱處理係可同時進行。就其他的例子而言,可舉出包含以下步驟之壓電材料的製造方法:混合步驟,將偏氟乙烯/三氟乙烯共聚物、構成前述特定丙烯酸系彈性體的單體、因應必要的溶媒混合;丙烯酸系彈性體獲得步驟,將前述單體聚合,獲得前述特定丙烯酸系彈性體;壓電特性產生步驟,藉由使偏氟乙烯/三氟乙烯共聚物結晶化而產生壓電特性。就其他的例子而言,可舉出包含以下步驟之壓電材料的製造方法:混合步驟,將前述特定丙烯酸系彈性體、構成偏氟乙烯/三氟乙烯共聚物的單體、因應必要的溶媒混合;偏氟乙烯/三氟乙烯共聚物獲得步驟,將前述單體聚合,獲得前述偏氟乙烯/三氟乙烯共聚物;壓電特性產生步驟,藉由使偏氟乙烯/三氟乙烯共聚物結晶化而產生壓電特性。將含有用於製造壓電材料時所需之偏氟乙烯/三氟乙烯共聚物、前述特定丙烯酸系彈性體及溶媒的溶液,於以下亦稱為「壓電材料用組成物」。於壓電材料用組成物中,可包含偏氟乙烯/三氟乙烯共聚物及前述特定丙烯酸系彈性體中的任一者、以及在構成各自的單體狀態下含有另一者之組合物。本發明亦提供壓電材料用組成物。又,在本說明書中,關於被含於本發明壓電材料之丙烯酸系彈性體及偏氟乙烯/三氟乙烯共聚物的記載,係能夠同樣地應用於關於被含於本發明壓電材料用組成物之丙烯酸系彈性體及偏氟乙烯/三氟乙烯共聚物的記載。(Composition for Piezoelectric Material and Piezoelectric Material) Although the method for producing the piezoelectric material of the present invention is not particularly limited, for example, the above-mentioned specific acrylic elastomer containing vinylidene fluoride/trifluoroethylene copolymer can be coated A piezoelectric material is produced by heat-treating and crystallizing a vinylidene fluoride/trifluoroethylene copolymer to develop piezoelectric properties after drying a solution of a solvent and a solvent. In addition, drying and heat treatment may be performed simultaneously. Another example includes a method for producing a piezoelectric material including a mixing step in which a vinylidene fluoride/trifluoroethylene copolymer, a monomer constituting the above-mentioned specific acrylic elastomer, and a solvent as necessary are mixed together. mixing; an acrylic elastomer obtaining step, polymerizing the aforementioned monomers to obtain the aforementioned specific acrylic elastomer; a piezoelectric characteristic generating step, generating piezoelectric characteristics by crystallizing a vinylidene fluoride/trifluoroethylene copolymer. Another example includes a method for producing a piezoelectric material including a mixing step in which the above-mentioned specific acrylic elastomer, a monomer constituting a vinylidene fluoride/trifluoroethylene copolymer, and a solvent as necessary are mixed together. mixing; a vinylidene fluoride/trifluoroethylene copolymer obtaining step of polymerizing the aforementioned monomers to obtain the aforementioned vinylidene fluoride/trifluoroethylene copolymer; a piezoelectric characteristic generating step, by making the vinylidene fluoride/trifluoroethylene copolymer Crystallization produces piezoelectric properties. The solution containing the vinylidene fluoride/trifluoroethylene copolymer, the above-mentioned specific acrylic elastomer, and a solvent required for the production of a piezoelectric material is also referred to as a "piezoelectric material composition" hereinafter. The composition for piezoelectric materials may contain any one of the vinylidene fluoride/trifluoroethylene copolymer and the specific acrylic elastomer described above, and a composition containing the other in the state of constituting each of the monomers. The present invention also provides a composition for a piezoelectric material. In addition, in this specification, the description about the acrylic elastomer and the vinylidene fluoride/trifluoroethylene copolymer contained in the piezoelectric material of the present invention can be similarly applied to the piezoelectric material contained in the present invention. Description of the composition of acrylic elastomer and vinylidene fluoride/trifluoroethylene copolymer.
針對可被包含在壓電材料用組成物的溶媒而言,雖然只要是能夠溶解偏氟乙烯/三氟乙烯共聚物及丙烯酸系彈性體的溶媒,就並未特別限定,但可舉出例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、1-甲基-2-吡咯烷酮等。The solvent that can be included in the composition for piezoelectric materials is not particularly limited as long as it can dissolve the vinylidene fluoride/trifluoroethylene copolymer and the acrylic elastomer. For example, N , N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc.
雖然並未特別限定,但可藉由將偏氟乙烯/三氟乙烯共聚物、丙烯酸系彈性體及因應必要的溶媒,因應必要而同時加熱並混合後,使偏氟乙烯/三氟乙烯共聚物及丙烯酸系彈性體溶解於溶媒,來製造本發明的壓電材料用組成物。又,可將偏氟乙烯/三氟乙烯共聚物、構成前述特定丙烯酸系彈性體的單體及溶媒,因應必要而同時加熱並混合後,來製造壓電材料用組成物。此時,被含於壓電材料用組成物之構成前述特定丙烯酸系彈性體的單體聚合後,所獲得之含有丙烯酸系彈性體的組成物亦為本發明的壓電材料用組成物。亦能夠同樣地製造包含構成偏氟乙烯/三氟乙烯共聚物的單體與含有前述特定丙烯酸系彈性體之壓電材料用組成物。Although not particularly limited, the vinylidene fluoride/trifluoroethylene copolymer can be prepared by heating and mixing the vinylidene fluoride/trifluoroethylene copolymer, the acrylic elastomer, and the necessary solvent as necessary. and the acrylic elastomer are dissolved in a solvent to produce the piezoelectric material composition of the present invention. In addition, the composition for piezoelectric materials can be produced by heating and mixing the vinylidene fluoride/trifluoroethylene copolymer, the monomer and solvent constituting the above-mentioned specific acrylic elastomer, if necessary, at the same time. In this case, the composition containing the acrylic elastomer obtained after being polymerized with the monomer constituting the above-mentioned specific acrylic elastomer contained in the composition for piezoelectric material is also the composition for piezoelectric material of the present invention. The composition for piezoelectric materials containing the monomer which comprises a vinylidene fluoride/trifluoroethylene copolymer and the said specific acrylic elastomer can also be manufactured similarly.
接著,將本發明的壓電材料用組成物塗佈於基材上,因應必要使構成丙烯酸系彈性體的單體或構成偏氟乙烯/三氟乙烯共聚物的單體聚合,並藉由乾燥及熱處理使其結晶化並產生壓電特性,而能夠製造本發明的壓電材料。舉例來說,在本發明的壓電材料係壓電膜的情況下,亦可將本發明的壓電材料用組成物塗佈於基材表面上。舉例來說,在本發明的壓電材料係壓電線的情況下,可使用習知的方法,將本發明的壓電材料用組成物塗佈於如銅線般的導電性線材上,例如塗佈於由導電性材料而成之單線上。Next, the composition for piezoelectric material of the present invention is applied on a substrate, and as necessary, the monomer constituting the acrylic elastomer or the monomer constituting the vinylidene fluoride/trifluoroethylene copolymer is polymerized, and dried by drying The piezoelectric material of the present invention can be produced by crystallization and heat treatment to develop piezoelectric properties. For example, in the case of the piezoelectric material-based piezoelectric film of the present invention, the composition for a piezoelectric material of the present invention may be coated on the surface of the substrate. For example, in the case of the piezoelectric material-based piezoelectric wire of the present invention, the composition for piezoelectric material of the present invention can be coated on a conductive wire such as a copper wire using a conventional method, such as Coated on a single wire made of conductive material.
將塗佈後之本發明的壓電材料用組成物乾燥的方法並未特別限制,可在大氣壓條件下或減壓條件下,以使溶媒蒸發的溫度加熱並乾燥。例如,較佳係在15~80℃的溫度下進行乾燥。The method for drying the piezoelectric material composition of the present invention after coating is not particularly limited, and it can be heated and dried under atmospheric pressure or reduced pressure at a temperature at which the solvent is evaporated. For example, drying is preferably carried out at a temperature of 15 to 80°C.
在製造本發明的壓電材料時熱處理的溫度較佳係偏氟乙烯/三氟乙烯共聚物之居里(Curie)點以上且熔點以下的溫度。加熱時間較佳係30分鐘以上,更佳係2小時以上。藉由進行如此之熱處理,能夠使偏氟乙烯/三氟乙烯共聚物結晶化,並發現壓電特性。The temperature of the heat treatment in the production of the piezoelectric material of the present invention is preferably a temperature equal to or higher than the Curie point of the vinylidene fluoride/trifluoroethylene copolymer and equal to or lower than the melting point. The heating time is preferably 30 minutes or more, more preferably 2 hours or more. By performing such a heat treatment, the vinylidene fluoride/trifluoroethylene copolymer can be crystallized, and piezoelectric properties can be found.
本發明的壓電材料係可為壓電膜、壓電線、壓電塊(block)。從容易活用具有優異柔軟性及伸縮性之本發明壓電材料的特徵的觀點來看,壓電材料較佳係壓電膜。The piezoelectric material of the present invention can be a piezoelectric film, a piezoelectric wire, or a piezoelectric block. The piezoelectric material is preferably a piezoelectric film from the viewpoint of easily utilizing the features of the piezoelectric material of the present invention having excellent flexibility and stretchability.
從容易獲得充分壓電特性的觀點來看,就本發明壓電材料的機電耦合係數k31 及kt 而言,較佳係k31 為0.03以上且kt 為0.1以上,更佳係k31 為0.045以上且kt 為0.15以上,特佳係k31 為0.06以上且kt 為0.2以上。機電耦合係數的測定方法係如同實施例所載。From the viewpoint of easily obtaining sufficient piezoelectric properties, the electromechanical coupling coefficients k 31 and k t of the piezoelectric material of the present invention are preferably k 31 of 0.03 or more and k t of 0.1 or more, more preferably k 31 It is 0.045 or more and k t is 0.15 or more, and it is especially preferable that k 31 is 0.06 or more and k t is 0.2 or more. The method for measuring the electromechanical coupling coefficient is as described in the Examples.
從容易獲得特別是可穿戴設備等領域中所要求之優異柔軟性、伸縮性的觀點來看,本發明壓電材料的楊氏率較佳係3.1GPa以下,更佳係2.9GPa以下,特佳係2.5GPa以下。楊氏率的測定方法係如同實施例所載。雖然楊氏率的下限值並未特別限定,但從容易提高壓電材料之尺寸安定性的觀點來看,可例如為0.1GPa以上。From the viewpoint of easily obtaining the excellent flexibility and stretchability required in the fields of wearable devices and the like, the Young's ratio of the piezoelectric material of the present invention is preferably 3.1 GPa or less, more preferably 2.9 GPa or less, and particularly preferably Department of 2.5GPa or less. The Young's ratio was measured as described in the Examples. The lower limit value of the Young's ratio is not particularly limited, but from the viewpoint of easily improving the dimensional stability of the piezoelectric material, it can be, for example, 0.1 GPa or more.
[實施例] 以下,雖然藉由實施例更詳細地說明本發明,但此等實施例係用於說明本發明,本發明並不僅限於下列實施例。又,只要並未特別註記,實施例中的「%」及「部」係各自表示「質量%」及「質量部」。[Examples] Hereinafter, the present invention will be described in more detail by way of examples, but these examples are intended to illustrate the present invention, and the present invention is not limited to the following examples. In addition, unless otherwise noted, "%" and "part" in the examples represent "mass %" and "quality part", respectively.
在後述之實施例及比較例中,使用以下聚合物。 ‧偏氟乙烯/三氟乙烯共聚物A1 VDF:TrFE = 85:15(莫耳比) 黏度平均分子量 65萬/mol ‧偏氟乙烯/三氟乙烯共聚物A2 VDF:TrFE = 75:25(莫耳比) 黏度平均分子量 35萬/mol ‧丙烯酸系彈性體B1 大阪有機化學工業(股)製「Suave-00」,丙烯酸乙酯的均聚物,重量平均分子量150~160萬In Examples and Comparative Examples to be described later, the following polymers were used. ‧Vinylidene fluoride/trifluoroethylene copolymer A1 VDF: TrFE = 85:15 (mol ratio) viscosity average molecular weight 650,000/mol ‧Vinylidene fluoride/trifluoroethylene copolymer A2 VDF: TrFE = 75:25 (mol ratio) Ear ratio) Viscosity average molecular weight 350,000/mol ‧Acrylic Elastomer B1 "Suave-00" manufactured by Osaka Organic Chemical Industry Co., Ltd., homopolymer of ethyl acrylate, weight average molecular weight 1.5-1.6 million
(丙烯酸系彈性體的重量平均分子量) 丙烯酸系彈性體的重量平均分子量係藉由凝膠滲透色譜法(GPC)測定。具體而言,使用將丙烯酸系彈性體溶解於四氫呋喃所獲得之0.05~0.1質量%的溶液作為測定試料。測定條件如下所述。 機器:東曹(股)製,型號:HLC-8320GPC 管柱:東曹(股)製,型號:TSKgel GMHHR 洗脫液:四氫呋喃 流量:0.6mL/min 溫度:40℃ 檢測器:折射率偵測器(RI, refractive index) 分子量標準:標準聚苯乙烯(Weight Average Molecular Weight of Acrylic Elastomer) The weight average molecular weight of the acrylic elastomer was measured by gel permeation chromatography (GPC). Specifically, a 0.05 to 0.1 mass % solution obtained by dissolving an acrylic elastomer in tetrahydrofuran is used as a measurement sample. The measurement conditions are as follows. Machine: Tosoh Corporation, Model: HLC-8320GPC Column: Tosoh Corporation, Model: TSKgel GMHHR Eluent: THF Flow Rate: 0.6mL/min Temperature: 40°C Detector: Refractive Index Detection Refractive index (RI, refractive index) Molecular weight standard: standard polystyrene
實施例1:壓電材料用組成物1及壓電材料1的製造 將5.5617g偏氟乙烯/三氟乙烯共聚物(P(VDF/TrFE)A1、0.2825g丙烯酸系彈性體B1、作為溶媒之53.9796g的N,N-二甲基甲醯胺,於帶栓之燒瓶內混合,並製造包含具有表1所示之質量比的偏氟乙烯/三氟乙烯共聚物A1及丙烯酸系彈性體B1之壓電材料用組成物1。Example 1: Production of piezoelectric material composition 1 and piezoelectric material 1 5.5617 g of vinylidene fluoride/trifluoroethylene copolymer (P(VDF/TrFE) A1, 0.2825 g of acrylic elastomer B1, and 53.9796g of N,N-dimethylformamide was mixed in a flask with a stopper, and the production of vinylidene fluoride/trifluoroethylene copolymer A1 and acrylic elastomer B1 having the mass ratio shown in Table 1 Composition 1 for piezoelectric materials.
將如上述般製造之壓電材料用組成物1塗佈於玻璃基板上成為0.9mm的厚度,在3hPa、65℃下加熱一小時以上,並將壓電材料用組成物中的溶媒乾燥。將獲得之塗膜,於大氣下,以142℃加熱兩小時,進行熱處理,並使偏氟乙烯/三氟乙烯共聚物結晶化,而發現壓電特性。接著,將熱處理後的塗膜從玻璃基板剝離,獲得膜。接著,使用電阻加熱式的真空氣相沉積機,在氣壓5x10-3 ~5x10-4 Pa的範圍,使鋁加熱蒸發,於膜的兩面形成電極被膜。於如此所獲得之膜兩面的電極間,直接在施加6個週期之電壓幅值為120MV/m、頻率為100mHz以下之三角波交流電的條件下(本公司:(股)伊雷阿爾史達製,使用輪詢(polling)處理系統),進行極化處理,獲得壓電材料1。以下,針對物性的測定方法、算出方法及評價方法,進行說明。The piezoelectric material composition 1 produced as described above was applied on a glass substrate to a thickness of 0.9 mm, heated at 3 hPa and 65° C. for one hour or more, and the solvent in the piezoelectric material composition was dried. The obtained coating film was heated at 142° C. for two hours in the atmosphere, and heat-treated to crystallize the vinylidene fluoride/trifluoroethylene copolymer, thereby finding piezoelectric properties. Next, the coating film after the heat treatment was peeled off from the glass substrate to obtain a film. Next, using a resistance heating type vacuum vapor deposition machine, the aluminum was heated and evaporated in a pressure range of 5x10 -3 to 5x10 -4 Pa, and electrode coatings were formed on both sides of the film. Between the electrodes on both sides of the film thus obtained, a triangular-wave alternating current with a voltage amplitude of 120 MV/m and a frequency of 100 mHz or less was directly applied for 6 cycles (Our company: (stock) Ire Alstar System, Using a polling processing system), polarization processing was performed, and piezoelectric material 1 was obtained. Hereinafter, the measurement method, calculation method, and evaluation method of physical properties will be described.
(殘留極化/抗電場) 殘留極化及抗電場係從D(電變位)-E(電場)的滯後曲線讀取。此處,D-E的滯後曲線,係以上述分法所進行之極化處理最終之6週期的值,且將朝試料的施加電壓與索耶塔(Sawyer-tower)電路側的電容器電壓之兩種電壓測定數據,換算成D(電變位)及E(電場)的值,來繪製而成者。(Residual polarization/Anti-electric field) Residual polarization and anti-electric field were read from a hysteresis curve of D (electrical displacement)-E (electric field). Here, the hysteresis curve of D-E is the value of the last 6 cycles of the polarization treatment performed by the above-mentioned division method, and the voltage applied to the sample and the capacitor voltage on the side of the Sawyer-tower circuit are two types. The voltage measurement data is converted into the values of D (electrical displacement) and E (electric field) and plotted.
(機電耦合係數) 將極化處理後的壓電材料1,作為延伸方向(k31 )之機電耦合係數的測料試料,而切出成30 x 5mm;又,作為厚度方向(kt )之機電耦合係數的測料試料,而切出成5 x 5mm。針對各測定試料,以阻抗分析儀(Agilent Technologies(現keysite‧technology)製,4294A)在1k~110MHz的範圍內,測定准入-位相數據(Admittance-phase data)。將獲得之測定結果適用於自由共振的導納方程式(Admittance formula),求得機電耦合係數。 具體而言,若以在厚度方向的情況為例,將阻抗分析儀所測定之准入數據的絕對值及位相的結果,以與下述式子的計算值一致的方式,代入各常數的值,並算出厚度方向的機電耦合係數。 [數1][式中,C0 =(εr ×S×ε0 )/t [式中,εr :相對介電常數,ε0 :真空介電常數「F/m」,S:電極面積「m2 」,t:膜厚「m」] Kt :機電耦合係數,ψ:機械損失,φ:介電損失,v:音速[m/s] ,ω:角速度[rad/s](=2πf,f:頻率[Hz])]。(Electromechanical Coupling Coefficient) The piezoelectric material 1 after polarization treatment was used as a test material for the electromechanical coupling coefficient in the extension direction ( k 31 ), and cut out into 30 x 5 mm; A sample of the test material for the electromechanical coupling coefficient, and cut out to 5 x 5mm. For each measurement sample, admission-phase data (Admittance-phase data) was measured in the range of 1 k to 110 MHz with an impedance analyzer (manufactured by Agilent Technologies (current keysite technology), 4294A). The obtained measurement results were applied to the admittance formula of free resonance to obtain the electromechanical coupling coefficient. Specifically, taking the case in the thickness direction as an example, the absolute value and phase result of the admission data measured by the impedance analyzer are substituted into the values of the respective constants so as to agree with the calculated values of the following equations , and calculate the electromechanical coupling coefficient in the thickness direction. [Number 1] [where, C 0 =(ε r ×S ×ε 0 )/t [where, ε r : relative permittivity, ε 0 : vacuum permittivity "F/m", S: electrode area "m 2 ”, t: film thickness “m”] K t : electromechanical coupling coefficient, ψ: mechanical loss, φ: dielectric loss, v: sound velocity [m/s], ω: angular velocity [rad/s] (=2πf, f : Frequency [Hz])].
(斷裂變形/楊氏率) 將壓電材料1切斷成尺寸為寬度15mm,長度100mm的試驗片。拉伸試驗係在夾盤(Chuck)間距離:50mm,且拉伸速度:50mm/分鐘的條件下,使用(股)島津製作所製作的Autograph AGS-1kNX進行。藉由獲得之荷重-變位量,求得斷裂變形及楊氏率。此處,將標點間距離作為夾盤間距離,使用楊氏率在應力5~15MPa間的數據並以最小平方法算出。又,楊氏率低係表示壓電材料的柔軟性及伸縮性優異。又,斷裂變形大係表示壓電材料難以因為應力而損壞,耐變形性優異。(Fracture Deformation/Young's Ratio) Piezoelectric material 1 was cut into test pieces having a size of 15 mm in width and 100 mm in length. The tensile test was performed using Autograph AGS-1kNX manufactured by Shimadzu Corporation under the conditions of distance between chucks: 50 mm and tensile speed: 50 mm/min. From the obtained load-displacement amount, fracture deformation and Young's ratio were obtained. Here, the distance between the punctuation points is used as the distance between the chucks, and it is calculated by the least squares method using the data of the Young's ratio in the stress range of 5 to 15 MPa. In addition, a low Young's ratio means that the piezoelectric material is excellent in flexibility and stretchability. In addition, the large fracture deformation means that the piezoelectric material is hardly damaged by stress and is excellent in deformation resistance.
針對實施例1的壓電材料1所獲得之結果顯示於表2。The results obtained for Piezoelectric Material 1 of Example 1 are shown in Table 2.
實施例2~4及比較例1~2 除了變更成表1所示的組成以外,與實施例1相同地,調製壓電材料。針對獲得之壓電材料進行同樣的測定,並將結果顯示於表2。Examples 2 to 4 and Comparative Examples 1 to 2 The piezoelectric materials were prepared in the same manner as in Example 1, except that the compositions shown in Table 1 were changed. The same measurement was performed for the obtained piezoelectric material, and the results are shown in Table 2.
[表1]
[表2]
無none
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