TWI500047B - A conductive composition, a conductive film, and the like - Google Patents
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H—ELECTRICITY
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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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
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- H—ELECTRICITY
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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
Description
本發明係有關於一種以多官能吖環丙烷衍生物作為主要成膜成分之導電性組成物、導電性皮膜及該等的製造方法。The present invention relates to a conductive composition containing a polyfunctional anthracene cyclopropane derivative as a main film-forming component, a conductive film, and a method for producing the same.
作為導電性組成物，先前，例如已知有金屬填料(銅粉等)在丙烯酸樹脂系乳液等的合成樹脂系媒液中分散而成之導電性組成物，但是因為必須用大量的金屬填料，而會有導電性皮膜的透明性或與基材的黏附性不充分之情形。As a conductive composition, for example, a conductive material in which a metal filler (such as copper powder) is dispersed in a synthetic resin-based medium such as an acrylic resin emulsion is known, but since a large amount of metal filler must be used, On the other hand, there is a case where the transparency of the conductive film or the adhesion to the substrate is insufficient.
又，已知有聚(苯胺)等的導電性聚合物在合成樹脂系媒液中分散而成者(參照專利文獻1及2)，但是因為從相溶性而言，導電性聚合物的使用量受到限制，而難以得到導電性高的皮膜。又，為了確保耐溶劑性等的皮膜性能，一般認為必須另外使用多官能異氰酸酯等硬化劑。In addition, it is known that a conductive polymer such as poly(aniline) is dispersed in a synthetic resin-based medium (see Patent Documents 1 and 2), but the amount of conductive polymer used is from compatibility. It is difficult to obtain a film having high conductivity. Further, in order to secure film properties such as solvent resistance, it is generally considered that a curing agent such as a polyfunctional isocyanate must be additionally used.
作為未使用合成樹脂系媒液或硬化劑之導電性組成物，例如已知導電性聚合物分散在三羥甲基丙烷三(甲基)丙烯酸酯等紫外線聚合型化合物中而成者(參照專利文獻3及4)。但是將該導電性組成物塗布在塑膠薄膜時，會有因導電性皮膜的硬化收縮致使薄膜產生翹曲或卷曲等之問題。As a conductive composition which does not use a synthetic resin-based medium or a curing agent, for example, it is known that a conductive polymer is dispersed in an ultraviolet-polymerizable compound such as trimethylolpropane tri(meth)acrylate (see Patent) Documents 3 and 4). However, when the conductive composition is applied to a plastic film, there is a problem that the film is warped or curled due to curing shrinkage of the conductive film.
[專利文獻1] 日本專利特開2001-55541號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-55541
[專利文獻2] 日本專利特開2003-321604號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-321604
[專利文獻3] 日本專利特開平6-162818號公報[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-126818
[專利文獻4] 日本專利特開2007-190716號公報[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-190716
本發明之課題係提供一種導電性組成物，該導電性組成物未使用合成樹脂系媒液或硬化劑、紫外線硬化型多官能化合物，而能夠形成平滑性、耐溶劑性、耐水性、與各種基材(金屬、玻璃、特別是塑膠薄膜)的黏附性、透明性等性能(以下總稱為皮膜性能)優良之導電性皮膜。An object of the present invention is to provide a conductive composition which can form smoothness, solvent resistance, water resistance, and various types without using a synthetic resin-based medium, a curing agent, or an ultraviolet curable polyfunctional compound. A conductive film having excellent properties such as adhesion, transparency, and the like (hereinafter collectively referred to as film properties) of a substrate (metal, glass, and particularly a plastic film).
本發明者發現藉由以下的導電性組成物時，能夠解決前述課題。The present inventors have found that the above problems can be solved by the following conductive composition.
亦即，本發明係有關於一種導電性組成物，其特徵係含有：在分子內至少具有3個特定結構的吖環丙烷基的多官能吖環丙烷衍生物(A)(以下稱為(A)成分)；吖環丙烷基開環觸媒(B)(以下稱為(B)成分)；含雜原子的π共軛系導電性聚合物(C)(以下稱為(C)成分)；及溶劑(D)(以下稱為(D)成分)，並且關於一種導電性皮膜，其係由該導電性組成物硬化而成，以及關於一種導電性皮膜的製造方法，其係將該導電性組成物塗布在基材上並使其硬化。That is, the present invention relates to an electroconductive composition characterized by comprising a polyfunctional anthracene cyclopropane derivative (A) having at least three specific structures of an indole cyclopropyl group in the molecule (hereinafter referred to as (A) a component)) a cyclopropane-based ring-opening catalyst (B) (hereinafter referred to as a component (B)); a hetero atom-containing π-conjugated conductive polymer (C) (hereinafter referred to as a component (C)); And a solvent (D) (hereinafter referred to as a component (D)), and a conductive film obtained by curing the conductive composition, and a method for producing a conductive film, which is the conductivity The composition is coated on the substrate and allowed to harden.
依照本發明的導電性組成物，能夠形成一種導電性皮膜，其具有廣闊範圍的導電性、皮膜性能優良且不會硬化收縮。因此，該導電性皮膜能夠提供於：製版用薄膜或包裝用薄膜、光學零件用薄膜、顯示器用保護薄膜、半導體加工膠黏帶用薄膜、熱衝壓用薄膜、塑膠成型裝飾薄膜、透明電極、電磁波屏蔽、電路成形材料等廣闊範圍的用途。According to the conductive composition of the present invention, it is possible to form a conductive film which has a wide range of conductivity, excellent film properties, and does not harden and shrink. Therefore, the conductive film can be provided for: a plate for film making or a film for packaging, a film for optical parts, a protective film for a display, a film for a semiconductor processed adhesive tape, a film for hot stamping, a plastic molded decorative film, a transparent electrode, and an electromagnetic wave. Wide range of applications such as shielding and circuit forming materials.
(A)成分係在(C)成分及(D)成分的存在下，藉由(B)成分的作用而自聚合(聚合物化)之成膜成分。作為(A)成分，係只要是在分子內具有至少3個下述結構的吖環丙烷基之多官能吖環丙烷衍生物時，則能夠使用各種眾所周知之物(例如美國專利第4382135號、日本專利特開2003-104970號、日本專利特開2009-256623號等)，The component (A) is a film-forming component which is self-polymerized (polymerized) by the action of the component (B) in the presence of the component (C) and the component (D). As the component (A), any polyfunctional anthracene cyclopropane derivative having at least three indole cyclopropyl groups having the following structure in the molecule can be used (for example, U.S. Patent No. 4382135, Japan) Patent Laid-Open No. 2003-104970, Japanese Patent Laid-Open No. 2009-256623, etc.)
(式中，R1 及R2 係各自表示氫或碳數1～6的烷基)。(wherein R 1 and R 2 each represent hydrogen or an alkyl group having 1 to 6 carbon atoms).
考慮導電性皮膜的耐溶劑性等，作為(A)成分，以3官能吖環丙烷化合物及/或4官能吖環丙烷化合物為特佳。The solvent resistance of the conductive film or the like is considered, and as the component (A), a trifunctional anthracene cyclopropane compound and/or a tetrafunctional anthracene cyclopropane compound are particularly preferable.
從容易取得的觀點而言，作為3官能吖環丙烷化合物，以下述通式(1)所示者為佳，From the viewpoint of being easily available, the trifunctional anthracene cyclopropane compound is preferably represented by the following formula (1).
(式(1)中，X係表示氫、碳數1～6的烷基、或碳數1～3的烷醇基。又，R1 及R2 係各自表示氫或碳數1～6的烷基。R3 係表示氫或甲基)。(In the formula (1), X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylol group having 1 to 3 carbon atoms. Further, R 1 and R 2 each represent hydrogen or a carbon number of 1 to 6. Alkyl. R 3 represents hydrogen or methyl).
具體上，可舉出：甘油-參(1-吖環丙烷基丙酸酯)、甘油-參[2-丙基-(1-吖環丙烷基)]丙酸酯、甘油-參[2,3-二甲基-(1-吖環丙烷基)]丙酸酯、三羥甲基丙烷-參(1-吖環丙烷基丙酸酯)、三羥甲基丙烷-參[2-己基-(1-吖環丙烷基)]丙酸酯、三羥甲基丙烷-參[2,3-二己基-(1-吖環丙烷基)]丙酸酯、四羥甲基甲烷-參(1-吖環丙烷基丙酸酯)、四羥甲基甲烷-參[2-己基-(1-吖環丙烷基)]丙酸酯、四羥甲基甲烷-參[2,3-二己基-(1-吖環丙烷基)]丙酸酯等。Specific examples include glycerol-gin (1-indolecyclopropanepropionate), glycerol-gin[2-propyl-(1-indolyl)propionate, and glycerol-parameter [2, 3-dimethyl-(1-indolyl)propionate, trimethylolpropane-gin (1-indolecyclopropanepropionate), trimethylolpropane-gin[2-hexyl- (1-indolecyclopropane)]propionate, trimethylolpropane-gin[2,3-dihexyl-(1-indolyl)propionate, tetramethylolethane-parameter (1 - anthracycline propionate), tetramethylolmethane-parade [2-hexyl-(1-indolyl)propionate, tetramethylolmethane-parade [2,3-dihexyl- (1-indolecyclopropane)]propionate and the like.
作為4官能吖環丙烷化合物，例如以下述通式(2)所示者為佳，The tetrafunctional anthracene cyclopropane compound is preferably, for example, represented by the following formula (2).
(式(2)中，R1 及R2 係各自表示氫或碳數1～6的烷基。又，R3 係表示氫或甲基)。(In the formula (2), R 1 and R 2 each represent hydrogen or an alkyl group having 1 to 6 carbon atoms. Further, R 3 represents hydrogen or a methyl group).
作為式(2)所示的化合物，可舉出例如：新戊四醇-四(1-吖環丙烷基丙酸酯)、新戊四醇-四[2-己基-(1-吖環丙烷基)]丙酸酯、新戊四醇-四[2,3-二己基-(1-吖環丙烷基)]丙酸酯)等。The compound represented by the formula (2) may, for example, be neopentyl alcohol-tetrakis(1-indolylcyclopropanepropionate) or neopentyl alcohol-tetrakis[2-hexyl-(1-anthracycline). Base)] propionate, neopentyl alcohol-tetrakis[2,3-dihexyl-(1-indolyl)propionate), and the like.
作為其他的(A)成分，可舉出：四吖環丙烷基間二甲苯二胺、四吖環丙烷基甲基對二甲苯二胺等其他4官能吖環丙烷化合物等、或前述日本專利特開2003-104970號所記載之6官能吖環丙烷化合物等。Examples of the other component (A) include tetradecylcyclopropane m-xylylenediamine, tetradecylcyclopropylmethyl-p-xylylenediamine, and the like, and other tetrafunctional anthracene cyclopropane compounds, or the aforementioned Japanese Patent. The 6-functional anthracycline compound described in 2003-104970 is opened.
又，按照必要亦可並用2-甲基吖環丙烷、2-乙基吖環丙烷、2-苯基吖環丙烷等單官能吖環丙烷類及新戊二醇二(β-吖環丙烷基丙酸酯)等2官能吖環丙烷化合物。Further, if necessary, a monofunctional anthracene cyclopropane such as 2-methyl anthracycline, 2-ethylcyclocyclopropane or 2-phenylanthracene or a neopentyl glycol bis(β-fluorenylcyclopropane group) may be used in combination. A 2-functional indole cyclopropane compound such as propionate).
(B)成分係促進(A)成分的吖環丙烷基的開環反應之化合物。具體上，可舉出二芳基碘鎓鹽、三芳基鋶鹽、二芳基鋶鹽等酸產生劑；對甲苯磺酸、鹽酸、溴酸、碘酸、硫酸、磷酸及該等的中和鹽等的非氟系酸觸媒；氟磺酸、三氟甲磺酸及該等的中和鹽等的氟系酸觸媒等。因為兼具使導電性皮膜的導電性提升之功能，以具有氟系酸觸媒為佳。The component (B) is a compound which promotes a ring-opening reaction of an indole cyclopropyl group of the component (A). Specific examples thereof include acid generators such as a diaryliodonium salt, a triarylsulfonium salt, and a diarylsulfonium salt; p-toluenesulfonic acid, hydrochloric acid, bromic acid, iodic acid, sulfuric acid, phosphoric acid, and the like. A non-fluorine-based acid catalyst such as a salt; a fluorine-based acid catalyst such as fluorosulfonic acid, trifluoromethanesulfonic acid or such a neutralized salt. It is preferable to have a fluorine-based acid catalyst because it has a function of improving the conductivity of the conductive film.
作為(B)成分，就導電性組成物的儲存安定性(使用期限(pot life))或處理性等而言，以前述非氟系酸觸媒及/或氟系酸觸媒、特別是對甲苯磺酸中和鹽及/或三氟甲磺酸中和鹽為佳。又，考慮導電性皮膜的導電性提升效果時，以單獨使用後者或並用兩者為佳。As the component (B), the non-fluorinated acid catalyst and/or the fluorine-based acid catalyst, especially the pair, are used for the storage stability (pot life) or handleability of the conductive composition. The toluenesulfonic acid neutralizing salt and/or the trifluoromethanesulfonic acid neutralizing salt is preferred. Moreover, in consideration of the effect of improving the conductivity of the conductive film, it is preferred to use the latter alone or in combination.
作為用以形成前述中和鹽之化合物(以下稱為鹼性化合物)，可舉出：氨；單甲胺、單乙胺、單丁胺、環己胺等一級胺類；二甲胺、二乙胺等二級胺類；三乙胺等三級胺類；苯胺、芳基胺、烷醇胺等其他胺類；氫氧化鈉、氫氧化鉀等鹼金屬化合物；氫氧化鎂等鹼土類金屬化合物等。其中，就使用期限(pot life)或導電性皮膜的耐溶劑性等而言，以前述氨及/或三級胺類(特別是三甲胺、三乙胺)為佳。Examples of the compound for forming the neutralized salt (hereinafter referred to as a basic compound) include ammonia; primary amines such as monomethylamine, monoethylamine, monobutylamine, and cyclohexylamine; dimethylamine and Secondary amines such as ethylamine; tertiary amines such as triethylamine; other amines such as aniline, arylamine, and alkanolamine; alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metals such as magnesium hydroxide Compounds, etc. Among them, the above-mentioned ammonia and/or tertiary amines (especially trimethylamine or triethylamine) are preferred in terms of pot life or solvent resistance of the conductive film.
作為(C)成分，只要是含雜原子的π共軛系導電性聚合物時，能夠使用各種眾所周知之物。「雜原子」係指氫及碳以外的原子(例如氮原子或硫原子等)。又，「含雜原子的π共軛系導電性聚合物」係指在分子內具有該雜原子，且分子主鏈係構成π共軛結構之有機高分子化合物。(C)成分係呈被各種摻雜劑摻雜之狀態。通常，(C)成分係作為不揮發分濃度為0.1～10重量%左右的水溶液而使用。As the component (C), any well-known thing can be used as long as it is a hetero atom-containing π-conjugated conductive polymer. "Hetero atom" means an atom other than hydrogen and carbon (for example, a nitrogen atom or a sulfur atom). In addition, the "heteroatom-containing π-conjugated conductive polymer" means an organic polymer compound having such a hetero atom in a molecule and a molecular main chain constituting a π-conjugated structure. The component (C) is in a state of being doped with various dopants. Usually, the component (C) is used as an aqueous solution having a nonvolatile content of about 0.1 to 10% by weight.
(C)成分的具體例可舉出例如：聚(噻吩)類、聚(噻吩伸乙烯基)類、聚(吡咯)類、聚(呋喃類)等雜環π共軛系導電性聚合物；或聚(苯胺類)等芳香環π共軛系導電性聚合物。又，在該雜環或芳香環，烷基、烷氧基、伸烷二氧基可以枝狀或環狀地鍵結。Specific examples of the component (C) include heterocyclic π-conjugated conductive polymers such as poly(thiophene), poly(thiophene vinyl), poly(pyrrole), and poly(furan); Or an aromatic ring π-conjugated conductive polymer such as poly(aniline). Further, in the heterocyclic ring or the aromatic ring, an alkyl group, an alkoxy group or an alkylenedioxy group may be bonded in a dendritic or cyclic manner.
作為聚(噻吩)類，可舉出：聚(噻吩)、聚(3-甲基噻吩)、聚(3-丁基噻吩)、聚(3-癸基噻吩)、聚(3,4-二甲基噻吩)、聚(3,4-二丁基噻吩)、聚(3-甲氧基噻吩)、聚(3-丁氧基噻吩)、聚(3-己氧基噻吩)、聚(3-庚氧基噻吩)、聚(3-辛氧基噻吩)、聚(3,4-二甲氧基噻吩)、聚(3,4-二乙氧基噻吩)、聚(3,4-乙烯二氧基噻吩)、聚(3,4-丙烯二氧基噻吩)、聚(3,4-丁烯二氧基噻吩)等。又，關於聚(噻吩伸乙烯基)、聚(吡咯)類、聚(呋喃)類，亦可舉出同樣的具體種。Examples of the poly(thiophene) include poly(thiophene), poly(3-methylthiophene), poly(3-butylthiophene), poly(3-mercaptothiophene), and poly(3,4-di). Methylthiophene), poly(3,4-dibutylthiophene), poly(3-methoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3) -heptyloxythiophene), poly(3-octyloxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-ethylene) Dioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene), and the like. Further, the same specific species may be mentioned for poly(thiophene vinyl), poly(pyrrole), and poly(furan).
作為聚(苯胺)類，可舉出：聚(苯胺)、聚(2-甲基苯胺)、聚(3-異丁基苯胺)、聚(2-苯胺磺酸)、聚(3-苯胺磺酸)等。Examples of the poly(aniline)s include poly(aniline), poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonate). Acid) and so on.
摻雜劑可舉出：HF、HCl、H2 SO4 等路易斯酸；Cl- 、Br- 、磺酸基陰離子(sulfoanion)等電解質陰離子；聚苯乙烯磺酸、聚乙烯基磺酸、聚丙烯酸丁基磺酸、聚甲基丙烯酸羧酸及該等的中和鹽等陰離子性聚合物等。Examples of the dopant include Lewis acids such as HF, HCl, and H 2 SO 4 ; electrolyte anions such as Cl − , Br − , and sulfoanion; polystyrenesulfonic acid, polyvinylsulfonic acid, and polyacrylic acid; An anionic polymer such as butylsulfonic acid, polymethacrylic acid carboxylic acid or such a neutralized salt.
從皮膜的帶電防止性(抗靜電性)或透明性等觀點而言，作為(C)成分，以聚(噻吩)類及/或聚(苯胺)類為佳。又，作為聚(噻吩)類，以使用前述陰離子性聚合物摻合而成之伸烷基二氧基聚(噻吩)為佳，以使用前述聚苯乙烯磺酸(鹽)摻合而成之聚(3,4-伸乙二氧基噻吩)(以下稱為PEDOT/PSS)為特佳。From the viewpoints of charge prevention (antistatic property) of the film, transparency, and the like, as the component (C), poly(thiophene) and/or poly(aniline) are preferred. Further, as the poly(thiophene), an alkylenedioxy poly(thiophene) obtained by blending the above anionic polymer is preferably used, and the polystyrenesulfonic acid (salt) is blended. Poly(3,4-extended ethylenedioxythiophene) (hereinafter referred to as PEDOT/PSS) is particularly preferred.
作為(D)成分，可舉出例如：水；甲醇、乙醇、正丙醇、異丙醇、丁醇、乙二醇、二伸乙甘醇、乙二醇一乙基醚、乙二醇一丙基醚等醇類；丙酮、甲基乙基酮等低級酮類；甲苯、苯等芳香族烴類；乙酸乙酯、氯仿、二甲基甲醯胺、二甲基亞碸、N-甲基吡咯啶酮等。該等之中，就使用期限而言，以水及/或碳數為1～4左右的醇類(特別是甲醇、乙醇、異丙醇、乙二醇)為佳。又，(D)成分亦可以是來自前述(A)成分～(C)成分者。Examples of the component (D) include water; methanol, ethanol, n-propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol. Alcohols such as propyl ether; lower ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and benzene; ethyl acetate, chloroform, dimethylformamide, dimethyl hydrazine, N-methyl Pyrrolidone and the like. Among these, an alcohol (especially methanol, ethanol, isopropanol, or ethylene glycol) having a water content and/or a carbon number of about 1 to 4 is preferred in terms of the duration of use. Further, the component (D) may be derived from the components (A) to (C) described above.
在本發明的導電性組成物，亦可按照必要，含有(C)成分以外的聚合物(聚(乙炔)類、聚(伸苯基)類、聚(伸苯伸乙烯基)類、聚(并苯)類等)或消泡劑、防滑劑、防腐劑、防鏽劑、pH調整劑、抗氧化劑、顏料、染料、滑劑。又，並未含有作為成膜成分的合成樹脂系媒液(丙烯酸樹脂乳液、含羧酸鹽陰離子基的丙烯酸樹脂、聚胺基甲酸酯樹脂、環氧樹脂等)。In the conductive composition of the present invention, a polymer other than the component (C) (poly(acetylene), poly(phenylene), poly(phenylene)), poly( Acetylenes, etc.) or defoamers, anti-slip agents, preservatives, rust inhibitors, pH adjusters, antioxidants, pigments, dyes, lubricants. Further, the synthetic resin-based vehicle (acrylic resin emulsion, carboxylate anion-based acrylic resin, polyurethane resin, epoxy resin, etc.) as a film-forming component is not contained.
在本發明的導電性組成物之各成分的含量係沒有特別限定，通常，考慮皮膜性能之平衡時，係如下。The content of each component of the conductive composition of the present invention is not particularly limited, and in general, when the balance of the film properties is considered, it is as follows.
(A)成分：0.1～20重量%左右，以0.5～7.5重量%為佳(A) component: about 0.1 to 20% by weight, preferably 0.5 to 7.5% by weight
(B)成分：0.01～3重量%左右，以0.05～0.5重量%為佳(B) component: about 0.01 to 3% by weight, preferably 0.05 to 0.5% by weight
(C)成分：0.05～5重量%左右，以0.1～2重量%為佳(C) component: about 0.05 to 5% by weight, preferably 0.1 to 2% by weight
(D)成分：72～99.84重量%左右，以90～99.35重量%為佳(D) component: about 72 to 99.84% by weight, preferably 90 to 99.35 wt%
又，鹼性化合物係通常以能夠使導電性組成物的pH為4～12左右的量來使用為佳。Further, the basic compound is usually used in an amount such that the pH of the conductive composition is about 4 to 12.
本發明的導電性組成物係藉由眾所周知的方式來混合前述(A)成分～(D)成分而得到。考慮(A)成分係自聚合性時，以混合：含有(A)成分及(D)成分的組成物、與含有(B)成分、(C)成分及(D)成分的組成物為佳。The conductive composition of the present invention is obtained by mixing the components (A) to (D) described above in a well-known manner. When the component (A) is self-polymerizable, it is preferred to mix: a composition containing the components (A) and (D), and a composition containing the component (B), the component (C), and the component (D).
本發明的導電性組成物之黏度係通常為1～50mPa‧s/秒(25℃、不揮發分為2%)左右。The viscosity of the conductive composition of the present invention is usually about 1 to 50 mPa·s/sec (25 ° C, nonvolatile content: 2%).
本發明的導電性皮膜能夠藉由在基材上塗布導電性組成物並使其硬化來得到。The conductive film of the present invention can be obtained by applying a conductive composition to a substrate and curing it.
作為基材，可舉出：鐵、銅、鋁、不鏽鋼、鉑、金等金屬基材；聚對酞酸乙二酯、聚碳酸酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚酯、聚烯烴、耐綸、環氧樹脂、三聚氰胺樹脂、三乙醯基纖維素樹脂、ABS樹脂、AS樹脂、降烯系樹脂等塑膠基材；玻璃等無機基材。又，塑膠基材亦可經表面處理(電暈放電處理等)。Examples of the substrate include metal substrates such as iron, copper, aluminum, stainless steel, platinum, and gold; polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, and polyester. Polyolefin, nylon, epoxy resin, melamine resin, triethylene glycol cellulose resin, ABS resin, AS resin, drop A plastic substrate such as an olefin resin or an inorganic substrate such as glass. Moreover, the plastic substrate can also be surface treated (corona discharge treatment, etc.).
塗布方法沒有特別限定，能夠使用各種眾所周知的方法。具體上，可舉出例如：輥塗布器、逆輥塗布器、凹版塗布器、刮刀塗布器、棒塗布器、旋轉塗布器、噴墨方式、噴霧塗布方式、直接浸漬方式等。The coating method is not particularly limited, and various well-known methods can be used. Specific examples thereof include a roll coater, a reverse roll coater, a gravure coater, a knife coater, a bar coater, a spin coater, an inkjet method, a spray coating method, and a direct dipping method.
導電性皮膜的硬化條件沒有特別限定，例如，厚度為0.01～10微米左右，黏附量為0.01～10克/平方公尺左右的導電性皮膜時，考慮到生產性，硬化條件通常為在80～140℃左右、數秒～1分鐘左右。The curing condition of the conductive film is not particularly limited. For example, when the thickness is about 0.01 to 10 μm and the amount of adhesion is about 0.01 to 10 g/m 2 , the curing condition is usually 80 to 80 in consideration of productivity. About 140 ° C, a few seconds ~ 1 minute or so.
導電性皮膜係按照(C)成分的含量而顯示廣闊範圍的導電性。亦即，(C)成分少的情況亦顯示帶電防止性。表面電阻值(Ω/□)係通常為102 ～1011 左右，以102 ～104 的範圍為佳。The conductive film system exhibits a wide range of conductivity in accordance with the content of the component (C). In other words, when the component (C) is small, the charge prevention property is also exhibited. The surface resistance value (Ω/□) is usually about 10 2 to 10 11 , preferably in the range of 10 2 to 10 4 .
[實施例][Examples]
以下，透過製造例、實施例及比較例來更詳細地說明本發明，但是本發明未限定於該等實施例。又，實施例中「%」、「份」係以重量份作為基準。Hereinafter, the present invention will be described in more detail by way of Production Examples, Examples and Comparative Examples, but the present invention is not limited to the Examples. In the examples, "%" and "parts" are based on parts by weight.
添加43份PEDOT/PSS的水溶液(不揮發分為0.52重量%)、46.3份離子交換水、0.1份對甲苯磺酸及0.6份三乙胺，並充分地混合。隨後，在所得到的水溶液中混合10份(不揮發分為1.4重量%)四羥甲基甲烷-參(1-吖環丙烷基丙酸酯)的異丙醇溶液，來製備導電性組成物1。該組成物1的原料種類及各自的重量%係如表1所示。(D)成分的值係來自(A)成分及(C)成分者與另外添加者之合計值。43 parts of an aqueous solution of PEDOT/PSS (nonvolatile fraction: 0.52% by weight), 46.3 parts of ion-exchanged water, 0.1 part of p-toluenesulfonic acid and 0.6 parts of triethylamine were added and thoroughly mixed. Subsequently, 10 parts (nonvolatile content: 1.4% by weight) of tetramethylolethane-paraxan (1-anthracyclopropanylpropionate) in an isopropanol solution was mixed in the obtained aqueous solution to prepare a conductive composition. 1. The types of raw materials and the respective weight % of the composition 1 are shown in Table 1. The value of the component (D) is the total value derived from the component (A) and the component (C) and the other additive.
除了將原料種類及重量%如表1所示般變更以外，與實施例1同樣地進行，來製備導電性組成物2~13及比較用的導電性組成物(I)~(II)。The conductive compositions 2 to 13 and the comparative conductive compositions (I) to (II) were prepared in the same manner as in Example 1 except that the types and weight % of the raw materials were changed as shown in Table 1.
表1中，各記號的意思如下。In Table 1, the meaning of each symbol is as follows.
TMMTAP：四羥甲基甲烷-參(1-吖環丙烷基丙酸酯)(商品名「TAZO」、相互藥工(股)製)TMMTAP: tetramethylolethane-sodium (1-anthracycline propionate) (trade name "TAZO", mutual pharmaceutical (manufactured by the company))
TMPTAP：三羥甲基丙烷-參(1-吖環丙烷基丙酸酯)(商品名「TAZM」、相互藥工(股)製)TMPTAP: trimethylolpropane-gin (1-indolecyclopropane propionate) (trade name "TAZM", mutual pharmaceutical (manufactured by the company))
PTS：對甲苯磺酸PTS: p-toluenesulfonic acid
TFMS：三氟甲磺酸TFMS: Trifluoromethanesulfonic acid
PEDOT/PSS：使用聚苯乙烯磺酸鹽摻雜而成之聚(3,4-乙烯二氧基噻吩)(商品名「CLEVIOS P」、Starck公司製)PEDOT/PSS: poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonate (trade name "CLEVIOS P", manufactured by Starck)
PANI：聚苯胺(商品名「ORMECON D1031W」、日產化學工業公司製)的水溶液(不揮發分為2%)PANI: An aqueous solution of polyaniline (trade name "ORMECON D1031W", manufactured by Nissan Chemical Industries Co., Ltd.) (nonvolatile content: 2%)
TEA：三乙胺TEA: Triethylamine
藉由使用棒塗布器No.10，將導電性組成物1塗刷在PET薄膜(38微米)上，並於100℃乾燥1分鐘，來製造具有導電性皮膜(0.4微米)的試驗用薄膜。對其他的導電性組成物亦藉由同樣的方法來製造試驗用薄膜。又，在各試驗薄膜中並無翹曲或卷曲。The conductive composition 1 was applied onto a PET film (38 μm) by using a bar coater No. 10, and dried at 100 ° C for 1 minute to produce a test film having a conductive film (0.4 μm). The test film was also produced by the same method for other conductive compositions. Further, there was no warpage or curl in each of the test films.
使用以下所示之市售的電阻率測定機來測定實施例1之試驗用薄膜的塗刷面之表面電阻率(Ω/□)。對其他的試驗用薄膜亦藉由同樣地進行測定。結果係如表2所示。The surface resistivity (Ω/□) of the coated surface of the test film of Example 1 was measured using a commercially available resistivity measuring machine shown below. The other test films were also measured in the same manner. The results are shown in Table 2.
表面電阻率為小於106 ‧‧‧製品名「ROLESTAR-EP」、DIA Instruments(股)製Surface resistivity is less than 10 6 ‧‧‧Product name "ROLESTAR-EP", DIA Instruments (share) system
表面電阻率為106 以上‧‧‧製品名「URTRAMEGOHM METER SM-8210、SME-8311」、東亞電波工業(股)製The surface resistivity is 10 6 or more. ‧‧‧Product name "URTRAMEGOHM METER SM-8210, SME-8311", East Asia Radio Industry Co., Ltd.
使用浸漬丙酮後的棉棒摩擦實施例1之試驗用薄膜的塗刷面。如表2，顯示至皮膜消失為止之次數。次數越多係表示耐溶劑性越優良。The coated surface of the test film of Example 1 was rubbed with a cotton swab impregnated with acetone. As shown in Table 2, the number of times until the film disappeared is shown. The more the number of times, the more excellent the solvent resistance.
使用浸漬水後的棉棒摩擦實施例1之試驗用薄膜的塗刷面。如表2，顯示至皮膜消失為止之次數。次數越多係表示耐水性越優良。The coated surface of the test film of Example 1 was rubbed with a cotton swab impregnated with water. As shown in Table 2, the number of times until the film disappeared is shown. The more the number of times, the more excellent the water resistance.
在實施例1之試驗用薄膜的皮膜面，壓黏上黏著膠帶(寬度為24毫米)後，將其強勁地拉取剝離，並依照以下基準目視評價殘留導電性皮膜的量。On the film surface of the test film of Example 1, after pressure-adhesive tape (having a width of 24 mm), the tape was strongly pulled and peeled off, and the amount of the residual conductive film was visually evaluated in accordance with the following criteria.
○‧‧‧殘留70%以上。○‧‧‧Residual 70% or more.
△‧‧‧殘留40%以上、小於70%。△‧‧‧ Residual 40% or more and less than 70%.
×‧‧‧殘留小於40%。×‧‧‧ Residues are less than 40%.
對各試驗用薄膜，以塗布於PET薄膜(霧度：3.0、總光線透射率：87.5)的狀態，使用村上色彩技術研究所製之霧度計(HM-150)來測定導電性皮膜的霧度值及總光線透射率。The film for each test was applied to a PET film (haze: 3.0, total light transmittance: 87.5), and a haze meter (HM-150) manufactured by Murakami Color Research Laboratory was used to measure the fog of the conductive film. Degree and total light transmittance.
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