TWI556261B - A conductive resin composition, a conductive resin cured product, and a pattern conductor circuit - Google Patents
A conductive resin composition, a conductive resin cured product, and a pattern conductor circuit Download PDFInfo
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本發明係關於導電性樹脂組成物、導電性樹 脂硬化物及圖型導體電路，詳細而言係關於一種可取耐磨耗性優異之硬化物之導電性樹脂組成物、使其硬化而得之導電性樹脂硬化物及使用該硬化物之圖型導體電路。 The present invention relates to a conductive resin composition and a conductive tree The grease-cured material and the pattern-type conductor circuit are, in particular, a conductive resin composition of a cured product excellent in abrasion resistance, a cured conductive resin obtained by hardening, and a pattern using the cured product. Conductor circuit.
作為網板印刷於印刷配線基板上而形成圖型 導體電路所使用之導電性樹脂組成物，以往係使用對由熱硬化性樹脂或熱可塑性樹脂所構成之黏合劑樹脂，配合‧分散有銀或銅等之金屬粉，或碳黑、石墨之碳導電粉者。 對導電性樹脂組成物要求要有導電性、印刷性、密著性、焊劑耐熱性、高溫耐熱性、耐濕性、耐熱衝擊性、耐磨耗性等之特性，故為了滿足此等要求之特性，而有提案出各種樹脂成分、導電粉。 Forming a screen as a screen printed on a printed wiring board In the conductive resin composition used for the conductor circuit, a binder resin composed of a thermosetting resin or a thermoplastic resin is used in the past, and a metal powder such as silver or copper or a carbon black or graphite carbon is dispersed. Conductive powder. The conductive resin composition is required to have characteristics such as conductivity, printability, adhesion, solder heat resistance, high temperature heat resistance, moisture resistance, thermal shock resistance, abrasion resistance, etc., so in order to satisfy these requirements Characteristics, and various resin components and conductive powders have been proposed.
作為黏合劑利用之熱硬化性樹脂，例如周知 有甲階酚醛型酚樹脂。甲階酚醛型酚樹脂之耐熱性優良，又，使用於導電性樹脂組成物時，期望因自我縮合所致之體積收縮之結果，所配合之導電粉彼此之接觸面積增大， 電阻值降低而使導電性變得良好。並且，較為低價之同時，除耐熱性以外，接著性、機械特性、電特性等亦優，不僅可作為黏合劑，亦可廣泛使用作為各種基材之成型材料或接著劑、塗覆劑。專利文獻1中揭示使用包含甲階酚醛型酚樹脂之樹脂組成物作為導電性樹脂組成物之黏合劑樹脂。 A thermosetting resin used as a binder, for example, well-known There is a resol type phenol resin. The resol type phenol resin is excellent in heat resistance, and when used in a conductive resin composition, it is desired that the contact area of the electrically conductive powders to be combined increases as a result of volume shrinkage due to self-condensation. The resistance value is lowered to make the conductivity good. In addition to heat resistance, it is excellent in adhesiveness, mechanical properties, electrical properties, and the like, and can be used not only as a binder but also as a molding material, an adhesive, and a coating agent for various substrates. Patent Document 1 discloses a binder resin using a resin composition containing a resol type phenol resin as a conductive resin composition.
導電性樹脂組成物所要求之特性之中，亦以 耐磨耗性，例如於滑動開關等之滑動用途等使用導電性樹脂組成物之情況時特別重要之特性，故自以往即要求提升該特性。作為使耐磨耗性提升之導電性樹脂組成物，例如，上述專利文獻1中揭示含有由甲階酚醛型酚樹脂及二氰二胺所構成之黏合劑樹脂組成物之導電性樹脂組成物。 又，專利文獻2中揭示含有具有一定以上之硬度與特定之長軸長度短軸長度之氧化鐵等之非導電性粉末之導電性樹脂組成物，專利文獻3中揭示以特定比例含有硼矽酸鋅系玻璃、硼矽酸鉛系玻璃及氧化鉍之導電性樹脂組成物。 Among the characteristics required for the conductive resin composition, The wear resistance is particularly important when a conductive resin composition is used for sliding applications such as a slide switch, and the like, it is required to improve the characteristics from the past. As a conductive resin composition which improves the abrasion resistance, for example, Patent Document 1 discloses a conductive resin composition containing a binder resin composition composed of a resol type phenol resin and dicyandiamide. Further, Patent Document 2 discloses a conductive resin composition containing a non-conductive powder such as iron oxide having a certain hardness and a short axis length of a specific major axis length, and Patent Document 3 discloses that boric acid is contained in a specific ratio. A conductive resin composition of zinc-based glass, lead borosilicate glass, and cerium oxide.
〔先行技術文獻〕 [prior technical literature]
〔專利文獻〕 [Patent Document]
〔專利文獻1〕日本特開平5-194822號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 5-194822
〔專利文獻2〕日本特開2000-67646號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-67646
〔專利文獻3〕日本特開2001-6434號公報 [Patent Document 3] JP-A-2001-6434
近年來伴隨電子機器之輕薄短小化，而對導 電性樹脂組成物要求高耐磨耗性。例如在膜片開關等之導電用途中，每次切換開關即會相互解觸之接點部所使用之導電性樹脂組成物則必須要有較高之耐磨耗性，但以往之導電性樹脂組成物之耐磨耗性仍尚存在改良之餘地。 In recent years, with the thin and light electronic devices, the guide The electrical resin composition requires high abrasion resistance. For example, in a conductive application such as a diaphragm switch, the conductive resin composition used in the contact portion that is mutually disconnected each time the switch is switched must have high wear resistance, but the conventional conductive resin There is still room for improvement in the wear resistance of the composition.
因此，本發明之目的在於提供一種可取得耐 磨耗性優異之硬化物之導電性樹脂組成物、使其硬化而得之導電性樹脂硬化物及使用該硬化物之圖型導體電路。 Accordingly, it is an object of the present invention to provide an endurance that can be achieved A conductive resin composition of a cured product having excellent abrasion resistance, a cured conductive resin obtained by curing the same, and a patterned conductor circuit using the cured product.
本發明者等為了解決上述課題經過精心研討之結果，發現丙烯酸酯化合物與異氰酸酯化合物之混合物在加熱時會引起固化現象，更發現、含有異氰酸酯化合物與丙烯酸酯化合物之導電性樹脂組成物之硬化物具有優良耐磨耗性，進而完成了本發明。 In order to solve the above problems, the inventors of the present invention have found that a mixture of an acrylate compound and an isocyanate compound causes a curing phenomenon upon heating, and a cured product of a conductive resin composition containing an isocyanate compound and an acrylate compound is also found. The invention has excellent wear resistance and thus completed the present invention.
即，本發明之導電性樹脂組成物，其特徵為包含(A)甲階酚醛型酚樹脂、(B)異氰酸酯化合物、(C)(甲基)丙烯酸酯化合物、及(D)導電粉。 That is, the conductive resin composition of the present invention is characterized by comprising (A) a resol type phenol resin, (B) an isocyanate compound, (C) a (meth) acrylate compound, and (D) a conductive powder.
本發明之導電性樹脂組成物，其中更以前述(B)異氰酸酯化合物係經吡唑所封閉之異氰酸酯化合物為佳。 In the conductive resin composition of the present invention, it is preferred that the (B) isocyanate compound is an isocyanate compound blocked by pyrazole.
本發明之導電性樹脂組成物，其中前述(D)導電粉係以碳黑、及、石墨中之1種以上為佳。 In the conductive resin composition of the present invention, the (D) conductive powder is preferably one or more of carbon black and graphite.
本發明之導電性樹脂組成物，其中更以包含 (E)聚乙烯縮醛樹脂為佳。 The conductive resin composition of the present invention, which further comprises (E) A polyvinyl acetal resin is preferred.
本發明之導電性樹脂硬化物，其特徵為使前 述之導電性樹脂組成物硬化而得者。 The conductive resin cured product of the present invention is characterized in that The conductive resin composition described above is cured.
本發明之圖型導體電路，其特徵為使用前述 導電性樹脂硬化物者。 The patterned conductor circuit of the present invention is characterized by using the foregoing Conductive resin cured.
根據本發明，可提供一種可取得耐磨耗性優異之硬化物之導電性樹脂組成物、使其硬化而得之導電性樹脂硬化物及使用該硬化物之圖型導體電路。 According to the present invention, it is possible to provide a conductive resin composition of a cured product excellent in abrasion resistance, a cured conductive resin obtained by curing the same, and a patterned conductor circuit using the cured product.
本發明之導電性樹脂組成物，其特徵為包含(A)甲階酚醛型酚樹脂、(B)異氰酸酯化合物、(C)(甲基)丙烯酸酯化合物、及(D)導電粉。 The conductive resin composition of the present invention is characterized by comprising (A) a resol type phenol resin, (B) an isocyanate compound, (C) a (meth) acrylate compound, and (D) a conductive powder.
以下，具體地說明關於各成分。 Hereinafter, each component will be specifically described.
尚且，於本發明中，樹脂係意指(A)、(B)、(C)及(E)。 Further, in the present invention, the resin means (A), (B), (C) and (E).
本發明中，(A)甲階酚醛型酚樹脂只要係使用於導電性樹脂組成物之黏合劑樹脂者，即可使用公知之任一者。又，亦可藉由烷氧基等而改質。(A)甲階酚醛型酚 樹脂之分子量並無特別限定，重量平均分子量Mw係以500~5000為佳。 In the present invention, any of the known (A) resol type phenol resin may be used as long as it is used as a binder resin for the conductive resin composition. Further, it may be modified by an alkoxy group or the like. (A) resol phenol The molecular weight of the resin is not particularly limited, and the weight average molecular weight Mw is preferably from 500 to 5,000.
甲階酚醛型酚樹脂例如係可使酚化合物在鹼存在下以甲醛類進行羥甲基化而得，藉由放置於酸性條件下或加熱引起縮合反應，進而產生膠化、硬化。 The resol type phenol resin is obtained, for example, by methylolation of a phenol compound in the presence of a base, and is subjected to a condensation reaction under acidic conditions or heating to cause gelation and hardening.
作為甲階酚醛型酚樹脂之原料之酚化合物， 例如可舉出酚、m-甲酚、o-甲酚、p-甲酚、p-tert-丁酚、p-乙酚、2,3-茬酚、2,5-茬酚、m-乙酚、3,5-茬酚、m-甲氧基酚、雙酚A、雙酚F。由硬化性與耐熱性之面觀之，以雙酚A、酚、m-甲酚、m-乙酚、3,5-茬酚、m-甲氧基酚為佳。 a phenol compound as a raw material of a resol type phenol resin, For example, phenol, m-cresol, o-cresol, p-cresol, p-tert-butanol, p-ethylphenol, 2,3-indophenol, 2,5-nonanol, m-B Phenol, 3,5-nonanol, m-methoxyphenol, bisphenol A, bisphenol F. From the viewpoint of hardenability and heat resistance, bisphenol A, phenol, m-cresol, m-ethylphenol, 3,5-nonanol, and m-methoxyphenol are preferred.
前述甲醛類可舉出如甲醛、三聚甲醛或三噁 烷等，此等可使用1種，亦可使用2種以上。取得之羥甲基係以每1個芳香環核心存有1.0個以上為理想。 The aforementioned formaldehyde may be, for example, formaldehyde, trioxane or trioxane. One type may be used, and two or more types may be used. The obtained methylol group is preferably 1.0 or more per one aromatic ring core.
(A)甲階酚醛型酚樹脂之配合量在以固形分 換算後，相對於導電性樹脂組成物中之樹脂固形分而言，以10~55質量%為佳，15~45質量%為較佳。甲階酚醛型酚樹脂之配合量在未滿10質量%時，則有圖型導體電路所必須之焊劑耐熱性、高溫耐熱性等之特性降低之情況，另一方面，若超過55質量%時，則有對耐煮沸性、彎曲性、印刷性等產生不良影響之情況，故不佳。又，(A)甲階酚醛型酚樹脂係以甲醛之含有量在0.1%以下者，因對環境性能優異而為佳。 (A) The amount of resol type phenol resin is in solid form After the conversion, the solid content of the resin in the conductive resin composition is preferably 10 to 55% by mass, and preferably 15 to 45% by mass. When the amount of the resol type phenol resin is less than 10% by mass, the characteristics such as flux heat resistance and high-temperature heat resistance which are necessary for the pattern conductor circuit are lowered. On the other hand, when it exceeds 55 mass% However, there is a case where the boiling resistance, the bendability, the printability, and the like are adversely affected, which is not preferable. Further, the (A) resol type phenol resin is preferably one having a formaldehyde content of 0.1% or less, and is excellent in environmental performance.
本發明中，(B)異氰酸酯化合物只要係使用於導電性樹脂組成物之黏合劑樹脂者，即可使用公知之任一者。 作為此種異氰酸酯化合物，可舉出如脂肪族異氰酸酯化合物、芳香族異氰酸酯化合物、由異氰酸酯化合物與聚羥基化合物或聚胺化合物所得之末端異氰酸酯預聚物或高分子量之含異氰酸酯基聚合物等。 In the present invention, any of the known (B) isocyanate compounds may be used as long as it is used as a binder resin for the conductive resin composition. Examples of such an isocyanate compound include an aliphatic isocyanate compound, an aromatic isocyanate compound, a terminal isocyanate prepolymer obtained from an isocyanate compound, a polyhydroxy compound or a polyamine compound, or a high molecular weight isocyanate group-containing polymer.
(B)異氰酸酯化合物之配合量在以固形分換算後，相對於組成物中之樹脂固形分而言，以20~85質量%為佳，35~80質量%為較佳。異氰酸酯化合物之配合量若未滿20質量%，則有引起耐煮沸性降低之情況，相對於此，若超出85質量%時，則有引起焊劑耐熱性、高溫耐熱性等之特性降低之情況，故不佳。 The blending amount of the (B) isocyanate compound is preferably from 20 to 85% by mass, and preferably from 35 to 80% by mass, based on the solid content of the resin in the composition. When the amount of the isocyanate compound is less than 20% by mass, the boiling resistance may be lowered. On the other hand, when it exceeds 85% by mass, the properties such as solder heat resistance and high-temperature heat resistance may be deteriorated. It is not good.
作為上述脂肪族異氰酸酯化合物，例如有 1,6-六亞甲基二異氰酸酯(HDI或HMDI)、異佛爾酮二異氰酸酯(IPDI)、甲基環己烷2,4-(2,6)-二異氰酸酯(氫化TDI)、4,4'-亞甲基雙(環己基異氰酸酯)(氫化MDI)、1,3-(異氰酸酯甲基)環己烷(氫化XDI)、降莰烯二異氰酸酯(NDI)、離胺酸二異氰酸酯(LDI)、三甲基六亞甲基二異氰酸酯(TMDI)、二聚物酸二異氰酸酯(DDI)、N,N’,N”-參(6-異氰酸酯、六亞甲基)雙脲等。 As the above aliphatic isocyanate compound, for example, 1,6-hexamethylene diisocyanate (HDI or HMDI), isophorone diisocyanate (IPDI), methylcyclohexane 2,4-(2,6)- Diisocyanate (hydrogenated TDI), 4,4 ' -methylene bis(cyclohexyl isocyanate) (hydrogenated MDI), 1,3-(isocyanate methyl)cyclohexane (hydrogenated XDI), norbornene diisocyanate (NDI) ), diazonic acid diisocyanate (LDI), trimethyl hexamethylene diisocyanate (TMDI), dimer acid diisocyanate (DDI), N, N', N"- gin (6-isocyanate, hexa Methyl) diurea and the like.
作為上述芳香族異氰酸酯化合物，例如可舉 出甲伸苯基二異氰酸酯(TDI)、4,4'-二苯基甲烷二異氰 酸酯(MDI)、伸茬基二異氰酸酯(XDI)等。 Examples of the aromatic isocyanate compounds, and examples thereof include methyl phenylene diisocyanate (TDI), 4,4 '- diphenylmethane diisocyanate (MDI), extending crop-yl diisocyanate (XDI) and the like.
作為用以取得上述末端異氰酸酯預聚物及聚 合物所使用之低分子量聚羥基化合物，可舉出如乙二醇、丙二醇、二乙二醇、二丙二醇、1,4-丁二醇、1,3-丁二醇、六亞甲基二醇、新戊二醇、丙三醇、三羥甲基丙烷、季戊四醇、聚乙二醇、聚丙二醇、聚乙烯己二酸酯‧二醇、聚丙烯己二酸酯‧二醇等。 Used to obtain the above terminal isocyanate prepolymer and poly The low molecular weight polyhydroxy compound used in the compound may, for example, be ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol or hexamethylene Alcohol, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, polyethylene glycol, polypropylene glycol, polyethylene adipate ‧ diol, polypropylene adipate ‧ diol, and the like.
又，由單液化‧儲存壽命之觀點，異氰酸酯 化合物係以使用藉由公知之封閉化劑(封端劑)所封閉之封閉化異氰酸酯為佳。作為封閉化劑，例如可舉出乙醇、n-丙醇、異丙醇、t-丁醇、異丁醇等之醇類、酚、氯酚、甲酚、茬酚、p-硝基酚等之酚類、p-t-丁酚、p-sec-丁酚、p-sec-胺基酚、p-辛酚、p-壬酚等之烷基酚類、3-羥基吡啶、8-羥基喹啉、8-羥基喹吶啶等之鹼性含氮化合物、丙二酸二乙酯、乙醯乙酸乙酯、乙醯丙酮等之活性亞甲基化合物、乙醯胺、丙烯醯胺、乙醯苯胺等之酸醯胺類、琥珀酸醯亞胺、馬來酸醯亞胺等之酸醯亞胺類、2-乙基咪唑、2-乙基-4-甲基咪唑等之咪唑類、吡唑、3-甲基吡唑、3,5-二甲基吡唑等之吡唑類、2-吡咯酮、ε-己內醯胺等之內醯胺類、丙酮肟、甲基乙基酮肟、環己酮肟、乙醛肟等之酮或醛之肟類、乙烯亞胺、重亞硫酸鹽等。其中異以經活性亞甲基化合物及/或吡唑類所封閉之封閉化異氰酸酯為佳，以經丙二酸二乙酯及/或3,5-二甲基吡唑所封閉之封閉化異氰酸酯為更佳，以經3,5-二甲基吡唑所封閉之封閉 化異氰酸酯為特佳。上述封閉劑可使用單獨1種類，亦可併用2種類以上。 Also, from the viewpoint of single liquefaction and storage life, isocyanate The compound is preferably a blocked isocyanate which is blocked by a known blocking agent (blocking agent). Examples of the blocking agent include alcohols such as ethanol, n-propanol, isopropanol, t-butanol, and isobutanol, phenol, chlorophenol, cresol, indophenol, p-nitrophenol, and the like. Alkyl phenols such as phenols, pt-butanol, p-sec-butanol, p-sec-aminophenol, p-octylphenol, p-nonanol, 3-hydroxypyridine, 8-hydroxyquinoline An active nitrogen compound such as an alkaline nitrogen-containing compound such as 8-hydroxyquinacridine, diethyl malonate, ethyl acetate, ethyl acetate or acetone, acetamide, acrylamide or acetanilide And other imidazoles such as acid amides, succinimide succinate, yttrium imide, etc., imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole, pyrazole , indoleamines such as 3-methylpyrazole and 3,5-dimethylpyrazole, 2-pyrrolidone, ε-caprolactam, etc., acetone oxime, methyl ethyl ketone oxime A ketone or an aldehyde such as cyclohexanone oxime or acetaldoxime, an ethylene imine or a bisulfite. The blocked isocyanate which is blocked by the active methylene compound and/or the pyrazole is preferably a blocked isocyanate blocked by diethyl malonate and/or 3,5-dimethylpyrazole. For better, closed by 3,5-dimethylpyrazole Isocyanates are particularly preferred. The above-mentioned blocking agent may be used alone or in combination of two or more.
又，上述吡唑化合物亦可不作為上述異氰酸 酯化合物之封閉劑，而單獨被包含於樹脂組成物中。 Further, the above pyrazole compound may not be used as the above isocyanic acid. A blocking agent for an ester compound, which is separately contained in the resin composition.
本發明中，作為吡唑化合物，例如可舉出無取代之吡唑、3-甲基吡唑、4-甲基吡唑、5-甲基吡唑、3-戊基吡唑、3,5-二甲基吡唑、3-氯吡唑、3,4-二溴吡唑等之吡唑環之3、4、5位之任一位之1個以上被碳原子數1~5之烷基、鹵素原子、苯基或乙醯基所取代之吡唑。此等吡唑環上之取代基可為1種，亦可為2種以上。吡唑化合物係以選自無取代吡唑、烷基取代吡唑及此等之衍生物之1個以上之吡唑化合物為佳，由作為封閉劑之熱解離性與熱安定性之平衡，以3,5-二甲基吡唑為特佳。 In the present invention, examples of the pyrazole compound include unsubstituted pyrazole, 3-methylpyrazole, 4-methylpyrazole, 5-methylpyrazole, 3-pentylpyrazole, and 3,5. - one or more of any of the 3, 4, and 5 positions of the pyrazole ring such as dimethylpyrazole, 3-chloropyrazole, or 3,4-dibromopyrazole, and an alkane having 1 to 5 carbon atoms a pyrazole substituted with a halogen atom, a phenyl group or an ethyl fluorenyl group. The substituent on the pyrazole ring may be one type or two or more types. The pyrazole compound is preferably one or more pyrazole compounds selected from the group consisting of an unsubstituted pyrazole, an alkyl-substituted pyrazole, and the like, and is balanced by thermal dissociation and thermal stability as a blocking agent. 3,5-Dimethylpyrazole is particularly preferred.
吡唑化合物之配合量以固形分換算後，相對於甲階酚醛型酚樹脂之固形分而言，以1~35質量%為佳，以10~30質量%為較佳。吡唑化合物之配合量若未滿1質量%時，在本發明之硬化條件下並無法充分抑制甲階酚醛樹脂之自我縮合，另一方面，若超出35質量%時，因過度抑制所需之反應性，而會造成塗膜特性降低，故不佳。 The amount of the pyrazole compound to be converted is preferably from 1 to 35% by mass, preferably from 10 to 30% by mass, based on the solid content of the resol type phenol resin. When the amount of the pyrazole compound is less than 1% by mass, the self-condensation of the resol phenolic resin is not sufficiently suppressed under the curing conditions of the present invention. On the other hand, when it exceeds 35% by mass, it is required to be excessively inhibited. Reactivity is caused by a decrease in film properties, which is not preferable.
其理由雖然並非十分明確，但已知異氰酸酯基會與羥基或胺基等之官能基反應，而本發明者等發現無論有無含有該者，丙烯酸酯化合物與異氰酸酯化合物之混合物在加 熱時會引起固化現象。又，使含有異氰酸酯化合物與丙烯酸酯化合物之樹脂組成物熱硬化時，可取得具有優良耐磨耗性之硬化物。 Although the reason is not very clear, it is known that an isocyanate group reacts with a functional group such as a hydroxyl group or an amine group, and the inventors have found that a mixture of an acrylate compound and an isocyanate compound is added with or without the inclusion of the isocyanate group. It causes curing when hot. Further, when the resin composition containing the isocyanate compound and the acrylate compound is thermally cured, a cured product having excellent abrasion resistance can be obtained.
本發明中，(C)(甲基)丙烯酸酯化合物只要係使用於導電性樹脂組成物者，即可使用公知之任一者，亦可為丙烯酸酯化合物、甲基丙烯酸酯化合物及該等混合物之任一者。 In the present invention, the (C) (meth) acrylate compound may be any one known to be used as the conductive resin composition, or may be an acrylate compound, a methacrylate compound, and the like. Either.
作為上述(甲基)丙烯酸酯化合物，可使用 於1分子中具有1個以上(甲基)丙烯醯基之(甲基)丙烯酸酯化合物，例如可舉出2-(2-乙氧基乙氧基)乙基丙烯酸酯、硬脂醯基丙烯酸酯、十三基丙烯酸酯、十二基丙烯酸酯、異莰基丙烯酸酯、2-羥基乙基丙烯酸酯、2-羥基丙基丙烯酸酯、2-苯氧基乙基丙烯酸酯等之單官能丙烯酸酯化合物、1,3-丁二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、二乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、貳三羥甲基丙烷四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯等之多官能丙烯酸酯化合物、及其所對應之甲基丙烯酸酯化合物等。又，可舉出三羥甲基丙烷、加氫雙酚A等之多官能醇或雙酚A、雙酚等之多價酚之環氧乙烷加成物及/或環氧丙烷加成物之丙烯酸酯類；上述含羥基丙烯酸酯之異氰酸酯變性物之多官能或單官能聚胺基甲酸酯丙烯酸酯；雙酚A二環氧丙基醚、加氫雙酚A二環氧丙基醚或苯酚酚 醛環氧樹脂之(甲基)丙烯酸加成物之環氧丙烯酸酯類；及其所對應之甲基丙烯酸酯化合物等。(甲基)丙烯酸酯化合物之市售品之製品名，例如可舉出NeomerDA-600(三洋化成工業(股)製)、AronixM-309、M-7100(以上、東亞合成(股)製)。上述(甲基)丙烯酸酯化合物可單獨使用1種類，亦可將2種類以上予以併用。 As the above (meth) acrylate compound, it can be used The (meth) acrylate compound having one or more (meth) acrylonitrile groups in one molecule may, for example, be 2-(2-ethoxyethoxy)ethyl acrylate or stearyl acrylate. Monofunctional acrylic acid such as ester, tridecyl acrylate, dodecyl acrylate, isodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-phenoxyethyl acrylate Ester compound, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trishydroxyl a polyfunctional acrylate compound such as propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like A methacrylate compound or the like. Further, examples thereof include polyfunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A, and ethylene oxide adducts and/or propylene oxide adducts of polyvalent phenols such as bisphenol A and bisphenol. Acrylates; polyfunctional or monofunctional polyurethane acrylates of the above-mentioned hydroxylated acrylate-containing isocyanate denatures; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether Phenol phenol An epoxy acrylate of an (meth)acrylic acid addition product of an aldehyde epoxy resin; and a corresponding methacrylate compound thereof. The name of the product of the commercially available product of the (meth) acrylate compound is, for example, Neomer DA-600 (manufactured by Sanyo Chemical Industries Co., Ltd.), Aronix M-309, and M-7100 (manufactured by Toago Seisakusho Co., Ltd.). The above (meth) acrylate compound may be used alone or in combination of two or more.
(C)(甲基)丙烯酸酯化合物之配合量以固形分換算後，相對於導電性樹脂組成物中之樹脂固形分而言，以0.2~30質量%為佳，2~20質量%為較佳。(甲基)丙烯酸酯化合物之配合量若未滿0.2質量%時，則有無法充分取得改善耐磨耗性之效果之情況，另一方面若超出30質量%時，則有無法取得充分電阻之值之情況。 (C) The amount of the (meth) acrylate compound is preferably 0.2 to 30% by mass, and 2 to 20% by mass, based on the solid content of the resin in the conductive resin composition. good. When the amount of the (meth) acrylate compound is less than 0.2% by mass, the effect of improving the abrasion resistance may not be sufficiently obtained. On the other hand, if it exceeds 30% by mass, sufficient resistance cannot be obtained. The value of the situation.
本發明中，(D)導電粉只要係使用於導電性樹脂組成物之黏合劑樹脂者，即可使用公知之任一者。作為導電粉，例如可舉出、金、銀、銅、鉑、鈀合金、鋁等之金屬粉、爐黑、熱裂碳黑、槽黑、乙缺黑、科琴黑等之碳黑、石墨、碳黑與石墨之混合物、奈米碳管等之碳粉末，以碳黑、石墨、碳黑與石墨之混合物為佳。上述導電粉可單獨使用1種類，亦可將2種類以上予以併用。 In the present invention, the (D) conductive powder may be any known one as long as it is used as a binder resin for the conductive resin composition. Examples of the conductive powder include carbon powder such as gold, silver, copper, platinum, palladium alloy, aluminum, furnace black, thermal black, black, black, and black. A carbon powder such as a mixture of carbon black and graphite or a carbon nanotube is preferably a mixture of carbon black, graphite, carbon black and graphite. The conductive powder may be used alone or in combination of two or more.
(D)導電粉之含有量，在使用金屬粉時之情況時，以導電性樹脂組成物中之固形分換算後，較佳為70~95質量%，更佳為75~90質量%，在使用碳粉時，以導電性樹 脂組成物中之固形分換算後，較佳為35~65質量%，更佳為45~55質量%。配合量若少於上述範圍時，則有無法取得充分導電性之情況，相對於此，若多於上述範圍時，則有硬化膜之機械強度降低之情況，故不佳。 (D) When the content of the conductive powder is used, when it is converted into a solid content in the conductive resin composition, it is preferably 70 to 95% by mass, more preferably 75 to 90% by mass. Conductive tree when using toner The conversion of the solid content in the lipid composition is preferably 35 to 65 mass%, more preferably 45 to 55 mass%. When the amount is less than the above range, sufficient conductivity may not be obtained. On the other hand, when the amount is more than the above range, the mechanical strength of the cured film may be lowered, which is not preferable.
本發明中，由導電粉之分散性或樹脂組成物之印刷特性等之觀點，以含有(E)聚乙烯縮醛樹脂為佳。(E)聚乙烯縮醛樹脂只要係使用於導電性樹脂組成物之黏合劑樹脂者，即可使用公知之任一者。(E)聚乙烯縮醛樹脂係例如可將聚乙烯醇樹脂以醛進行縮醛化而得。 In the present invention, it is preferred to contain (E) a polyvinyl acetal resin from the viewpoints of dispersibility of the conductive powder, printing characteristics of the resin composition, and the like. (E) The polyvinyl acetal resin may be any one known as long as it is used as a binder resin for the conductive resin composition. The (E) polyvinyl acetal resin can be obtained, for example, by acetalizing a polyvinyl alcohol resin with an aldehyde.
作為上述醛，並無特別限定，例如可舉出甲 醛、乙醛、丙醛、丁醛、戊醛、己醛、庚醛、2-乙基己醛、環己醛、糠醛、苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲基苯甲醛、p-羥基苯甲醛、m-羥基苯甲醛、苯基乙醛、β-苯基丙醛等，以丁醛為佳。此等之醛可單獨使用1種類，亦可將2種類以上予以併用。 The aldehyde is not particularly limited, and for example, a Aldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptaldehyde, 2-ethylhexanal, cyclohexanal, furfural, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropanal, etc., preferably butyraldehyde. These aldehydes may be used alone or in combination of two or more.
聚乙烯縮醛樹脂之市售品之製品名，例如可 舉出S-lec BL-1、BL-1H、BL-2、BL-2H、BL-5、BL-10、BL-S、BM-1、BM-2、BM-S、BH-3、BX-1、BX-2、BX-5、BX-55、BX-L、BH-3、BH-S、BM-S、KS-3Z、KS-5、KS-5Z、KS-8、KS-23Z(以上，積水化學工業(股)製)、電化丁醛4000-2、5000A、6000C、6000EP(以上，電氣化學工業(股)製)等。又，此等樹脂可單獨使 用1種類，亦可將2種類以上予以併用。 The name of the product of the commercial product of the polyvinyl acetal resin, for example, S-lec BL-1, BL-1H, BL-2, BL-2H, BL-5, BL-10, BL-S, BM-1, BM-2, BM-S, BH-3, BX -1, BX-2, BX-5, BX-55, BX-L, BH-3, BH-S, BM-S, KS-3Z, KS-5, KS-5Z, KS-8, KS-23Z (The above, Sekisui Chemical Industry Co., Ltd.), electrochemical butyraldehyde 4000-2, 5000A, 6000C, 6000EP (above, electrical chemical industry (stock) system). Also, these resins can be made separately Two types or more may be used in combination with one type.
(E)聚乙烯縮醛樹脂之配合量以固形分換算 後，相對於導電性樹脂組成物中之樹脂固形分而言，以1.5~20質量%為佳，3~15質量%為較佳。配合量若未滿1.5質量%，有無法在導電粉之分散性或印刷特性等上發現添加效果之情況，若配合量超出20質量%時，則有使焊劑耐熱性等塗膜之耐熱性降低之情況，故不佳。 (E) The amount of polyvinyl acetal resin blended in solid content After that, the solid content of the resin in the conductive resin composition is preferably 1.5 to 20% by mass, and preferably 3 to 15% by mass. When the blending amount is less than 1.5% by mass, the effect of adding the conductive powder to the dispersibility or the printing property may not be found. When the blending amount exceeds 20% by mass, the heat resistance of the coating film such as solder heat resistance may be lowered. The situation is not good.
本發明之導電性樹脂組成物除上述各成分以外，尚亦可含有導電性樹脂組成物通常所使用之其他成分。作為其他成分，可舉出如溶劑、消泡劑、搖變劑、耦合劑、防氧化劑、分散劑、均染劑等，可使用公知者之任一者。 The conductive resin composition of the present invention may contain other components generally used in the conductive resin composition in addition to the above components. Examples of the other component include a solvent, an antifoaming agent, a rocking agent, a coupling agent, an antioxidant, a dispersing agent, a leveling agent, and the like, and any of those known can be used.
本發明之導電性樹脂硬化物係藉由使上述導電性樹脂組成物熱硬化而得者。因應必要，亦可含有公知之熱硬化觸媒。熱硬化之溫度係以100~200℃為佳，120~180℃為較佳。又，本發明之圖型導體電路係在印刷配線基板上具有本發明之導電性樹脂硬化物者。本發明之圖型導體電路係可在公知之印刷配線基板上，藉由網板印刷等塗布本發明之導電性樹脂組成物，且使其熱硬化而得。 The conductive resin cured product of the present invention is obtained by thermally curing the above-mentioned conductive resin composition. A heat-hardening catalyst known in the art may also be included as necessary. The temperature of the heat curing is preferably 100 to 200 ° C, and preferably 120 to 180 ° C. Moreover, the pattern conductor circuit of the present invention is a cured conductive resin of the present invention on a printed wiring board. The patterned conductor circuit of the present invention can be obtained by applying the conductive resin composition of the present invention to a known printed wiring board by screen printing or the like and thermally curing the conductive resin composition.
本發明之導電性硬化物之製造方法係將包含 (A)甲階酚醛型酚樹脂、(B)異氰酸酯化合物、(C) (甲基)丙烯酸酯化合物、及(D)導電粉之導電性樹脂 組成物以100~200℃加熱並使其硬化之方法為佳。導電性樹脂組成物之各成分係如以上所述般。又，亦可含有上述般之其他成分。硬化溫度係以120~180℃為較佳。加熱方法並無特別限定，可採用批次式烤箱、熱風循環式乾燥爐、遠紅外線之輸送式烤箱等公知之任一方法。 The method for producing a conductive cured product of the present invention will contain (A) resol type phenol resin, (B) isocyanate compound, (C) (meth) acrylate compound, and (D) conductive powder of conductive resin It is preferred that the composition is heated at 100 to 200 ° C and hardened. The components of the conductive resin composition are as described above. Further, it may contain other components as described above. The hardening temperature is preferably 120 to 180 °C. The heating method is not particularly limited, and any known method such as a batch oven, a hot air circulation drying oven, or a far infrared ray conveying oven can be employed.
以下，根據實施例更具體地說明本發明。 Hereinafter, the present invention will be more specifically described based on examples.
測量將異氰酸酯化合物、甲階酚醛樹脂、丁醛樹脂與分別添加有各種丙烯酸酯化合物之系統加熱至150℃時至膠化為止之時間(膠化時間)。本參考例中之膠化係指表示到液狀組成物固化且引起性狀變化為止之時間，其係藉由目視進行確認。其結果如下述表1及表2所示。表中之配合量之單位為質量份。又，於15分以上性狀無變化時，則評價為「無變化」。 The time (gelation time) until the gelation of the isocyanate compound, the resol resin, the butyral resin, and the system in which various acrylate compounds were respectively added was heated to 150 ° C. The gelation in the present reference example means the time until the liquid composition is cured and the properties are changed, which is confirmed by visual observation. The results are shown in Tables 1 and 2 below. The unit of the amount in the table is parts by mass. In addition, when there is no change in the trait of 15 or more, the evaluation is "no change".
由參考例1可知，即使分別將異氰酸酯化合 物、(甲基)丙烯酸酯化合物加熱至150℃仍不會引起性狀變化(參考例1-1、1-2)，但對此進行混合時，確認到轉為固形物之性狀變化(參考例1-3~1-5)。另一方面，由參考例2可知，混合有甲階酚醛樹脂與(甲基)丙烯酸酯化合物之系統中，在與甲階酚醛樹脂單獨之情況相比，顯現伴隨系統中之(甲基)丙烯酸酯濃度變高而膠化時間變慢之傾向(參考例2-1~2-5)。此現象教示由於(甲基)丙烯酸酯化合物單獨無法硬化，藉由混合而單純地組成內之甲階酚醛樹脂濃度減少導致膠化時間變慢。並且， 在丁醛樹脂方面，即便在單獨‧混合系統中亦未發現變化(參考例2-6、2-7)。由此參考例之結果，雖然現象之反應機制並非明確，但可確認到異氰酸酯化合物因(甲基)丙烯酸酯化合物之添加而受到熱性影響。 It can be seen from Reference Example 1 that even if isocyanate is separately combined When the (meth) acrylate compound was heated to 150 ° C, it did not cause a change in properties (Reference Examples 1-1 and 1-2), but when it was mixed, the change in the properties of the solid matter was confirmed (Reference example) 1-3~1-5). On the other hand, as is understood from Reference Example 2, in the system in which the resole phenol resin and the (meth) acrylate compound are mixed, the (meth)acrylic acid in the accompanying system is visualized as compared with the case of the resol phenol resin alone. The tendency of the ester concentration to become high and the gelation time to be slow (Reference Examples 2-1 to 2-5). This phenomenon teaches that since the (meth) acrylate compound alone cannot be hardened, the concentration of the resol phenol resin in the simple composition by mixing is reduced, resulting in a slow gelation time. and, Regarding the butyral resin, no change was observed even in the separate ‧ mixing system (Reference Examples 2-6 and 2-7). As a result of the reference example, although the reaction mechanism of the phenomenon was not clear, it was confirmed that the isocyanate compound was thermally affected by the addition of the (meth) acrylate compound.
以下，根據實施例更具體地說明本發明。將下述表3所示之比較例1、2、及實施例1~7之成分以三輥式滾磨機進行混合分散而製成導電性樹脂組成物。表中之配合量之單位為質量份。 Hereinafter, the present invention will be more specifically described based on examples. The components of Comparative Examples 1 and 2 and Examples 1 to 7 shown in Table 3 below were mixed and dispersed in a three-roll mill to obtain a conductive resin composition. The unit of the amount in the table is parts by mass.
基卡必醇乙酸酯稀釋清漆(NV=20%) Kikabi alcohol acetate dilute varnish (NV=20%)
※3：Baxenden公司製BI-7982(NV=70%) *3: BI-7982 manufactured by Baxenden Co., Ltd. (NV=70%)
※4：Baxenden公司製BI-7992(NV=70%) *4: BI-7992 manufactured by Baxenden Co., Ltd. (NV=70%)
※5：獅王股份有限公司製科琴黑EC-300J *5: Kewang Black EC-300J made by Lion King Co., Ltd.
※6：日本石墨股份有限公司製SP-20 *6: SP-20 manufactured by Nippon Graphite Co., Ltd.
※7：三洋化成工業股份有限公司製NeomerDA-600(NV=100%)(二季戊四醇五丙烯酸酯) *7: NanoerDA-600 (NV=100%) manufactured by Sanyo Chemical Industry Co., Ltd. (dipentaerythritol pentaacrylate)
※8：東亞合成股份有限公司製AronixM-309(NV=100%)(三羥甲基丙烷三丙烯酸酯) *8: Aronix M-309 (NV=100%) manufactured by Toagosei Co., Ltd. (trimethylolpropane triacrylate)
※9：東亞合成股份有限公司製AronixM-7100(NV=100%)(3官能以上之聚酯丙烯酸酯) *9: Aronix M-7100 (NV=100%) manufactured by Toagosei Co., Ltd. (3 or more polyester acrylates)
※10：協和發酵化學股份有限公司製Butysenol 20 acetate(丁基卡必醇乙酸酯) *10: Butysenol 20 acetate (butyl carbitol acetate) manufactured by Xiehe Fermentation Chemical Co., Ltd.
運用由使用此等導電性樹脂組成物所製成之印刷配線板，根據下述之評價試驗法，施行體積電阻值、密著性、耐膠帶剝離性、焊劑耐熱性、煮沸耐性、鉛筆硬度試驗。其結果係如下述表4所示。 Using a printed wiring board made of such a conductive resin composition, volume resistance, adhesion, tape peeling resistance, flux heat resistance, boiling resistance, pencil hardness test were performed according to the following evaluation test method. . The results are shown in Table 4 below.
藉由網板印刷法分別將上述實施例1~7及比較例1~2之導電性樹脂組成物塗布於形成有電極之玻璃環氧基板之銅電路部上，使其形成寬1mm×長100mm之圖型皮膜。其次，在熱風循環式乾燥爐中，以150℃加熱30分鐘使其硬化。其次，藉由Milliohm HiTESTER(HIOKI公司製 3540mΩHiTESTER)測量取得之硬化膜之電阻值(R)，並算出體積電阻值。體積電阻值之算出係使用Surcoder測量導電成形體之厚度(t)，使用光學顯微鏡測量基於反射光之導電成形體之正確線寬度(w)及長度(1)，且基於此等測定值使用式「ρ=R‧w‧t/1」算出體積電阻值。在此，ρ為體積電阻值(Ω‧cm)、R為電阻值(Ω)、w為寬度(cm)、t為厚度(cm)、1為長度(cm)。尚且，體積電阻值係數值越小越佳。 The conductive resin compositions of the above Examples 1 to 7 and Comparative Examples 1 and 2 were applied to a copper circuit portion of a glass epoxy substrate on which an electrode was formed by a screen printing method to form a width of 1 mm × a length of 100 mm. The pattern of the film. Next, it was hardened by heating at 150 ° C for 30 minutes in a hot air circulating drying oven. Second, by Milliohm HiTESTER (made by HIOKI) 3540 mΩ HiTESTER) The resistance value (R) of the obtained cured film was measured, and the volume resistance value was calculated. The volume resistance value is calculated by measuring the thickness (t) of the conductive molded body using a Surcoder, and measuring the correct line width (w) and length (1) of the conductive molded body based on the reflected light using an optical microscope, and using the measured value based on the measured value "ρ=R‧w‧t/1" calculates the volume resistance value. Here, ρ is a volume resistance value (Ω·cm), R is a resistance value (Ω), w is a width (cm), t is a thickness (cm), and 1 is a length (cm). Also, the smaller the value of the volume resistance value coefficient, the better.
與上述(1)同樣地藉由網板印刷法在玻璃環氧貼銅層合板之銅箔面上形成15mm×15mm之圖型皮膜並加熱硬化。對取得之硬化膜以切割刀切出1mm×1mm之方格100個，且調查自此之上以透明膠帶撕離塗膜時之在基板上殘留之方格個數，並評價密著性(JIS K5400-8.5)。方格殘留越多者代表越佳之結果。 In the same manner as in the above (1), a 15 mm × 15 mm pattern film was formed on the surface of the copper foil of the glass epoxy copper-clad laminate by screen printing, and heat-hardened. 100 pieces of a square of 1 mm × 1 mm were cut out with a dicing blade, and the number of squares remaining on the substrate when the coating film was peeled off with a transparent tape was investigated, and the adhesion was evaluated ( JIS K5400-8.5). The more squares remain, the better the results.
將與以上述(1)同樣地方式所製成印刷配線板浸漬於260℃之焊劑槽10秒鐘後，使用Milliohm HiTESTER(HIOKI公司製3540mΩHiTESTER)測量處理後之硬化膜之電阻值。根據算出之體積電阻值，以處理前之體積電阻值為基準再算出變化率。尚且，焊劑處理後之變化率係以絕對值越小越佳。 The printed wiring board produced in the same manner as in the above (1) was immersed in a solder bath at 260 ° C for 10 seconds, and then the resistance value of the cured film after the treatment was measured using a Milliohm HiTESTER (3540 mΩ HiTESTER manufactured by HIOKI Co., Ltd.). Based on the calculated volume resistance value, the rate of change is calculated based on the volume resistance value before the treatment. Moreover, the rate of change after flux treatment is preferably as small as possible.
將與以上述(1)同樣地方式所製成印刷配線板浸漬於煮沸水中2小時浸漬並煮沸。使用Milliohm HiTESTER(HIOKI公司製3540mΩHiTESTER)測量煮沸處理後之硬化膜之電阻值，且算出變化率。尚且，焊劑處理後之變化率係以絕對值越小越佳。 The printed wiring board produced in the same manner as in the above (1) was immersed in boiling water for 2 hours, and immersed and boiled. The resistance value of the cured film after the boiling treatment was measured using a Milliohm HiTESTER (3540 mΩ HiTESTER manufactured by HIOKI Co., Ltd.), and the rate of change was calculated. Moreover, the rate of change after flux treatment is preferably as small as possible.
以依循JIS K5600-5-6之試驗方法，使用鉛筆硬度試驗機，對與以上述(1)同樣地方式所製成印刷配線板掛上荷重1kg時之塗膜上不會附著傷痕之最高硬度表示。使用之鉛筆為三菱Hi-Uni(三菱鉛筆(股)製)。 According to the test method of JIS K5600-5-6, the maximum hardness of the coating film which does not adhere to the coating film when the load is 1 kg is applied to the printed wiring board produced in the same manner as in the above (1) using a pencil hardness tester. Said. The pencil used was Mitsubishi Hi-Uni (Mitsubishi Pencil Co., Ltd.).
使用NORMAN TOOL,INC.公司製RCA磨耗試驗機及RCA磨耗試驗機用專用磨耗紙，對以上述方法所製成之導電圖型表面以175g之荷重磨耗100次，且測量其前後之阻抗值，並算出作為變化率。 Using a special abrasion paper made by NORMAN TOOL, INC. company RCA abrasion tester and RCA abrasion tester, the surface of the conductive pattern prepared by the above method was worn 100 times with a load of 175 g, and the impedance values before and after the measurement were measured. And calculated as the rate of change.
○：100回磨耗後之阻抗值對初期阻抗值之變化率在±10%以內 ○: The change rate of the impedance value after 100 wear is less than ±10% of the initial impedance value
×：100回磨耗後之阻抗值對初期阻抗值之變化率超過±10% ×: The change rate of the impedance value after 100 wear to the initial impedance value exceeds ±10%
若比較比較例1與實施例1~3時，可知藉由 添加(甲基)丙烯酸酯化合物而表面硬度(鉛筆硬度)提升且耐磨耗性亦提高。而此係於先前參考例所示般，認為係源自異氰酸酯化合物與(甲基)丙烯酸酯化合物之共存下因加熱時引起之固化現象所致者。又，由於此一事項亦可在比較例2與實施例4之比較中獲得確認，故可預測廣泛異氰酸酯類與(甲基)丙烯酸酯類之組合可利用於耐磨耗性之提升。因此，本發明之對導電性組成物添加(甲基)丙烯酸酯化合物係可有效提升硬化塗膜表面之耐磨耗性，並可利用於要求如膜片開關用途等之耐磨耗性般之導電用途。 Comparing Comparative Example 1 with Examples 1 to 3, it can be seen that The (meth) acrylate compound is added and the surface hardness (pencil hardness) is improved and the abrasion resistance is also improved. This is considered to be caused by the solidification phenomenon caused by heating in the coexistence of the isocyanate compound and the (meth) acrylate compound, as shown in the previous reference examples. Moreover, since this matter can also be confirmed in comparison between Comparative Example 2 and Example 4, it can be predicted that a combination of a wide range of isocyanates and (meth) acrylates can be utilized for improvement in abrasion resistance. Therefore, the addition of the (meth) acrylate compound to the conductive composition of the present invention can effectively improve the abrasion resistance of the surface of the cured coating film, and can be utilized for the wear resistance such as the use of a diaphragm switch. Conductive use.
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