TW201835218A - Resin composition, cured product, electroconductive film, electroconductive pattern and clothes - Google Patents
Resin composition, cured product, electroconductive film, electroconductive pattern and clothes Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
Description
本發明係關於一種樹脂組成物，其可用以在可伸縮及/或彎曲之基材形成電極。本發明係關於含有該樹脂組成物之導電性膏及該導電性膏之硬化物。本發明係關於含有該樹脂組成物之導電性膜或導電性圖案。本發明係關於含有該硬化物、導電性膜或導電性圖案之衣服。 The present invention relates to a resin composition which can be used to form an electrode on a stretchable and/or curved substrate. The present invention relates to a conductive paste containing the resin composition and a cured product of the conductive paste. The present invention relates to a conductive film or a conductive pattern containing the resin composition. The present invention relates to a garment containing the cured product, a conductive film or a conductive pattern.
近年來開發有一種導電性膏，其可用以於可伸縮及彎曲之基材形成電極。 In recent years, a conductive paste has been developed which can be used to form electrodes on a stretchable and curved substrate.
例如專利文獻1中記載一種聚合物厚膜組成物，其含有(a)功能性成分及(b)將5至50重量%(相對於有機媒體合計重量之重量百分率)之熱塑性聚胺甲酸乙酯樹脂溶解於有機溶媒而得之有機媒體。專利文獻1中記載熱塑性聚胺甲酸乙酯樹脂之伸長率為200%以上，熱塑性聚胺甲酸乙酯樹脂達到100%伸長時之拉伸應力為1000psi以下(約6.895MPa以下)。 For example, Patent Document 1 describes a polymer thick film composition containing (a) a functional component and (b) a thermoplastic polyurethane having 5 to 50% by weight (by weight based on the total weight of the organic medium). The resin is dissolved in an organic solvent to obtain an organic medium. Patent Document 1 discloses that the elongation of the thermoplastic polyurethane resin is 200% or more, and the tensile stress when the thermoplastic polyurethane resin reaches 100% elongation is 1000 psi or less (about 6.895 MPa or less).
專利文獻2中記載一種導電性膏，其係於 樹脂(A)中均一分散有導電性填料(B)。專利文獻2中記載：樹脂(A)係為基於碸化或硫酸化之橡膠，並含有聚陰離子作為摻雜物之共軛雙鍵高分子之水分散體(A1)，導電性填料(B)為平均粒徑0.5至10μm之金屬粉(B1)，及導電性膏固體含量中之樹脂(A)及導電性填料(B)之各調配量分別為50至80體積%及20至50體積%。 Patent Document 2 describes a conductive paste in which a conductive filler (B) is uniformly dispersed in a resin (A). Patent Document 2 discloses that the resin (A) is an aqueous dispersion of a conjugated double bond polymer (A1) based on a deuterated or sulfated rubber and containing a polyanion as a dopant, and a conductive filler (B) The metal powder (B1) having an average particle diameter of 0.5 to 10 μm, and the respective amounts of the resin (A) and the conductive filler (B) in the solid content of the conductive paste are 50 to 80% by volume and 20 to 50% by volume, respectively. .
專利文獻3中記載一種伸縮性配線板，係具備由第1彈性體所構成之伸縮性基材及含有導電性填料及第2彈性體之伸縮性配線，其中僅在前述伸縮性基材與伸縮性配線之間且前述伸縮性配線下形成有伸縮性密著層。 Patent Document 3 discloses a stretchable wiring board including a stretchable base material composed of a first elastic body and a stretchable wiring including a conductive filler and a second elastic body, wherein only the stretchable base material and the stretchable body are provided. A stretchable adhesive layer is formed between the flexible wirings and under the stretchable wiring.
專利文獻1：國際公開第2016/073465號 Patent Document 1: International Publication No. 2016/073465
專利文獻2：日本特開2015-65139號公報。 Patent Document 2: Japanese Laid-Open Patent Publication No. 2015-65139.
專利文獻3：日本特開2014-151617號公報。 Patent Document 3: Japanese Laid-Open Patent Publication No. 2014-151617.
近年來已嘗試於可伸縮及/或彎曲之基材表面形成電氣電路及/或電子電路之配線。於此類基材形成配線時，會因基材之伸縮及/或彎曲而有配線斷線之虞。 In recent years, attempts have been made to form wiring for electrical circuits and/or electronic circuits on the surface of a retractable and/or curved substrate. When wiring is formed on such a substrate, there is a possibility that the wiring is broken due to expansion and contraction and/or bending of the substrate.
因此，本發明之目的在於提供可於伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電 子電路之配線的樹脂組成物及其硬化物。又，本發明之目的在於提供用以於可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之配線的導電性膜或導電性圖案。又，本發明之目的在於提供含有導電性膜或導電性圖案之衣服。 Accordingly, it is an object of the present invention to provide a resin composition and a cured product thereof which can form wiring of an electric circuit and/or an electronic circuit which is less likely to be broken on the surface of a substrate which is stretched and/or bent. Further, an object of the present invention is to provide a conductive film or a conductive pattern for forming wiring of an electric circuit and/or an electronic circuit which is less likely to be broken on the surface of a stretchable and/or curved substrate. Further, it is an object of the invention to provide a garment comprising a conductive film or a conductive pattern.
為了解決上述課題，本發明具有以下構成。 In order to solve the above problems, the present invention has the following configuration.
(構成1) (Composition 1)
本發明之構成1為一種樹脂組成物，係含有(A)導電性粒子、(B)100%模數為7MPa以上之熱塑性聚胺甲酸乙酯樹脂及(C)溶劑，相對於(A)導電性粒子與(B)熱塑性聚胺甲酸乙酯樹脂之合計，(A)導電性粒子之比率為90重量%以上未達100重量%。 The constitution 1 of the present invention is a resin composition containing (A) conductive particles, (B) a thermoplastic polyurethane resin having a 100% modulus of 7 MPa or more, and (C) a solvent, which is electrically conductive with respect to (A) In the total of the particles and the (B) thermoplastic polyurethane resin, the ratio of the (A) conductive particles is 90% by weight or more and less than 100% by weight.
根據本發明之構成1可提供一種樹脂組成物，係可於可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之配線。 According to the constitution 1 of the present invention, it is possible to provide a resin composition which can form wiring of an electric circuit and/or an electronic circuit which is less likely to be broken on the surface of the stretchable and/or curved substrate.
(構成2) (constituent 2)
本發明之構成2係構成1之樹脂組成物，其中，相對於(A)導電性粒子與(B)熱塑性聚胺甲酸乙酯樹脂之合計，(A)導電性粒子之比率為90重量%以上95重量%以下。 The composition of the present invention is a resin composition of the first aspect, wherein the ratio of the (A) conductive particles is 90% by weight or more based on the total of the (A) conductive particles and the (B) thermoplastic polyurethane resin. 95% by weight or less.
將使用本發明之構成2之樹脂組成物形成之配線伸長時，可降低伸長所造成配線電阻之增加。 When the wiring formed using the resin composition of the constitution 2 of the present invention is elongated, the increase in wiring resistance due to elongation can be reduced.
(構成3) (constitution 3)
本發明之構成3係構成1或2之樹脂組成物，其中， (A)導電性粒子含有由Ag、Au、Cu、Ni及Ti所選擇之至少一種。 The composition 3 of the present invention is a resin composition of the first or second embodiment, wherein the conductive particles (A) contain at least one selected from the group consisting of Ag, Au, Cu, Ni, and Ti.
根據本發明之構成3，金屬被覆層含有特定金屬，藉此可形成低電阻之電氣電路及/或電子電路之配線。 According to the constitution 3 of the present invention, the metal coating layer contains a specific metal, whereby the wiring of the low-resistance electrical circuit and/or the electronic circuit can be formed.
(構成4) (construction 4)
本發明之構成4係構成1至3中任一項之樹脂組成物，其中，(B)熱塑性聚胺甲酸乙酯樹脂係由己內酯系、酯系、醚系及碳酸酯系所選擇之至少一種。 The resin composition according to any one of claims 1 to 3, wherein the (B) thermoplastic polyurethane resin is selected from at least a caprolactone system, an ester system, an ether system, and a carbonate system. One.
根據本發明之構成4，樹脂組成物係使用特定種類之聚胺甲酸乙酯作為(B)熱塑性聚胺甲酸乙酯樹脂，藉由使用該樹脂組成物而可確實地於可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之配線。 According to the constitution 4 of the present invention, the resin composition is a specific type of polyurethane as the (B) thermoplastic polyurethane resin, and can be reliably stretched and/or bent by using the resin composition. The surface of the substrate forms wiring of an electrical circuit and/or an electronic circuit that is less likely to be broken.
(構成5) (Constituent 5)
本發明之構成5係構成1至4中任一項之樹脂組成物，其中，(C)溶劑為由環己酮、二甲基甲醯胺、二甲基乙醯胺及苄醇所選擇之至少一種。 The composition 5 of the present invention is the resin composition of any one of 1 to 4, wherein the solvent (C) is selected from cyclohexanone, dimethylformamide, dimethylacetamide, and benzyl alcohol. At least one.
根據本發明之構成5，藉由使用特定溶媒而可確實溶解特定之熱塑性聚胺甲酸乙酯樹脂。其結果可使用以形成配線之樹脂組成物之網版印刷等較為容易。 According to the constitution 5 of the present invention, a specific thermoplastic polyurethane resin can be surely dissolved by using a specific solvent. As a result, it is easy to use screen printing or the like which forms a resin composition of wiring.
(構成6) (constituent 6)
本發明之構成6係一種導電性膏，係含有構成1至5中任一項之樹脂組成物。 The composition 6 of the present invention is a conductive paste containing the resin composition of any one of 1 to 5.
藉由使用本發明之構成6之導電性膏，可以網版印刷等手段於可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之配線。 By using the conductive paste of the constitution 6 of the present invention, wiring of an electric circuit and/or an electronic circuit having a low possibility of disconnection can be formed on the surface of the stretchable and/or curved substrate by means of screen printing or the like.
(構成7) (constituent 7)
本發明之構成7係構成6之導電性膏之硬化物。將本發明之導電性膏以網版印刷等手段形成為電氣電路及/或電子電路之配線之形狀並硬化，藉此可於可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之配線。 The constitution 7 of the present invention constitutes a cured product of the conductive paste of 6. The conductive paste of the present invention is formed into a shape of a wiring of an electric circuit and/or an electronic circuit by means of screen printing or the like, and is cured, whereby a possibility of disconnection on the surface of the stretchable and/or curved substrate can be made low. Wiring of electrical circuits and/or electronic circuits.
(構成8) (Composition 8)
本發明之構成8係一種導電性膜或導電性圖案，係含有構成1至5中任一項之樹脂組成物。 The constitution 8 of the present invention is a conductive film or a conductive pattern, and the resin composition of any one of the components 1 to 5 is contained.
若於可伸縮及/或彎曲之基材表面形成本發明之構成8之導電性膜或導電性圖案，並成為電氣電路及/或電子電路之配線，則可得斷線可能性低之配線。 When the conductive film or the conductive pattern of the structure 8 of the present invention is formed on the surface of the stretchable and/or curved substrate and the wiring of the electric circuit and/or the electronic circuit is formed, wiring having a low possibility of disconnection can be obtained.
(構成9) (constituent 9)
本發明之構成9係一種衣服，係含有構成7之導電性膏硬化物、或構成8之導電性膜或導電性圖案。 The constitution 9 of the present invention is a garment comprising a conductive paste cured material of the seventh structure or a conductive film or a conductive pattern of the composition 8.
若使用本發明之樹脂組成物之導電性膏，則可於可伸縮及/或彎曲之衣服形成配線，而作為導電性膏硬化物、或導電性膜或導電性圖案。 When the conductive paste of the resin composition of the present invention is used, wiring can be formed in a stretchable and/or curved garment as a conductive paste cured material, or a conductive film or a conductive pattern.
根據本發明可提供可於可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之 配線的樹脂組成物及其硬化物。又，根據本發明可提供用以在可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之配線的導電性膜或導電性圖案。又，根據本發明可提供含有導電性膜或導電性圖案之衣服。 According to the present invention, it is possible to provide a resin composition and a cured product thereof which can form wiring of an electric circuit and/or an electronic circuit which are less likely to be broken on the surface of a stretchable and/or curved substrate. Further, according to the present invention, it is possible to provide a conductive film or a conductive pattern for forming wiring of an electric circuit and/or an electronic circuit which is less likely to be broken on the surface of a stretchable and/or curved substrate. Further, according to the present invention, a garment containing a conductive film or a conductive pattern can be provided.
本發明係含有(A)導電性粒子、(B)100%模數為7MPa以上之熱塑性聚胺甲酸乙酯樹脂及(C)溶劑之樹脂組成物。本發明之樹脂組成物中，相對於(A)導電性粒子與(B)熱塑性聚胺甲酸乙酯樹脂之合計，(A)導電性粒子之比率為90重量%以上未達100重量%。 The present invention is a resin composition containing (A) conductive particles, (B) a thermoplastic polyurethane resin having a 100% modulus of 7 MPa or more, and (C) a solvent. In the resin composition of the present invention, the ratio of the (A) conductive particles is 90% by weight or more to less than 100% by weight based on the total of the (A) conductive particles and the (B) thermoplastic polyurethane resin.
使用含有本發明之樹脂組成物之導電性膏形成電氣電路及/或電子電路之配線(亦簡稱為「配線」)時，可形成伸縮性及彎曲性優異之斷線可能性低之配線。因此，為了於可伸縮及/或彎曲之基材表面形成配線可適合使用本發明之樹脂組成物。 When a wiring (also simply referred to as "wiring") for forming an electric circuit and/or an electronic circuit using the conductive paste containing the resin composition of the present invention, it is possible to form a wiring having a low possibility of disconnection and excellent flexibility. Therefore, the resin composition of the present invention can be suitably used in order to form a wiring on the surface of the stretchable and/or curved substrate.
本說明書中，「可伸縮及/或彎曲之基材」可舉出用以構成衣服等之布、樹脂製平板等可彎曲及/或伸縮之素材及紙等。但可使用本發明之樹脂組成物形成配線之基材並不限定於該等，可使用含有其他可伸縮及/或彎曲之素材的基材。又，亦可於不可伸縮及/或彎曲之基材使用本發明之樹脂組成物形成配線。 In the present specification, the "retractable and/or curved base material" may be a material for bending and/or stretching, such as a cloth for forming clothes or the like, or a resin plate. However, the substrate on which the wiring can be formed using the resin composition of the present invention is not limited thereto, and a substrate containing other stretchable and/or curved materials can be used. Further, the wiring may be formed using the resin composition of the present invention on a substrate which is not stretchable and/or bendable.
本發明之樹脂組成物中，相對於(A)導電性 粒子與(B)熱塑性聚胺甲酸乙酯樹脂之合計，(A)導電性粒子之比率(亦有簡稱為「導電性粒子之比率」之情況)為90重量%以上未達100重量%。為了降低使用本發明之樹脂組成物所形成配線由於伸長所造成之配線電阻之增加，導電性粒子之比率較佳為90重量%以上99重量%以下，更佳為90重量%以上98重量%以下，又更佳為90重量%以上95重量%以下。 In the resin composition of the present invention, the ratio of (A) conductive particles (referred to simply as "the ratio of conductive particles" to the total of (A) conductive particles and (B) thermoplastic polyurethane resin. The case) is 90% by weight or more and less than 100% by weight. In order to reduce the increase in wiring resistance due to elongation of the wiring formed by using the resin composition of the present invention, the ratio of the conductive particles is preferably 90% by weight or more and 99% by weight or less, more preferably 90% by weight or more and 98% by weight or less. More preferably, it is 90% by weight or more and 95% by weight or less.
本發明之樹脂組成物係含有導電性粒子作為(A)成分。 The resin composition of the present invention contains conductive particles as the component (A).
本發明之樹脂組成物所含之導電性粒子較佳為含有由Ag、Au、Cu、Ni及Ti所選擇之至少一種金屬。導電性粒子藉由含有特定金屬，可形成電阻低之配線。本發明之樹脂組成物所含之導電性粒子更佳為由Ag、Au、Cu、Ni及Ti所選擇之至少一種金屬所構成。尤其銀(Ag)係導電率較高。因此，導電性粒子較佳為使用Ag粒子(亦即Ag所構成之金屬粒子)。又，本說明書中「金屬A所構成之金屬粒子」並未意指排除含有無法避免地含有不純物的情形。金屬粒子以外之成分亦同。 The conductive particles contained in the resin composition of the present invention preferably contain at least one metal selected from the group consisting of Ag, Au, Cu, Ni, and Ti. The conductive particles can form a wiring having a low electrical resistance by containing a specific metal. The conductive particles contained in the resin composition of the present invention are more preferably composed of at least one metal selected from the group consisting of Ag, Au, Cu, Ni, and Ti. In particular, the silver (Ag) system has a high electrical conductivity. Therefore, it is preferable to use Ag particles (that is, metal particles composed of Ag) as the conductive particles. Further, the term "metal particles composed of metal A" in the present specification does not mean that the inclusion of impurities inevitably is excluded. The components other than metal particles are the same.
導電性粒子之粒子形狀及粒子尺寸(亦稱為粒徑或粒子徑)並無特別限定。粒子形狀例如可使用球狀及鱗片狀等者。導電性粒子之粒子尺寸可藉由全粒子累積值50%之粒子尺寸(D50)加以定義。本說明書中，D50亦稱為平均粒徑。又，平均粒徑(D50)可以microtrac法(雷射繞射散射法)進行粒度分佈測定，並由粒度分佈測定之結果而求 得。 The particle shape and particle size (also referred to as particle diameter or particle diameter) of the conductive particles are not particularly limited. For the particle shape, for example, a spherical shape or a scaly shape can be used. The particle size of the conductive particles can be defined by a particle size (D50) of 50% of the total particle cumulative value. In the present specification, D50 is also referred to as an average particle diameter. Further, the average particle diameter (D50) can be measured by a microtrac method (laser diffraction scattering method), and is obtained from the results of particle size distribution measurement.
以對於伸縮及/或彎曲之耐性及操作性之點等而言，導電性粒子之平均粒徑(D50)較佳為0.5至30μm，更佳為1至20μm，又更佳為5至15μm，特佳為5至10μm。平均粒徑(D50)大於上述範圍時，在網版印刷時會產生阻塞等問題。又，平均粒徑小於上述範圍時，燒成時粒子之燒結變得過度，無法充分形成對伸縮及/或彎曲具有耐性的配線。 The average particle diameter (D50) of the conductive particles is preferably from 0.5 to 30 μm, more preferably from 1 to 20 μm, still more preferably from 5 to 15 μm, in terms of resistance to stretching and/or bending, and the like. Particularly preferred is 5 to 10 μm. When the average particle diameter (D50) is larger than the above range, problems such as clogging may occur during screen printing. In addition, when the average particle diameter is less than the above range, the sintering of the particles at the time of firing becomes excessive, and it is not possible to sufficiently form a wiring resistant to expansion and contraction and/or bending.
又，導電性粒子之大小可表示為BET值(BET比表面積)。導電性粒子之BET值較佳為0.1至5m2/g，更佳為0.2至2m2/g，又更佳為0.5至1.5m2/g。 Further, the size of the conductive particles can be expressed as a BET value (BET specific surface area). The BET value of the conductive particles is preferably from 0.1 to 5 m 2 /g, more preferably from 0.2 to 2 m 2 /g, still more preferably from 0.5 to 1.5 m 2 /g.
本發明之樹脂組成物係含有100%模數為7MPa以上之熱塑性聚胺甲酸乙酯樹脂作為(B)成分。 The resin composition of the present invention contains 100% of a thermoplastic polyurethane resin having a modulus of 7 MPa or more as the component (B).
本說明書中，「100%模數」是指使用樹脂組成物形成特定形狀之圖案時，當圖案延伸100%時(亦即圖案長度成為2倍時)之配線拉伸應力。因此，「100%模數」係與專利文獻1(國際公開第2016/073465號)所記載達到100%伸長時之拉伸應力同義。 In the present specification, the "100% modulus" refers to a wiring tensile stress when the pattern is stretched by 100% (that is, when the pattern length is doubled) when a pattern of a specific shape is formed using a resin composition. Therefore, the "100% modulus" is synonymous with the tensile stress at 100% elongation described in Patent Document 1 (International Publication No. 2016/073465).
本發明人等發現藉由使用100%模數為7MPa以上之熱塑性聚胺甲酸乙酯樹脂，並使熱塑性聚胺甲酸乙酯樹脂與導電性粒子之比率成為特定範圍，可獲得可於可伸縮及/或彎曲之基材表面形成配線之樹脂組成物，從而完成本發明。 The present inventors have found that by using a thermoplastic polyurethane resin having a 100% modulus of 7 MPa or more and setting the ratio of the thermoplastic polyurethane resin to the conductive particles to a specific range, it is possible to obtain a stretchable and The resin composition of the wiring is formed on the surface of the curved substrate to complete the present invention.
本發明之樹脂組成物中，(B)熱塑性聚胺甲 酸乙酯樹脂較佳為由己內酯系、酯系、醚系及碳酸酯系所選擇之至少一種。藉由使用以特定種類之聚胺甲酸乙酯作為熱塑性聚胺甲酸乙酯樹脂的樹脂組成物，可在可伸縮及/或彎曲之基材表面形成斷線可能性低之配線。 In the resin composition of the present invention, the (B) thermoplastic polyurethane resin is preferably at least one selected from the group consisting of a caprolactone system, an ester system, an ether system and a carbonate system. By using a resin composition having a specific type of polyurethane as the thermoplastic polyurethane resin, it is possible to form wiring having a low possibility of disconnection on the surface of the stretchable and/or curved substrate.
在不妨礙本發明效果之範圍內，本發明之樹脂組成物可含有熱塑性樹脂、熱硬化性樹脂及/或光硬化性樹脂等其他樹脂。但為了獲得較佳之配線，樹脂組成物所含之樹脂較佳為上述熱塑性聚胺甲酸乙酯樹脂所構成之樹脂。 The resin composition of the present invention may contain other resins such as a thermoplastic resin, a thermosetting resin, and/or a photocurable resin, within a range that does not impair the effects of the present invention. However, in order to obtain a preferable wiring, the resin contained in the resin composition is preferably a resin composed of the above thermoplastic polyurethane resin.
本發明之樹脂組成物係含有溶劑作為(C)成分。 The resin composition of the present invention contains a solvent as the component (C).
本發明之樹脂組成物所含之溶劑只要為可溶解特定熱塑性聚胺甲酸乙酯樹脂之溶劑則無特別限定。本發明之樹脂組成物中，溶劑較佳為由環己酮、二甲基甲醯胺、二甲基乙醯胺及苄醇所選擇之至少一種，更佳為二甲基乙醯胺。藉由使用特定溶媒而可確實溶解特定熱塑性聚胺甲酸乙酯樹脂。其結果可容易進行用以形成配線之樹脂組成物之網版印刷等。 The solvent contained in the resin composition of the present invention is not particularly limited as long as it is a solvent capable of dissolving a specific thermoplastic polyurethane resin. In the resin composition of the present invention, the solvent is preferably at least one selected from the group consisting of cyclohexanone, dimethylformamide, dimethylacetamide and benzyl alcohol, more preferably dimethylacetamide. The specific thermoplastic polyurethane resin can be reliably dissolved by using a specific solvent. As a result, screen printing or the like for forming a resin composition of wiring can be easily performed.
相對於熱塑性聚胺甲酸乙酯樹脂100重量份，溶劑添加量為100至1000重量份，較佳為200至600重量份。通常使用熱塑性聚胺甲酸乙酯樹脂重量4倍左右重量之溶劑，藉此可適當溶解熱塑性聚胺甲酸乙酯樹脂。 The solvent is added in an amount of 100 to 1000 parts by weight, preferably 200 to 600 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane resin. A solvent having a weight of about 4 times by weight of the thermoplastic polyurethane resin is usually used, whereby the thermoplastic polyurethane resin can be appropriately dissolved.
又，為了調整樹脂組成物之黏度，可對樹脂組成物適當的另外添加溶劑。 Further, in order to adjust the viscosity of the resin composition, a solvent may be appropriately added to the resin composition.
本發明係含有上述樹脂組成物之導電性膏。 The present invention is a conductive paste containing the above resin composition.
本發明之導電性膏可為僅由上述樹脂組成物所構成之導電性膏。但在不妨礙本發明效果之範圍內或為了提高本發明之效果，本發明之導電性膏可含有上述樹脂組成物以外之成分。例如本發明之導電性膏可進一步含有由無機顏料、有機顏料、矽烷耦合劑、調平劑、搖變劑及消泡劑所成群組所選擇之至少1種。 The conductive paste of the present invention may be a conductive paste composed only of the above resin composition. However, the conductive paste of the present invention may contain components other than the above resin composition, within the scope of not impairing the effects of the present invention or in order to enhance the effects of the present invention. For example, the conductive paste of the present invention may further contain at least one selected from the group consisting of an inorganic pigment, an organic pigment, a decane coupling agent, a leveling agent, a shaker, and an antifoaming agent.
本發明之導電性膏係將上述樹脂組成物所含成分及視需要之其他成分投入行星型攪拌機、溶解器、珠磨機、擂潰機、三輥磨機、旋轉式混合機、或雙軸混合器等混合機並混合，即可製造。如此可調製適於網版印刷、浸漬、其他所需塗膜或配線形成方法之導電性膏。 In the conductive paste of the present invention, the components contained in the resin composition and other components as needed are put into a planetary mixer, a dissolver, a bead mill, a crusher, a three-roll mill, a rotary mixer, or a twin shaft. A mixer such as a mixer can be produced by mixing and mixing. Thus, a conductive paste suitable for screen printing, dipping, other desired coating films or wiring forming methods can be prepared.
本發明之導電性膏之黏度可調整為適合用於網版印刷等特定之塗膜或配線形成方法之黏度。黏度調整可藉由適當控制溶劑量而進行。 The viscosity of the conductive paste of the present invention can be adjusted to a viscosity suitable for a specific coating film or wiring forming method such as screen printing. The viscosity adjustment can be carried out by appropriately controlling the amount of the solvent.
本發明之導電性膏之黏度為100至250Pa‧sec(1rpm測定)，較佳為25至60Pa‧sec(10rpm測定)及/或5至40Pa‧sec(100rpm測定)，更佳為120至200Pa‧sec(1rpm測定)、30至50Pa‧sec(10rpm測定)及/或7至30Pa‧sec(100rpm測定)。又，黏度之「(1rpm測定)」是表示以旋轉數1rpm進行測定。 The conductive paste of the present invention has a viscosity of 100 to 250 Pa sec (measured at 1 rpm), preferably 25 to 60 Pa sec (measured at 10 rpm) and/or 5 to 40 Pa sec (measured at 100 rpm), more preferably 120 to 200 Pa. ‧ sec (1 rpm measurement), 30 to 50 Pa sec (measured at 10 rpm), and/or 7 to 30 Pa sec (measured at 100 rpm). Further, "(1 rpm measurement)" of the viscosity means that the measurement was performed at a number of revolutions of 1 rpm.
本發明之導電性膏之搖變性指數較佳為1至25(1rpm/100rpm)，更佳為2至23(1rpm/100rpm)。搖變 性指數之「(1rpm/100rpm)」是表示1rpm測定黏度測定值除以100rpm測定黏度測定值的值(1rpm之黏度與100rpm之黏度的比)。本說明書中，以使用Brookfield黏度計：B型(Brookfield公司製)在25℃測定的值表示黏度。 The conductive paste of the present invention preferably has a shake index of from 1 to 25 (1 rpm / 100 rpm), more preferably from 2 to 23 (1 rpm / 100 rpm). The "(1 rpm/100 rpm)" of the rocking property index is a value (measured as a ratio of a viscosity of 1 rpm to a viscosity of 100 rpm) at which the viscosity measurement value is measured by 1 rpm divided by 100 rpm. In the present specification, the viscosity is expressed by a value measured at 25 ° C using a Brookfield viscometer: Type B (manufactured by Brookfield).
藉由使用本發明之導電性膏而可以網版印刷等手段於可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之配線。 By using the conductive paste of the present invention, wiring of an electric circuit and/or an electronic circuit having a low possibility of disconnection can be formed on the surface of the stretchable and/or curved substrate by means of screen printing or the like.
本發明係上述導電性膏之硬化物。 The present invention is a cured product of the above conductive paste.
將本發明之導電性膏以網版印刷等手段形成為電氣電路及/或電子電路之配線形狀並加以硬化，藉此可於可伸縮及/或彎曲之基材表面形成斷線可能性低之電氣電路及/或電子電路之配線。使導電性膏硬化之溫度及時間可因應樹脂組成物所含熱塑性聚胺甲酸乙酯樹脂之種類適當選擇。使導電性膏硬化之溫度及時間可考慮基材之耐熱性而適宜調整決定。例如使導電性膏硬化之溫度及時間可為60至180℃、5至60分鐘，較佳為80至140℃、5至60分鐘，更佳為110至130℃、20至40分鐘。 The conductive paste of the present invention is formed into a wiring shape of an electric circuit and/or an electronic circuit by means of screen printing or the like and is cured, whereby the possibility of disconnection on the surface of the stretchable and/or curved substrate can be low. Wiring of electrical circuits and/or electronic circuits. The temperature and time for curing the conductive paste can be appropriately selected depending on the type of the thermoplastic polyurethane resin contained in the resin composition. The temperature and time at which the conductive paste is cured can be appropriately adjusted in consideration of the heat resistance of the substrate. For example, the temperature and time for curing the conductive paste may be 60 to 180 ° C, 5 to 60 minutes, preferably 80 to 140 ° C, 5 to 60 minutes, more preferably 110 to 130 ° C, 20 to 40 minutes.
本發明係含有上述樹脂組成物之導電性膜或導電性圖案。 The present invention relates to a conductive film or a conductive pattern containing the above resin composition.
將含有上述樹脂組成物之導電性膏以成為特定之導電性膜或導電性圖案之方式以網版印刷等方法印刷於特定基材表面，並以上述方式硬化，藉此可形成導電性膜或導電性圖案。 The conductive paste containing the resin composition is printed on a specific substrate surface by a method such as screen printing so as to be a specific conductive film or a conductive pattern, and is cured in the above manner, whereby a conductive film or a conductive film can be formed. Conductive pattern.
將本發明之導電性膜或導電性圖案形成於 可伸縮及/或彎曲之基材表面並成為電氣電路及/或電子電路之配線時，可獲得斷線可能性低之配線。 When the conductive film or the conductive pattern of the present invention is formed on the surface of the stretchable and/or curved substrate and becomes a wiring of an electric circuit and/or an electronic circuit, wiring having a low possibility of disconnection can be obtained.
本發明係含有上述本發明之導電性膏硬化物或上述本發明之導電性膜或導電性圖案之衣服。 The present invention is a garment comprising the above-described conductive paste cured product of the present invention or the above-described conductive film or conductive pattern of the present invention.
若使用本發明之樹脂組成物之導電性膏，則可於可伸縮及/或彎曲之衣服形成配線作為導電性膏硬化物、或導電性膜或導電性圖案。 When the conductive paste of the resin composition of the present invention is used, a wiring can be formed as a conductive paste cured product, or a conductive film or a conductive pattern in a stretchable and/or curved garment.
以下藉由實施例具體說明本發明，但本發明並不限定於該等。 Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto.
<導電性膏之材料及調製比例> <Material and Modulation Ratio of Conductive Paste>
表1及表2表示實施例及比較例之導電性膏之組成。又，實施例及比較例之導電性膏係由銀粒子(導電性粒子)、熱塑性聚胺甲酸乙酯樹脂及溶劑所構成之樹脂組成物。 Tables 1 and 2 show the compositions of the conductive pastes of the examples and comparative examples. Further, the conductive pastes of the examples and the comparative examples are resin compositions composed of silver particles (conductive particles), a thermoplastic polyurethane resin, and a solvent.
表3表示實施例及比較例所使用銀粒子之比表面積、敲緊(TAP)密度及平均粒徑(D50)。敲緊密度係將裝入粉體試料之容器機械性敲緊後所得之體密度。實施例及比較例所使用之銀粒子如下。 Table 3 shows the specific surface area, the tapping (TAP) density, and the average particle diameter (D50) of the silver particles used in the examples and comparative examples. The knocking degree is a bulk density obtained by mechanically kneading a container filled with a powder sample. The silver particles used in the examples and comparative examples are as follows.
銀粒子A：AA-40719(Metalor公司製)。粒子形狀為鱗片狀。 Silver particle A: AA-40719 (manufactured by Metalor Co., Ltd.). The particle shape is scaly.
銀粒子B：SF135(technic公司製)。粒子形狀為鱗片狀。 Silver particle B: SF135 (manufactured by technic). The particle shape is scaly.
表4表示實施例及比較例所使用熱塑性聚胺甲酸乙酯樹脂之100%模數。實施例及比較例所使用之熱塑性聚胺甲酸乙酯樹脂如下。 Table 4 shows the 100% modulus of the thermoplastic polyurethane resin used in the examples and comparative examples. The thermoplastic polyurethane resin used in the examples and comparative examples was as follows.
聚胺甲酸乙酯樹脂A：熱塑性胺甲酸乙酯彈性體，P-4090(大日精化工業股份有限公司製，己內酯系胺甲酸乙酯樹脂) Polyurethane resin A: Thermoplastic urethane elastomer, P-4090 (manufactured by Dairi Seiki Co., Ltd., caprolactone urethane resin)
聚胺甲酸乙酯樹脂B：熱塑性胺甲酸乙酯彈性體，P-2294(大日精化工業股份有限公司製，醚系胺甲酸乙酯樹脂) Polyurethane resin B: Thermoplastic urethane elastomer, P-2294 (manufactured by Dairi Seiki Co., Ltd., ether urethane resin)
聚胺甲酸乙酯樹脂C：DESMOCOLL 406(Covestro公司製，酯系胺甲酸乙酯樹脂) Polyurethane resin C: DESMOCOLL 406 (manufactured by Covestro, ester urethane resin)
實施例及比較例所使用之聚胺甲酸乙酯樹脂係使用溶解於聚胺甲酸乙酯樹脂重量4倍之溶劑的聚胺甲酸乙酯樹脂溶液。因此，例如實施例1之情況，使用於20重量份溶劑(N,N-二甲基乙醯胺)中溶解5重量份聚胺甲酸乙酯樹脂A之聚胺甲酸乙酯樹脂溶液。實施例1中，將聚胺甲酸乙酯樹脂溶液與銀粒子混合時，為了調整黏度再進一步追加6.5重量份之溶劑。因此，實施例1之導電性膏(樹脂組成物)所含溶劑之重量比例為26.5重量份。 The polyurethane resin used in the examples and the comparative examples was a polyurethane resin solution dissolved in a solvent having a weight four times that of the polyurethane resin. Therefore, for example, in the case of Example 1, a polyurethane resin solution in which 5 parts by weight of the polyurethane resin A is dissolved in 20 parts by weight of a solvent (N,N-dimethylacetamide) is used. In the first embodiment, when the polyurethane resin solution and the silver particles were mixed, a solvent of 6.5 parts by weight was further added in order to adjust the viscosity. Therefore, the weight ratio of the solvent contained in the conductive paste (resin composition) of Example 1 was 26.5 parts by weight.
實施例及比較例所使用之溶劑為N,N-二甲基乙醯胺(和光純藥股份有限公司製)。 The solvent used in the examples and the comparative examples was N,N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd.).
接著將上述以特定調製比例之材料以行星混合器混合，進一步以三輥磨機分散、膏化，藉此調製導電性膏。 Then, the above materials having a specific modulation ratio were mixed in a planetary mixer, and further dispersed and pasteified in a three-roll mill to prepare a conductive paste.
<黏度之測定方法> <Method for measuring viscosity>
實施例及比較例之導電性膏之黏度係使用Brookfield公司製(B型)黏度計於25℃溫度測定。對於實施例及比較例個別之樹脂組成物，黏度測定係以1rpm、10rpm及 100rpm之旋轉速度進行。搖變性指數為1rpm之黏度測定值除以100rpm之黏度測定值的值。 The viscosity of the conductive paste of the examples and the comparative examples was measured at a temperature of 25 ° C using a Brookfield (B type) viscometer. For the resin compositions of the respective examples and comparative examples, the viscosity measurement was carried out at a rotation speed of 1 rpm, 10 rpm, and 100 rpm. The viscosity index of the shear index is 1 rpm divided by the value of the viscosity measurement value of 100 rpm.
<電阻值及比電阻之測定方法> <Measurement method of resistance value and specific resistance>
於氧化鋁基板上將實施例及比較例之導電性膏(樹脂組成物)以網版印刷機印刷成寬度：1mm、長度：71mm之配線圖案，以定溫乾燥機於120℃加熱硬化30分鐘。所得配線圖案之硬化物(簡稱為「配線圖案」)之膜厚係使用東京精密股份有限公司製表面粗度形狀測定機(型號：surfcom 1500SD-2)測定。以不伸長配線圖案狀態之電阻值為「初期電阻值」。又，配線圖案之電阻值係使用TFF Keithley Instruments股份有限公司製數位萬用表(型號：2001)測定。由電阻值及配線圖案之尺寸計算比電阻。表1及表2表示實施例及比較例之初期電阻值及比電阻。 The conductive paste (resin composition) of the examples and the comparative examples was printed on a alumina substrate by a screen printing machine into a wiring pattern having a width of 1 mm and a length of 71 mm, and heat-hardened at 120 ° C for 30 minutes in a constant temperature dryer. . The film thickness of the cured product of the obtained wiring pattern (abbreviated as "wiring pattern") was measured using a surface roughness measuring machine (model: surfcom 1500SD-2) manufactured by Tokyo Seimitsu Co., Ltd. The resistance value in the state in which the wiring pattern is not elongated is the "initial resistance value". Further, the resistance value of the wiring pattern was measured using a digital multimeter (Model: 2001) manufactured by TFF Keithley Instruments Co., Ltd. The specific resistance is calculated from the resistance value and the size of the wiring pattern. Tables 1 and 2 show the initial resistance values and specific resistances of the examples and comparative examples.
接著測定將配線圖案往縱向伸長30%後之電阻值，藉由自伸長後之電阻值減去初期電阻值而計算電阻值之差(△Ω)。表1及表2表示實施例及比較例之電阻值之差(△Ω)。又，為了將配線圖案伸長而於胺甲酸乙酯片表面印刷配線圖案。藉由將胺甲酸乙酯片伸長而將配線圖案伸長至特定長度，並測定伸長後之電阻值。 Next, the resistance value after the wiring pattern was elongated by 30% in the longitudinal direction was measured, and the difference (ΔΩ) of the resistance value was calculated by subtracting the initial resistance value from the resistance value after the elongation. Tables 1 and 2 show the difference (??) between the resistance values of the examples and the comparative examples. Further, in order to extend the wiring pattern, a wiring pattern was printed on the surface of the urethane sheet. The wiring pattern was elongated to a specific length by elongating the urethane sheet, and the resistance value after elongation was measured.
<實施例及比較例之測定結果> <Measurement Results of Examples and Comparative Examples>
相對於導電性粒子及熱塑性聚胺甲酸乙酯樹脂之合計，比較例1及2之導電性膏係導電性粒子之比率為90重量%以下。比較例1及2之電阻值之差(△Ω)分別為296Ω及445Ω，隨著圖案之伸長電阻值大幅上升。又，比較例2 之導電性膏係比電阻高達41μΩ‧cm之值。 The ratio of the conductive paste-based conductive particles of Comparative Examples 1 and 2 was 90% by weight or less based on the total of the conductive particles and the thermoplastic polyurethane resin. The difference (ΔΩ) between the resistance values of Comparative Examples 1 and 2 was 296 Ω and 445 Ω, respectively, and the resistance value of the pattern greatly increased as the pattern. Further, the conductive paste of Comparative Example 2 had a specific resistance of up to 41 μΩ·cm.
比較例3及4之導電性膏中之熱塑性聚胺甲酸乙酯樹脂之100%模數為未達7MPa(3MPa)。比較例3及4之比電阻分別高達63μΩ‧cm及40μΩ‧cm之值。又，電阻值之差(△Ω)分別為128Ω及144Ω，隨著配線圖案之伸長，電阻值比較性地大幅上升。 The 100% modulus of the thermoplastic polyurethane resin in the conductive pastes of Comparative Examples 3 and 4 was less than 7 MPa (3 MPa). The specific resistances of Comparative Examples 3 and 4 were as high as 63 μΩ ‧ cm and 40 μΩ ‧ cm, respectively. Further, the difference in resistance values (ΔΩ) was 128 Ω and 144 Ω, respectively, and the resistance value relatively increased as the wiring pattern was elongated.
反之，本發明之實施例1至5之比電阻係31μΩ‧cm以下之較低值，係較比較例2至4之比電阻低。又，本發明之實施例1至5之電阻值之差(△Ω)為120Ω以下，相較於比較例1至4，電阻值上升較小。 On the other hand, the lower specific values of the specific resistance of Examples 1 to 5 of the present invention of 31 μΩ·cm or less were lower than those of Comparative Examples 2 to 4. Further, the difference (ΔΩ) between the resistance values of Examples 1 to 5 of the present invention was 120 Ω or less, and the resistance value rise was small as compared with Comparative Examples 1 to 4.
由以上明顯可知，使用本發明之實施例1至5之導電性膏時，可獲得比電阻低之配線圖案，即使將配線圖案伸長時將電阻值之增加可被抑制為較低。因此，若使用本發明之樹脂組成物，則可於可伸縮及/或彎曲之基材表面形成電阻低、斷線可能性低之電氣電路及/或電子電路之配線。 As apparent from the above, when the conductive pastes of Examples 1 to 5 of the present invention are used, a wiring pattern having a lower specific resistance can be obtained, and the increase in the resistance value can be suppressed to be low even when the wiring pattern is elongated. Therefore, when the resin composition of the present invention is used, wiring of an electric circuit and/or an electronic circuit having low electric resistance and low possibility of disconnection can be formed on the surface of the stretchable and/or curved substrate.
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| JP2016-253320 | 2016-12-27 | ||
| JP2016253320A JP6889902B2 (en) | 2016-12-27 | 2016-12-27 | Resin composition, cured product, conductive film, conductive pattern and garment |
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| US11629455B2 (en) | 2020-04-22 | 2023-04-18 | Taiwan Textile Research Institute | Conductive textile and method for fabricating the same |
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| US11932771B2 (en) | 2020-09-18 | 2024-03-19 | Namics Corporation | Stretchable conductive paste and film |
| JPWO2022153925A1 (en) | 2021-01-14 | 2022-07-21 | ||
| CN112980126B (en) * | 2021-02-22 | 2022-12-02 | 青岛科技大学 | Self-repairing stretchable electrode and preparation method and application thereof |
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| JPS6162558A (en) * | 1984-09-04 | 1986-03-31 | Muromachi Kagaku Kogyo Kk | Electroconductive resin composition |
| EP1927621B1 (en) * | 2006-12-01 | 2010-03-24 | Dow Global Technologies Inc. | Metal filled polyurethane composition and moulds prepared therefrom |
| JP5767498B2 (en) * | 2011-03-31 | 2015-08-19 | 太陽ホールディングス株式会社 | Conductive paste |
| TWI570197B (en) * | 2011-03-31 | 2017-02-11 | Taiyo Holdings Co Ltd | Conductive paste |
| CN106947409B (en) * | 2012-06-29 | 2018-12-11 | 大自达电线股份有限公司 | Conductive adhesive composition, conductive adhesive film, adhesive method and circuit base plate |
| JP6233792B2 (en) * | 2013-01-28 | 2017-11-22 | 国立大学法人群馬大学 | Conductive paste |
| JP6343903B2 (en) * | 2013-10-17 | 2018-06-20 | 東洋紡株式会社 | Conductive paste and printed circuit using the same |
| JP6592328B2 (en) * | 2014-10-30 | 2019-10-16 | 昭和電工株式会社 | Polyurethane resin, method for producing polyurethane resin, and resin composition |
| US10119045B2 (en) * | 2015-01-14 | 2018-11-06 | Toyobo Co., Ltd. | Electroconductive silver paste |
| JP6690528B2 (en) * | 2015-01-14 | 2020-04-28 | 東洋紡株式会社 | Conductive film |
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