TW202112854A - Novel firing temperature reducing agent for conductive material - Google Patents
Novel firing temperature reducing agent for conductive material Download PDFInfo
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Abstract
Description
本發明係關於一種新穎導電材燒成溫度降低劑及新穎導電率提昇劑、以及相關技術。更特定而言，本發明係關於一種用以降低導電材燒成溫度及提昇導電材之導電率之組合物等，該組合物包含說明書中記載之由式(4)表示之化合物。The present invention relates to a novel conductive material firing temperature reducing agent and a novel conductivity enhancing agent, and related technologies. More specifically, the present invention relates to a composition for reducing the firing temperature of a conductive material and increasing the conductivity of the conductive material, etc. The composition includes the compound represented by formula (4) described in the specification.
針對導電材或導電體進行過各種改良。然而，現狀是目前所提供之導電材受限於包含特定組合之導電成分及基材者。 [先前技術文獻] [專利文獻]Various improvements have been made to conductive materials or conductors. However, the current situation is that the currently provided conductive materials are limited to those containing specific combinations of conductive components and substrates. [Prior Technical Literature] [Patent Literature]
專利文獻1：日本專利特開2019-102719號公報 專利文獻2：國際公開第2015/099049號 專利文獻3：國際公開第2019/039511號 專利文獻4：國際公開第2017/163615號 專利文獻5：日本專利特開2017-183207號公報Patent Document 1: Japanese Patent Laid-Open No. 2019-102719 Patent Document 2: International Publication No. 2015/099049 Patent Document 3: International Publication No. 2019/039511 Patent Document 4: International Publication No. 2017/163615 Patent Document 5: Japanese Patent Laid-Open No. 2017-183207
[解決問題之技術手段][Technical means to solve the problem]
本發明提供一種包含所需組合之導電成分及基材之導電材。The present invention provides a conductive material comprising a conductive component and a substrate in a desired combination.
本發明例如提供以下。The present invention provides the following, for example.
(項A1a)一種組合物，其係用以降低導電材之燒成溫度者，其包含由式(4)
[化1]
又，本發明例如提供以下。In addition, the present invention provides, for example, the following.
(項1)一種用以降低導電材之燒成溫度之組合物，其包含經含氧環取代之(甲基)丙烯酸烷基酯。
(項2)如上述項所記載之組合物，其中上述導電材包含上述經含氧環取代之(甲基)丙烯酸烷基酯之共聚物及導電成分。
(項3)如上述項中任一項所記載之組合物，其中上述共聚物為上述經含氧環取代之(甲基)丙烯酸烷基酯與第2(甲基)丙烯酸系單體之共聚物。
(項4)如上述項中任一項所記載之組合物，其中上述含氧環為環氧乙烷環或氧雜環丁烷環。
(項5)如上述項中任一項所記載之組合物，其中上述經含氧環取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化15]
於本發明中，關於上述1個或複數個特徵，意指除已明示之組合以外，還可進一步加以組合來提供。關於本發明之進一步之實施方式及優勢，業者只要視需要閱讀以下之詳細說明進行理解便可認識到。 [發明之效果]In the present invention, with regard to the above-mentioned one or more features, it means that in addition to the clearly indicated combination, it can be further provided in combination. Regarding the further embodiments and advantages of the present invention, the industry can recognize them by reading the following detailed descriptions as needed. [Effects of Invention]
根據本發明，可提供一種導電材燒成溫度降低劑及導電性提昇劑，且藉由使用該等，可提供一種能夠提昇導電性之技術。According to the present invention, it is possible to provide a conductive material firing temperature reducing agent and a conductivity enhancing agent, and by using these, a technology capable of improving conductivity can be provided.
以下，一面揭示最佳之形態一面說明本發明。於整個本說明書中，關於單數形式之表達，只要未特別提及，則應理解為亦包含其複數形式之概念。因此，單數形式之冠詞(例如，於英語之情形時，「a」、「an」、「the」等)只要未特別提及，則應理解為亦包含其複數形式之概念。又，關於本說明書中所使用之用語，只要未特別提及，則應理解為可以該領域中通常使用之含義來使用。因此，只要未進行其他定義，則本說明書中所使用之所有專業用語及科學技術用語與本發明所屬領域之業者通常所理解之含義相同。於矛盾之情形時，本說明書(包括定義)優先。Hereinafter, the present invention will be explained while revealing the best form. Throughout this specification, the expression of the singular form, as long as it is not specifically mentioned, should be understood to include the concept of the plural form. Therefore, articles in the singular form (for example, in the case of English, "a", "an", "the", etc.) should be understood as including the concept of the plural form as long as they are not specifically mentioned. In addition, as long as the terms used in this specification are not specifically mentioned, it should be understood that they can be used in the meaning generally used in the field. Therefore, as long as no other definitions are made, all professional terms and scientific and technical terms used in this specification have the same meanings as commonly understood by those in the field to which the present invention belongs. In case of conflict, this specification (including definitions) takes precedence.
以下適當地說明本說明書中所特別使用之用語之定義及/或基礎技術內容。The following appropriately explains the definitions and/or basic technical content of the terms specially used in this specification.
(用語之定義) 於本說明書中，「導電性」係以該領域中通常之含義來使用，意指導電之性質，將其物性量稱為「導電率」，且定義為關於某一對象(亦被稱為導體)之電阻率(比電阻，樹脂領域中亦被稱為體積電阻率)之反數。本說明書中，導電率(或電阻率)係以如下方式進行測定。具體而言，只要未特別說明，則採用藉由如下方式所測得之值，即，將測定對象(例如，膜等)切取成縱0.5 cm×橫2.00 cm×厚0.2 cm，並藉由四端子測定法(例如可使用Loresta GP[Mitsubishi Chemical Analytech公司製造]，但並不限定於此)進行測定。(Definition of terms) In this specification, "conductivity" is used in the usual meaning in this field, which means to guide the properties of electricity, and its physical properties are called "conductivity", and it is defined as the relation to a certain object (also known as conductor). ) Is the inverse of resistivity (specific resistance, also known as volume resistivity in the field of resin). In this specification, the conductivity (or resistivity) is measured as follows. Specifically, unless otherwise specified, the value measured by the following method is used, that is, the measurement object (for example, a film, etc.) is cut into a length of 0.5 cm × a width of 2.00 cm × a thickness of 0.2 cm. The terminal measurement method (for example, Loresta GP [manufactured by Mitsubishi Chemical Analytech Co., Ltd.] can be used, but it is not limited to this).
於本說明書中，「導電材」係指具有導電性之任意材料。本說明書中，導電材係以具有1.0×10-1 Ω・cm以下、通常為1.0×10-2 Ω・cm以下、較佳為1.0×10-3 Ω・cm以下之電阻率者為對象，但並不限定於此。導電材包含會賦予導電性之導電成分。代表性而言，導電材通常包含基材及導電成分而構成。In this specification, "conductive material" refers to any material with conductivity. In this manual, conductive materials are targeted for those having a resistivity of 1.0×10 -1 Ω·cm or less, usually 1.0×10 -2 Ω·cm or less, preferably 1.0×10 -3 Ω·cm or less. But it is not limited to this. The conductive material contains a conductive component that imparts conductivity. Typically, the conductive material is usually composed of a base material and a conductive component.
於本說明書中，「提昇導電率」係指於導電成分或導電材中添加有本發明之成分時，與未添加之情形相比，導電率顯著地增加，例如指使導電率至少提昇約1%、約2%、約3%、約4%、約5%、約6%、約7%、約8%、約9%、約10%、約15%、約20%、約25%、約30%、約35%、約40%、約45%、約50%、約55%、約60%、約65%、約70%、約75%、約80%、約85%、約90%、約95%、約99%，且體積電阻率之降低亦能夠表達出「提昇導電率」。例如指與比較對象相比，使體積電阻率降低約1%、約2%、約3%、約4%、約5%、約6%、約7%、約8%、約9%、約10%、約15%、約20%、約25%、約30%、約35%、約40%、約45%、約50%、約55%、約60%、約65%、約70%、約75%、約80%、約85%、約90%、約95%、約99%。In this specification, "increase the conductivity" means that when the conductive component or the conductive material is added with the component of the present invention, the conductivity is significantly increased compared to the case without addition, for example, it means that the conductivity is increased by at least about 1% , About 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90% , About 95%, about 99%, and the decrease in volume resistivity can also express "increased conductivity". For example, it means that the volume resistivity is reduced by about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70% , About 75%, about 80%, about 85%, about 90%, about 95%, about 99%.
於本說明書中，「降低燒成溫度」係指於導電成分或導電材中加入本發明之成分時，即便以低於未加入之情形時之溫度進行加熱之情形時，亦能夠達成相同或更小之體積電阻率。例如指使燒成溫度至少降低約1%、約2%、約3%、約4%、約5%、約6%、約7%、約8%、約9%、約10%、約15%、約20%、約25%、約30%、約35%、約40%、約45%、約50%、約55%、約60%、約65%、約70%、約75%、約80%、約85%、約90%、約95%、約99%。關於導電材，以去除所包含之溶劑等為目的進行加熱處理之情形較多。加熱處理之溫度越低，越不易對導電材本身或塗佈過導電材之材料等產生損傷，因而較佳。又，於導電成分為下文所述之金屬系成分之情形時，為了使導電材表現出導電性，需要進行加熱處理使金屬系成分之粒子彼此燒結之情況較多。因此，若即便降低燒成溫度亦能夠使粒子彼此燒結，則不易對導電材本身或塗佈過導電材之材料等產生損傷，因而較佳。In this specification, "reducing the firing temperature" means that when the components of the present invention are added to the conductive component or the conductive material, the same or higher temperature can be achieved even when heating is performed at a temperature lower than when it is not added. Small volume resistivity. For example, it means that the firing temperature is reduced by at least about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15% , About 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 99%. Regarding the conductive material, heat treatment is often performed for the purpose of removing the contained solvent or the like. The lower the temperature of the heating treatment, the less likely it is to damage the conductive material itself or the material coated with the conductive material, which is preferable. In addition, when the conductive component is a metal-based component described below, in order to make the conductive material exhibit conductivity, it is often necessary to perform heat treatment to sinter the particles of the metal-based component. Therefore, if the particles can be sintered even if the firing temperature is lowered, the conductive material itself or the material coated with the conductive material will not be easily damaged, which is preferable.
於本說明書中，「基材」亦稱為基質，係指導電材之結構之基礎性部分。作為基材，可使用各種聚合物。於基材為聚合物之情形時，有時將基材稱為聚合物基質。In this manual, the "substrate" is also referred to as the matrix, which is the basic part that guides the structure of electrical materials. As the substrate, various polymers can be used. When the substrate is a polymer, the substrate is sometimes referred to as a polymer matrix.
於本說明書中，「導電成分」意指賦予導電性之任意成分。作為導電成分，例如可例舉：任意金屬成分、金屬氧化物、金屬碳化物等金屬系成分、導電性碳系成分、導電性有機化合物、導電性聚合物等，但並不限定於該等。In this specification, "conductive component" means any component that imparts conductivity. Examples of the conductive component include arbitrary metal components, metal oxides, metal carbides and other metal-based components, conductive carbon-based components, conductive organic compounds, conductive polymers, etc., but are not limited to these.
於本說明書中，「金屬系成分」係以某種形式包含金屬原子作為其構成要素之成分，此概念包括金屬等金屬成分，此外還包括源自金屬之成分(例如，金屬氧化物、金屬碳化物、金屬硫化物等)。In this specification, "metal-based components" contain metal atoms in some form as components of its constituent elements. This concept includes metal components such as metals, as well as components derived from metals (for example, metal oxides, metal carbides, etc.). Materials, metal sulfides, etc.).
於本說明書中，「金屬成分」包含金屬或合金。In this specification, "metal component" includes metal or alloy.
於本說明書中，「導電性碳系成分」意指含有碳之導電性材料。作為其具體例，可例舉：鱗片狀石墨等天然石墨、人造石墨等石墨、乙炔黑、科琴黑、煙囪黑、爐黑、燈黑、熱碳黑等碳黑、石墨烯、奈米碳管、富勒烯等碳系材料；碳纖維；氟化碳等，但並不限定於該等。金屬碳化物不包含於導電性碳系成分中。「導電性碳系成分」有時亦稱為「碳系成分」。In this specification, "conductive carbon-based component" means a conductive material containing carbon. Specific examples include: natural graphite such as flake graphite, graphite such as artificial graphite, acetylene black, Ketjen black, chimney black, furnace black, lamp black, thermal black and other carbon blacks, graphene, nanocarbon Carbon-based materials such as tubes and fullerenes; carbon fibers; fluorocarbons, etc., but are not limited to these. Metal carbides are not included in the conductive carbon-based components. The "conductive carbon-based component" is sometimes also referred to as the "carbon-based component".
於本說明書中，「(甲基)丙烯酸系單體」係包含丙烯醯基及/或甲基丙烯醯基之單體，作為其例，可例舉：丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯、丙烯醯胺、甲基丙烯酸醯胺等。In this specification, "(meth)acrylic monomers" are monomers containing acrylic groups and/or methacrylic groups. Examples of such monomers include acrylic acid, methacrylic acid, acrylate, and methacrylic acid. Acrylate, acrylamide, methacrylate, etc.
於本說明書中，「(甲基)丙烯酸」意指「丙烯酸」或「甲基丙烯酸」，「(甲基)丙烯酸酯」意指「丙烯酸酯」或「甲基丙烯酸酯」。In this specification, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid", and "(meth)acrylate" means "acrylate" or "methacrylate".
例如，又，(甲基)丙烯酸系單體由式(2)表示，
[化21]
例如，又，(甲基)丙烯酸系單體由式(2)表示，
[化22]
本說明書中「經含氧環取代之(甲基)丙烯酸烷基酯」之代表性之一例為由式(1)表示之(甲基)丙烯酸酯，
[化23]
於本說明書中，「能夠取代之數量」係指於利用取代基取代某基上之氫之情形時，以所產生之基在化學上穩定為條件，所能夠取代之氫之最大數量。In this specification, "substitutable quantity" refers to the maximum quantity of hydrogen that can be substituted when the hydrogen on a certain group is substituted with a substituent, provided that the generated group is chemically stable.
於本說明書中，「烷基」係指自甲烷、乙烷、丙烷之類之脂肪族烴(烷烴)中失去一個氫原子所產生之1價基，通常以Cn H2n+1 -表示(此處，n為正整數)。烷基可為直鏈或支鏈。作為碳數1～4之烷基(C1 ～ 4 烷基)，例如可例舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、第二丁基等，但本發明並不僅限定於上述例示。作為碳數1～6之烷基(C1 ～ 6 烷基)，例如可例舉：C1 ～ 4 烷基、正戊基、異戊基、正己基、異己基等，但本發明並不僅限定於上述例示。作為碳數1～10之烷基(C1 ～ 10 烷基)，例如可例舉：C1 ～ 6 烷基、正辛基、正壬基、異壬基、分支型壬基、正癸基、異癸基等，但本發明並不僅限定於上述例示。作為碳數1～18之烷基(C1 ～ 18 烷基)，例如可例舉：C1 ～ 10 烷基、十一烷基、月桂基、十三烷基、肉豆蔻基、十五烷基、棕櫚基、十七烷基、硬脂基、異硬脂基等，但本發明並不僅限定於上述例示。In this specification, "alkyl" refers to a monovalent group resulting from the loss of a hydrogen atom from aliphatic hydrocarbons (alkanes) such as methane, ethane, and propane, and is usually represented by C n H 2n+1- ( Here, n is a positive integer). The alkyl group can be straight or branched. Examples of the alkyl group having 1 to 4 carbon atoms (C 1 to 4 alkyl group) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, The second butyl group, etc., but the present invention is not limited to the above-mentioned examples. Examples of alkyl groups having 1 to 6 carbon atoms (C 1 to 6 alkyl groups) include C 1 to 4 alkyl groups, n-pentyl groups, isopentyl groups, n-hexyl groups, isohexyl groups, etc. However, the present invention is not limited to Limited to the above example. Examples of alkyl groups having 1 to 10 carbon atoms (C 1 to 10 alkyl groups) include C 1 to 6 alkyl groups, n-octyl groups, n-nonyl groups, isononyl groups, branched nonyl groups, and n-decyl groups. , Isodecyl, etc., but the present invention is not limited to the above-mentioned examples. Examples of alkyl groups having 1 to 18 carbon atoms (C 1 to 18 alkyl groups) include C 1 to 10 alkyl groups, undecyl groups, lauryl groups, tridecyl groups, myristyl groups, and pentadecane groups. However, the present invention is not limited to the above-mentioned examples.
於本說明書中，「烯基」係指自乙烯、丙烯、丁烯之類之含有至少一個雙鍵之脂肪族烴(烯烴)中失去一個氫原子所產生之1價基，通常以Cm H2m-1 表示(此處，m為2以上之整數)。烯基可為直鏈或支鏈。作為碳數2～6之烯基，例如可例舉：乙烯基、1-丙烯基、2-丙烯基、丁烯基、戊烯基、己烯基等，但本發明並不僅限定於上述例示。作為碳數2～10之烯基，例如可例舉：碳數2～6之烯基、庚烯基、辛烯基、壬烯基、癸烯基等，但本發明並不僅限定於上述例示。In this specification, "alkenyl" refers to a monovalent group resulting from the loss of a hydrogen atom from aliphatic hydrocarbons (alkenes) containing at least one double bond such as ethylene, propylene, butene, etc., usually in terms of C m H 2m-1 means (here, m is an integer of 2 or more). Alkenyl groups can be straight or branched. Examples of alkenyl groups having 2 to 6 carbon atoms include vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, hexenyl, etc., but the present invention is not limited to the above examples. . Examples of alkenyl groups having 2 to 10 carbon atoms include alkenyl groups having 2 to 6 carbon atoms, heptenyl groups, octenyl groups, nonenyl groups, and decenyl groups. However, the present invention is not limited to the above examples. .
於本說明書中，「烷氧基」係指醇類之羥基失去氫原子而產生之1價基，通常以Cn H2n+1 O-表示(此處，n為1以上之整數)。作為碳數1～6之烷氧基，例如可例舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基、第二丁氧基、正戊氧基、異戊氧基、正己氧基、異己氧基等，但本發明並不僅限定於上述例示。In the present specification, "alkoxy" refers to a monovalent group generated by the hydroxyl group of alcohols losing a hydrogen atom, and is usually represented by C n H 2n+1 O- (here, n is an integer of 1 or more). Examples of alkoxy groups having 1 to 6 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, The second butoxy group, n-pentoxy group, isopentoxy group, n-hexoxy group, isohexoxy group, etc., but the present invention is not limited to the above-mentioned examples.
於本說明書中，「鹵烷基」係指上述烷基上之1個或者複數個氫原子被取代為鹵素原子之烷基。又，「全鹵烷基」係指上述烷基上之所有氫原子被取代為鹵素原子之烷基。作為碳數1～6之鹵烷基(C1-6 鹵烷基)，例如可例舉：三氟甲基、三氟乙基(2,2,2-三氟乙基等)、全氟乙基、三氟正丙基、四氟丙基(2,2,3,3-四氟丙基等)、全氟正丙基、三氟異丙基、全氟異丙基、三氟正丁基、全氟正丁基、三氟異丁基、全氟異丁基、三氟第三丁基、全氟第三丁基、三氟正戊基、八氟戊基(2,2,3,3,4,4,5,5-八氟戊基等)、全氟正戊基、三氟正己基、全氟正己基等，但本發明並不僅限定於上述例示。作為碳數1～8之鹵烷基(C1-8 鹵烷基)，可例舉：C1-6 鹵烷基、十一氟正庚基、全氟正庚基、十三氟辛基(3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛基等)、全氟正辛基等，但本發明並不僅限定於上述例示。In the present specification, "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms on the above-mentioned alkyl group are substituted with halogen atoms. In addition, "perhaloalkyl" refers to an alkyl group in which all hydrogen atoms on the above-mentioned alkyl group are substituted with halogen atoms. Examples of haloalkyl groups having 1 to 6 carbon atoms (C 1-6 haloalkyl groups) include trifluoromethyl, trifluoroethyl (2,2,2-trifluoroethyl, etc.), perfluoromethyl Ethyl, trifluoropropyl, tetrafluoropropyl (2,2,3,3-tetrafluoropropyl, etc.), perfluoropropyl, trifluoroisopropyl, perfluoroisopropyl, trifluoropropyl Butyl, perfluoron-butyl, trifluoroisobutyl, perfluoroisobutyl, trifluorotertiary butyl, perfluorotertiary butyl, trifluoropentyl, octafluoropentyl (2,2, 3,3,4,4,5,5-octafluoropentyl, etc.), perfluoro-n-pentyl, trifluoro-n-hexyl, perfluoro-n-hexyl, etc., but the present invention is not limited to the above examples. Examples of haloalkyl groups having 1 to 8 carbon atoms (C 1-8 haloalkyl groups) include C 1-6 haloalkyl groups, undecafluoro-n-heptyl groups, perfluoro-n-heptyl groups, and tridecafluorooctyl groups (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, etc.), perfluoro-n-octyl, etc., but the present invention is not limited to the above Exemplify.
於本說明書中，「環烷基」意指單環或多環式飽和烴基，亦包含經交聯之結構者。例如，「C3-12 環烷基」意指碳原子數為3～12之環狀烷基。作為C6-12 環烷基之具體例，可例舉：環己基、環庚基、環辛基、金剛烷基、異𦯉基、2-甲基-2-金剛烷基、2-乙基-2-金剛烷基等，但本發明並不僅限定於上述例示。作為C5-12 環烷基之具體例，可例舉：環戊基、C6-12 環烷基等，但本發明並不僅限定於上述例示。作為C3-12 環烷基之具體例，可例舉：環丙基、環丁基、C5-12 環烷基等。較佳為可例舉「C6-12 環烷基」，但本發明並不僅限定於上述例示。In this specification, "cycloalkyl" means a monocyclic or polycyclic saturated hydrocarbon group, which also includes a crosslinked structure. For example, "C 3-12 cycloalkyl" means a cyclic alkyl group having 3 to 12 carbon atoms. Specific examples of C 6-12 cycloalkyl groups include cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, iso?, 2-methyl-2-adamantyl, 2-ethyl -2-adamantyl and the like, but the present invention is not limited to the above-mentioned examples. As specific examples of C 5-12 cycloalkyl, cyclopentyl, C 6-12 cycloalkyl, etc. may be mentioned, but the present invention is not limited to the above-mentioned examples. Specific examples of C 3-12 cycloalkyl include cyclopropyl, cyclobutyl, C 5-12 cycloalkyl and the like. Preferably, a "C 6-12 cycloalkyl group" can be exemplified, but the present invention is not limited to the above exemplification.
於本說明書中，「環烯基」意指包含雙鍵之單環或多環式不飽和烴基，亦包含經交聯之結構者。可例舉上述「環烷基」之碳間鍵之1個以上成為雙鍵者。例如，「C3-12 環烯基」意指碳原子數為3～12之環狀烯基。作為具體例，於「C6-12 環烯基」之情形時，可例舉：1-環己烯基、2-環己烯基、3-環己烯基、環庚烯基、環辛烯基、環壬烯基等。於「C3-12 環烷基」之情形時，可例舉：環丙烯基、環丁烯基、環戊烯基、C6-12 環烯基等。較佳為可例舉「C6-12 環烯基」，但本發明並不僅限定於上述例示。In this specification, "cycloalkenyl" means a monocyclic or polycyclic unsaturated hydrocarbon group containing a double bond, and also includes a crosslinked structure. One or more of the inter-carbon bonds of the above-mentioned "cycloalkyl" may be a double bond. For example, "C 3-12 cycloalkenyl" means a cyclic alkenyl group having 3 to 12 carbon atoms. As a specific example, in the case of "C 6-12 cycloalkenyl", examples include 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, cycloheptenyl, and cyclooctyl Alkenyl, cyclononenyl, etc. In the case of "C 3-12 cycloalkyl", cyclopropenyl, cyclobutenyl, cyclopentenyl, C 6-12 cycloalkenyl and the like can be exemplified. Preferably, the "C 6-12 cycloalkenyl group" can be exemplified, but the present invention is not limited to the above exemplification.
於本說明書中，「非芳基雜環烷基」及「非芳基雜環」意指於其環內具有1～3個選自氮原子、氧原子及硫原子之同種或異種原子之環式基，該基可包含1個或複數個不飽和鍵，但不含芳香族基。例如，「3～8員非芳基雜環烷基」意指構成環之原子數為3～8個之非芳基雜環烷基。作為「非芳基雜環烷基」之具體例，可例舉：環氧乙烷基、氧雜環丁基、吡喃基、吡咯啶基、咪唑啶基、哌啶基、𠰌啉基、硫代𠰌啉基、六亞甲基亞胺基、噻唑啶基、四氫呋喃基、四氫吡啶基、四氫吡喃基、1,3-二氧戊環基、1,3-二氧雜環己基、1,4-二氧雜環己基等，但本發明並不僅限定於上述例示。再者，該基亦包含具有交聯結構者。In this specification, "non-arylheterocycloalkyl" and "non-arylheterocycle" mean a ring having 1 to 3 atoms of the same or different species selected from nitrogen atoms, oxygen atoms and sulfur atoms in the ring. Formula base, the base may contain one or more unsaturated bonds, but does not contain an aromatic group. For example, "3- to 8-membered non-arylheterocycloalkyl" means a non-arylheterocycloalkyl with 3-8 atoms constituting the ring. Specific examples of "non-aryl heterocycloalkyl" include: oxiranyl, oxetanyl, pyranyl, pyrrolidinyl, imidazolidinyl, piperidinyl, linolinyl, Thiothiolinyl, hexamethyleneimino, thiazolidinyl, tetrahydrofuranyl, tetrahydropyridinyl, tetrahydropyranyl, 1,3-dioxolane, 1,3-dioxanyl Hexyl, 1,4-dioxanyl, etc., but the present invention is not limited to the above-mentioned examples. Furthermore, the base also includes those having a cross-linked structure.
於本說明書中，「含氧基」意指具有碳原子及氧原子(例如1～5個、1～4個、或1～3個)作為構成原子之基，該基可包含1個或複數個不飽和鍵，亦可不包含碳原子，但不含芳香族基。作為「含氧基」之具體例，可例舉：羥基、烷氧基(例如，甲氧基、乙氧基等)、烯基氧基(例如，乙烯氧基、丙烯基氧基等)、環氧乙烷基、氧雜環丁基、四氫呋喃基、烯基氧基烷基-環烷基-烷基(例如，4-(乙烯氧基甲基)環己烷-1-基等)、-(OCH2 CH2 )x -OH、-(OCH2 CH2 )x -OCH=CH2 (此處，x為1～4之整數)等，但本發明並不僅限定於上述例示。In this specification, "oxygen-containing" means a group having carbon atoms and oxygen atoms (for example, 1 to 5, 1 to 4, or 1 to 3) as constituent atoms, and the group may contain 1 or more An unsaturated bond may not contain carbon atoms, but does not contain an aromatic group. Specific examples of "oxygen-containing" include hydroxyl, alkoxy (for example, methoxy, ethoxy, etc.), alkenyloxy (for example, vinyloxy, propenyloxy, etc.), Ethylene oxide, oxetanyl, tetrahydrofuranyl, alkenyloxyalkyl-cycloalkyl-alkyl (for example, 4-(vinyloxymethyl)cyclohexane-1-yl, etc.), -(OCH 2 CH 2 ) x -OH, -(OCH 2 CH 2 ) x -OCH=CH 2 (here, x is an integer of 1 to 4), etc. However, the present invention is not limited to the above examples.
於本說明書中，「含氧環」及「含氧環式基」意指具有碳原子及1～3個氧原子作為構成環之原子之環式基，該基可包含1個或複數個不飽和鍵，但不含芳香族基。例如，「3～8員含氧環」意指構成環之原子數量為3～8個之含氧環。「含氧環」可例舉：環氧乙烷基、四氫呋喃基、氧雜環丁基、1,3-二氧戊環基、1,3-二氧雜環己基、1,4-二氧雜環己基等，但本發明並不僅限定於上述例示。再者，該基亦包含具有交聯結構者。In this specification, "oxygen-containing ring" and "oxygen-containing cyclic group" mean a cyclic group having carbon atoms and 1 to 3 oxygen atoms as the atoms constituting the ring, and the group may include one or more Saturated bond, but does not contain aromatic groups. For example, "3-8 member oxygen-containing ring" means an oxygen-containing ring with 3-8 atoms constituting the ring. "Oxygen-containing ring" may be exemplified by oxirane group, tetrahydrofuranyl group, oxetanyl group, 1,3-dioxolane group, 1,3-dioxanyl group, 1,4-dioxyl group Heterocyclic hexyl, etc., but the present invention is not limited to the above examples. Furthermore, the base also includes those having a cross-linked structure.
於本說明書中，「芳基」係指與芳香族烴之環鍵結之氫原子脫離1個所產生之基。例如，由苯衍生出苯基(C6
H5
-)，由甲苯衍生出甲苯基(CH3
C6
H4
-)，由二甲苯衍生出二甲苯基((CH3
)2
C6
H3
-)，由萘衍生出萘基(C10
H8
-)。「C6 ～ 14
芳基」意指碳數為6～14之芳香族烴基。作為「C6 ～ 14
芳基」之具體例，例如可例舉：苯基、1-萘基、2-萘基、薁基、二氫苊基、苊基、蒽基、茀基、丙烯合萘基、菲基等。作為「C6 ～ 18
芳基」之具體例，例如可例舉：C6 ～ 14
芳基、苯并[a]蒽基、苯并[a]茀基、苯并[c]菲基、
於本說明書中，「雜芳基」意指單環式或者多環式之含雜原子芳香族基，該基包含1個以上(例如1～4個)選自氮原子、硫原子及氧原子之同種或異種雜原子。例如，「5～18員雜芳基」意指構成環之原子數為5～18個之雜芳基。「鹵雜芳基」係指構成環之原子上之1個或複數個氫被取代為鹵素者。作為「雜芳基」之具體例，例如可例舉：吡咯基、噻吩基、苯并噻吩基、苯并呋喃基、苯并㗁唑基、苯并噻唑基、呋喃基、㗁唑基、噻唑基、異㗁唑基、異噻唑基、苯并異㗁唑基、苯并異噻唑基、咪唑基、吡唑基、吡啶基、吡𠯤基、嘧啶基、嗒𠯤基、喹啉基、異喹啉基、三唑基、三𠯤基、四唑基、吲哚基、咪唑[1,2-a]吡啶基、吡唑并[1,5-a]吡啶基、[1,2,4]三唑并[1,5-a]吡啶基、苯并咪唑基、喹㗁啉基、噌啉基、喹唑啉基、吲唑基、㖠啶基、喹啉醯基、異喹啉醯基等，但本發明並不僅限定於上述例示。In this specification, "heteroaryl" means a monocyclic or polycyclic heteroatom-containing aromatic group, which contains one or more (for example, 1 to 4) selected from nitrogen atoms, sulfur atoms and oxygen atoms The same or different heteroatoms. For example, "5- to 18-membered heteroaryl group" means a heteroaryl group with 5 to 18 atoms constituting the ring. "Haloheteroaryl" means one or more hydrogens on the atoms constituting the ring are substituted with halogen. Specific examples of "heteroaryl" include, for example, pyrrolyl, thienyl, benzothienyl, benzofuranyl, benzoazolyl, benzothiazolyl, furyl, oxazolyl, and thiazole. Group, isothiazolyl, isothiazolyl, benzisothiazolyl, benzisothiazolyl, imidazolyl, pyrazolyl, pyridyl, pyridyl, pyrimidinyl, pyridyl, quinolinyl, iso Quinolinyl, triazolyl, triazolyl, tetrazolyl, indolyl, imidazole[1,2-a]pyridyl, pyrazolo[1,5-a]pyridyl, [1,2,4 ]Triazolo[1,5-a]pyridyl, benzimidazolyl, quinazolinyl, cinnolinyl, quinazolinyl, indazolyl, pyridinyl, quinolinyl, isoquinolinyl However, the present invention is not limited to the above-mentioned examples.
通常，用語「(經)取代」係指藉由特定取代基之自由基來取代給定結構中之1個以上之氫自由基。關於語句「可經取代」，可以理解為可與語句「未經取代或經取代(之)」互換地使用。例如，「可經C1 ～ 10 烷基取代之C6 ～ 18 芳基」與「未經取代之C6 ～ 18 芳基、或經C1 ～ 10 烷基取代之C6 ～ 18 芳基」同義。於本說明書中，關於使用「(經)取代」或「可經取代」進行定義之基中之取代基之數量，只要能夠取代，則並無特別限制，為1個或複數個。又，除特別指示之情形以外，各基之說明亦適用於該基為其他基之一部分或取代基之情形。亦存在將「取代基」之定義中之碳原子之數量表述為例如「C1-6 」等之情況。具體而言，「C1-6 烷基」之表述係與碳數1至6之烷基同義。又，於本說明書中，關於未特別明示用語「(經)取代」或「可經取代」之取代基，意指「未經取代」之取代基。Generally, the term "(by) substitution" refers to the substitution of more than one hydrogen radical in a given structure by radicals of specific substituents. Regarding the sentence "may be substituted", it can be understood that it can be used interchangeably with the sentence "unsubstituted or substituted (of)". For example, "it may be substituted by C 1 ~ 10 alkyl C 6 ~ 18 aryl group" and "substituted of unsubstituted of C 6 ~ 18 aryl group, or with C 1 ~ 10 alkyl C 6 ~ 18 aryl group." Synonymous. In this specification, the number of substituents in a group defined using "() substituted" or "substitutable" is not particularly limited as long as it can be substituted, and it is one or plural. In addition, except in the case of special instructions, the description of each group also applies to the case where the group is a part of other groups or substituents. There are also cases where the number of carbon atoms in the definition of "substituent" is expressed as, for example, "C 1-6 ". Specifically, the expression of "C 1-6 alkyl" is synonymous with an alkyl having 1 to 6 carbon atoms. In addition, in this specification, the term "(substitutable)" or "substitutable" substituents which are not expressly indicated in particular means "unsubstituted" substituents.
於本說明書中，「經含氧基取代之烷基」係指上述烷基上之1個氫原子被取代為含氧基之烷基、及(2)烷基之同一碳上之2個氫原子被取代而形成包含該碳作為環原子之含氧環之烷基。經含氧基取代之烷基之含氧基可未經取代，亦可經C1 ～ 6 烷基及/或乙烯氧基取代。作為經含氧基取代之烷基之例，可例舉：2-甲氧基乙基、2-羥基乙基、3-羥基丙基、3-(乙烯氧基)丙基、4-羥基丁基、4-(乙烯氧基)丁基、2,3-環氧丙基、(3-乙基氧雜環丁烷-3-基)甲基、四氫呋喃甲基、(2-乙基-2-甲基-1,3-二氧雜環戊烷-4-基)甲基、[4-(乙烯氧基甲基)環己基]甲基、[4-(羥甲基)環己基]甲基、-(CH2 CH2 O)x -H、-(CH2 CH2 O)x -CH=CH2 (此處，x為1～5之整數)等，但本發明並不僅限定於上述例示。In this specification, "alkyl group substituted with an oxy group" means that one hydrogen atom on the above-mentioned alkyl group is replaced with an oxy group-containing alkyl group, and (2) two hydrogens on the same carbon of the alkyl group The atom is substituted to form an oxygen-containing ring alkyl group containing the carbon as a ring atom. Alkyl group containing substituted by the group containing the group may be unsubstituted, may also be substituted by C 1 ~ 6 alkyl group and / or an ethylene group. Examples of alkyl groups substituted with oxygen-containing groups include: 2-methoxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 3-(vinyloxy)propyl, 4-hydroxybutyl Group, 4-(vinyloxy)butyl, 2,3-epoxypropyl, (3-ethyloxetan-3-yl)methyl, tetrahydrofuranmethyl, (2-ethyl-2 -Methyl-1,3-dioxolane-4-yl)methyl, [4-(vinyloxymethyl)cyclohexyl]methyl, [4-(hydroxymethyl)cyclohexyl]methyl Group, -(CH 2 CH 2 O) x -H, -(CH 2 CH 2 O) x -CH=CH 2 (here, x is an integer of 1 to 5), etc., but the present invention is not limited to the above Exemplify.
於本說明書中，「經含氧基取代之環烷基」係指上述環烷基上之1個氫原子被取代為含氧基之烷基、及(2)環烷基之同一碳上之2個氫原子被取代而形成包含該碳作為環原子之含氧環之環烷基。經含氧基取代之環烷基之含氧基可未經取代，亦可經C1 ～ 6 烷基及/或乙烯氧基取代。作為經含氧基取代之環烷基之例，可例舉：4-(乙烯氧基甲基)環己基、4-(羥甲基)環己基等，但本發明並不僅限定於上述例示。In the present specification, "cycloalkyl substituted with an oxygen-containing group" means that one hydrogen atom on the above-mentioned cycloalkyl group is substituted with an oxygen-containing alkyl group, and (2) a cycloalkyl group on the same carbon Two hydrogen atoms are substituted to form a cycloalkyl group of an oxygen-containing ring containing the carbon as a ring atom. The oxygen-containing group substituted by the cycloalkyl group-containing group may be unsubstituted, may be substituted with C 1 ~ 6 alkyl group and / or an ethylene group. Examples of the cycloalkyl group substituted with an oxygen-containing group include 4-(vinyloxymethyl)cyclohexyl, 4-(hydroxymethyl)cyclohexyl, etc., but the present invention is not limited to the above-mentioned examples.
於本說明書中，「經含氧環取代之烷基」係指(1)上述烷基上之1個氫原子被取代為含氧環之烷基、及(2)烷基之同一碳上之2個氫原子被取代而形成包含該碳作為環原子之含氧環之烷基。經含氧環取代之烷基之含氧環可未經取代，亦可經C1 ～ 6 烷基取代。作為經含氧環取代之烷基之例，可例舉：2,3-環氧丙基、(3-乙基氧雜環丁烷-3-基)甲基、四氫呋喃甲基、(2-乙基-2-甲基-1,3-二氧雜環戊烷-4-基)甲基、(5-乙基-1,3-二㗁烷-5-基)甲基等，但本發明並不僅限定於上述例示。In this specification, the "alkyl group substituted with an oxygen-containing ring" means (1) one hydrogen atom on the above-mentioned alkyl group is substituted with an oxygen-containing ring alkyl group, and (2) the alkyl group on the same carbon Two hydrogen atoms are substituted to form an oxygen-containing ring alkyl group containing the carbon as a ring atom. The oxygen-oxygen-substituted cycloalkyl the cycloalkyl group may be unsubstituted, may be substituted with C 1 ~ 6 alkyl group. Examples of alkyl groups substituted with oxygen-containing rings include 2,3-epoxypropyl, (3-ethyloxetan-3-yl)methyl, tetrahydrofuranmethyl, (2- Ethyl-2-methyl-1,3-dioxolane-4-yl)methyl, (5-ethyl-1,3-dioxan-5-yl)methyl, etc., but this The invention is not limited to the above-mentioned examples.
於本說明書中，「聚合物」係指藉由使複數個單體聚合所產生之化合物。於此情形時，單體為「起始物質(材料)」，聚合物為產物(最終產物)。In this specification, "polymer" refers to a compound produced by polymerizing a plurality of monomers. In this case, the monomer is the "starting substance (material)" and the polymer is the product (final product).
於本說明書中，「均聚物」係藉由使僅1種單體聚合所產生之化合物，「共聚物」係藉由使2種或者超過2種之單體聚合所產生之化合物。In this specification, "homopolymer" is a compound produced by polymerizing only one monomer, and "copolymer" is a compound produced by polymerizing two or more monomers.
於本說明書中，「包含單體成分之共聚物」係指使該單體成分聚合所生成之共聚物。In this specification, "a copolymer containing a monomer component" refers to a copolymer produced by polymerizing the monomer component.
於本說明書中，單體A之共聚物意指所包含之單體之一種為單體A之共聚物。In this specification, the copolymer of monomer A means that one of the contained monomers is a copolymer of monomer A.
於本說明書中，「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯，丙烯酸酯及甲基丙烯酸酯可分別單獨使用，亦可併用。「(甲基)丙烯醯氧基」意指丙烯醯氧基或甲基丙烯醯氧基，丙烯醯氧基及甲基丙烯醯氧基可分別單獨使用，亦可併用。「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸，丙烯酸及甲基丙烯酸可分別單獨使用，亦可併用。In this specification, "(meth)acrylate" means acrylate or methacrylate, and acrylate and methacrylate may be used alone or in combination. The "(meth)acryloxy group" means an acryloxy group or a methacryloxy group, and the acryloxy group and the methacryloxy group may be used alone or in combination. "(Meth)acrylic acid" means acrylic acid or methacrylic acid, and acrylic acid and methacrylic acid may be used alone or in combination.
於本說明書中，「(甲基)丙烯酸聚合物」及「(甲基)丙烯酸系聚合物」係指(甲基)丙烯酸或者(甲基)丙烯酸酯或其鹽或者衍生物等均聚物或共聚物。In this specification, "(meth)acrylic polymer" and "(meth)acrylic polymer" refer to homopolymers or homopolymers such as (meth)acrylic acid or (meth)acrylic acid esters or their salts or derivatives. Copolymer.
於本說明書中，「單體」係指其2個以上聚合而會產生聚合物之化合物。作為本發明之單體之例，可例舉：(甲基)丙烯酸系單體、乙烯系單體、胺基甲酸酯系單體、醯胺系單體、酯系單體、醚系單體、醯亞胺系單體、醯胺-醯亞胺系單體、碳酸酯系單體、縮醛系單體、碸系單體、苯硫醚系單體、乙烯基醚系單體、醚醚酮系單體、聚矽氧系單體、苯乙烯系單體、丁二烯系單體及藉由聚合會形成AES(Acrylonitrile-EPDM-Styrene，丙烯腈-三元乙丙橡膠-苯乙烯)樹脂、鄰苯二甲酸二烯丙酯樹脂、ABS(Acrylonitrile-Butadiene-Styrene，丙烯腈-丁二烯-苯乙烯)樹脂、或者聚矽氧樹脂等之單體。In this specification, "monomer" refers to a compound that polymerizes two or more of them to produce a polymer. Examples of monomers of the present invention include (meth)acrylic monomers, vinyl monomers, urethane-based monomers, amide-based monomers, ester-based monomers, and ether-based monomers. Monomers, amide-based monomers, amide-imid-based monomers, carbonate-based monomers, acetal-based monomers, sulfide-based monomers, phenylsulfide-based monomers, vinyl ether-based monomers, Ether ether ketone monomers, silicone monomers, styrene monomers, butadiene monomers and AES (Acrylonitrile-EPDM-Styrene, acrylonitrile-ethylene propylene rubber-benzene Ethylene) resin, diallyl phthalate resin, ABS (Acrylonitrile-Butadiene-Styrene, acrylonitrile-butadiene-styrene) resin, or monomers such as polysiloxane resin.
於本說明書中，「乙烯基醚單體」與「乙烯基醚系單體」可交換使用，為包含乙烯氧基(即，-O-CH=CH2 )之單體。作為其例，可例舉：4-羥基丁基乙烯基醚(HBVE)、以及2-羥基乙基乙烯基醚(HEVE)、二乙二醇單乙烯基醚(DEGV)、正丙基乙烯基醚(NPVE)、異丙基乙烯基醚(IPVE)、正丁基乙烯基醚(NBVE)、異丁基乙烯基醚(IBVE)、2-乙基己基乙烯基醚(2-EHVE)、環己基乙烯基醚(CHVE)、1,4-環己烷二甲醇單乙烯基醚(CHMVE)、1,4-丁二醇二乙烯基醚(BDVE)、三乙二醇二乙烯基醚(TEGDVE)、二乙二醇二乙烯基醚(DEGDVE)、1,4-環己烷二甲醇二乙烯基醚(CHDVE)等，但本發明並不僅限定於上述例示。In this specification, "vinyl ether monomer" and "vinyl ether-based monomer" are used interchangeably, and are monomers containing vinyloxy groups (ie, -O-CH=CH 2 ). Examples include: 4-hydroxybutyl vinyl ether (HBVE), 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), n-propyl vinyl ether Ether (NPVE), isopropyl vinyl ether (IPVE), n-butyl vinyl ether (NBVE), isobutyl vinyl ether (IBVE), 2-ethylhexyl vinyl ether (2-EHVE), ring Hexyl vinyl ether (CHVE), 1,4-cyclohexanedimethanol monovinyl ether (CHMVE), 1,4-butanediol divinyl ether (BDVE), triethylene glycol divinyl ether (TEGDVE) ), diethylene glycol divinyl ether (DEGDVE), 1,4-cyclohexanedimethanol divinyl ether (CHDVE), etc., but the present invention is not limited to the above examples.
於本說明書中，「燒結」(sintering)係指原料粉末於高溫下煅燒凝固之現象，於原料粉末之粒子間可觀察到間隙，但若於高溫環境下(低於熔點之溫度)發生燒結，則粒子間之接觸面積增加而間隙減少，從而煅燒凝固。將殘留之間隙稱為「空隙」或「孔隙」。In this specification, "sintering" refers to the phenomenon of raw material powder being calcined and solidified at a high temperature. Gaps can be observed between the particles of the raw material powder, but if sintering occurs in a high temperature environment (a temperature below the melting point), Then the contact area between the particles increases and the gap decreases, thereby calcining and solidifying. The remaining gaps are called "voids" or "pores".
於本說明書中，「套組」係指會提供通常應分為2個以上之區塊來提供之部分(例如塗佈成分、導電成分、溶劑、說明書等)之單元。為了穩定性等，不應混合來提供，較佳為於即將使用之前混合使用，以提供此種組合物為目的時，該套組之形態較佳。較為有利的是此種套組具備指示書或說明書，該指示書或說明書較佳為記載以何種方式使用所提供之部分(例如導電成分、塗佈成分)、或者應以何種方式處理試劑或者使用後之廢液。於本說明書中，於使用套組之情形時，套組中通常可包含記載有溶劑等之使用方法等之指示書等。In this manual, "set" refers to a unit that provides parts (such as coating components, conductive components, solvents, manuals, etc.) that should usually be divided into two or more blocks to provide. For stability, etc., it should not be mixed and provided, and it is preferable to mix and use immediately before use. When the purpose is to provide such a composition, the form of the kit is preferred. It is more advantageous that such a kit has instructions or instructions, and the instructions or instructions preferably record how to use the provided parts (such as conductive components, coating components), or how to treat the reagents Or waste liquid after use. In this manual, in the case of using the set, the set can usually include instructions that describe how to use the solvent, etc., etc.
(導電材之基本說明) 本發明中所提供之導電材包含該領域中能夠獲取之任意導電成分。本發明之導電材之特徵在於：藉由包含本發明中所提供之用以降低燒成溫度之組合物(亦稱為燒成溫度降低劑)而降低用以獲得導電材之燒成溫度。(Basic description of conductive material) The conductive material provided in the present invention contains any conductive component that can be obtained in the field. The conductive material of the present invention is characterized in that the firing temperature for obtaining the conductive material is lowered by including the composition for lowering the firing temperature provided in the present invention (also referred to as the firing temperature reducer).
關於本發明之導電材，代表性而言，可包含導電成分之其他基材。Regarding the conductive material of the present invention, representatively, other substrates containing conductive components may be included.
(燒成溫度降低劑之基本說明)
本發明中所提供之用以降低導電材之燒成溫度之組合物(燒成溫度降低劑)包含由式(4)
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於代表性之實施方式中，本發明中所提供之由式(4)表示之化合物無論所包含之含氧基或者含氧環之種類、烷基之形態(碳數、分支/直鏈之狀態等)、環烷基之形態(碳數等)、甲基丙烯醯氧基(n＝1，R1 ＝甲基)、丙烯醯氧基(n＝1，R1 ＝H)、乙烯氧基(n＝0，R1 ＝H)、1-丙烯-2-基氧基(n＝0，R1 ＝甲基)之有何差別等，均會降低燒成溫度。In a representative embodiment, the compound represented by formula (4) provided in the present invention does not matter whether it contains the oxygen-containing or oxygen-containing ring type, the form of the alkyl group (carbon number, branched/straight chain state etc.), a cycloalkyl group of the form (carbon number, etc.), Bing Xixi methyl group (n = 1, R 1 = methyl), Bing Xixi group (n = 1, R 1 = H), an ethylene group, (n = 0, R 1 = H), 1- propen-2-yl group (n = 0, R 1 = methyl) in place of the difference and the like, will decrease the firing temperature.
於一實施方式中，R2 為可經含氧基取代之烷基或環烷基。In one embodiment, R 2 is an alkyl group or a cycloalkyl group which may be substituted with an oxygen-containing group.
於一實施方式中，R2 為經含氧基取代之烷基。In one embodiment, R 2 is an alkyl group substituted with an oxygen-containing group.
於一實施方式中，R2 為經含氧環取代之烷基。In one embodiment, R 2 is an alkyl group substituted with an oxygen-containing ring.
於一實施方式中，由式(4)表示之化合物為經含氧基取代之(甲基)丙烯酸烷基酯。In one embodiment, the compound represented by formula (4) is an alkyl (meth)acrylate substituted with an oxygen-containing group.
於一實施方式中，由式(4)表示之化合物為經含氧環取代之(甲基)丙烯酸烷基酯。In one embodiment, the compound represented by formula (4) is an alkyl (meth)acrylate substituted with an oxygen-containing ring.
於一實施方式中，n＝0。於一實施方式中，n＝0，R2 為可經含氧基取代之烷基或環烷基。In one embodiment, n=0. In one embodiment, n=0, and R 2 is an alkyl group or a cycloalkyl group which may be substituted by an oxygen-containing group.
於一實施方式中，n＝0，由式(4)表示之化合物具有1個或者2個或多於2個乙烯氧基。In one embodiment, n=0, and the compound represented by formula (4) has 1 or 2 or more than 2 vinyloxy groups.
於一實施方式中，上述組合物(燒成溫度降低劑)包含經含氧基取代之(甲基)丙烯酸烷基酯。於一實施方式中，上述組合物(燒成溫度降低劑)亦包含經含氧環取代之(甲基)丙烯酸烷基酯。於一實施方式中，上述組合物(燒成溫度降低劑)包含n為0且由式(4)表示之化合物。於一實施方式中，上述組合物(燒成溫度降低劑)包含n為0且R1 為氫原子之由式(4)表示之化合物。In one embodiment, the composition (calcination temperature reducing agent) includes an alkyl (meth)acrylate substituted with an oxygen-containing group. In one embodiment, the above composition (calcination temperature reducing agent) also includes an alkyl (meth)acrylate substituted with an oxygen-containing ring. In one embodiment, the above-mentioned composition (calcination temperature reducing agent) contains a compound whose n is 0 and represented by formula (4). In one embodiment, the composition (calcination temperature reducing agent) includes a compound represented by formula (4) in which n is 0 and R 1 is a hydrogen atom.
於一實施方式中，本發明中所提供之經含氧環取代之(甲基)丙烯酸烷基酯之一例由式(1)表示，
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於一實施方式中，上述導電材包含由式(4)表示之化合物之均聚物或者共聚物及導電成分。In one embodiment, the above-mentioned conductive material includes a homopolymer or copolymer of the compound represented by formula (4) and a conductive component.
於一實施方式中，上述導電材包含上述經含氧基取代之(甲基)丙烯酸烷基酯之均聚物或者共聚物及導電成分。In one embodiment, the above-mentioned conductive material includes the above-mentioned homopolymer or copolymer of the above-mentioned oxygen-containing substituted alkyl (meth)acrylate and a conductive component.
於一實施方式中，上述導電材包含上述經含氧環取代之(甲基)丙烯酸烷基酯之均聚物或者共聚物及導電成分。In one embodiment, the conductive material includes the homopolymer or copolymer of the alkyl (meth)acrylate substituted with the oxygen-containing ring and a conductive component.
於一實施方式中，上述共聚物為由式(4)表示之化合物與第2(甲基)丙烯酸系單體之共聚物。In one embodiment, the above-mentioned copolymer is a copolymer of a compound represented by formula (4) and a second (meth)acrylic monomer.
於一實施方式中，上述共聚物為上述經含氧基取代之(甲基)丙烯酸烷基酯與第2(甲基)丙烯酸系單體之共聚物。In one embodiment, the above-mentioned copolymer is a copolymer of the above-mentioned oxygen-containing substituted alkyl (meth)acrylate and a second (meth)acrylic monomer.
於一實施方式中，上述共聚物為上述經含氧環取代之(甲基)丙烯酸烷基酯與第2(甲基)丙烯酸系單體之共聚物。In one embodiment, the above-mentioned copolymer is a copolymer of the above-mentioned oxygen-containing ring-substituted alkyl (meth)acrylate and a second (meth)acrylic monomer.
於一實施方式中，R2 為可經含氧基取代之烷基或環烷基，上述含氧基為羥基、羥烷基、乙烯氧基烷基、烷氧基、環氧乙烷環或者氧雜環丁烷環、或-(CH2 CH2 O)y -R7 ，R7 為氫或乙烯基，y為1至5之整數。In one embodiment, R 2 is an alkyl group or a cycloalkyl group that may be substituted with an oxygen-containing group, and the aforementioned oxygen-containing group is a hydroxy group, a hydroxyalkyl group, a vinyloxyalkyl group, an alkoxy group, an oxirane ring, or Oxetane ring, or -(CH 2 CH 2 O) y -R 7 , R 7 is hydrogen or vinyl, and y is an integer of 1 to 5.
於一實施方式中，上述含氧基為烷氧基、環氧乙烷環或氧雜環丁烷環。In one embodiment, the above-mentioned oxygen-containing group is an alkoxy group, an oxirane ring or an oxetane ring.
於一實施方式中，上述含氧環為環氧乙烷環或氧雜環丁烷環。In one embodiment, the above-mentioned oxygen-containing ring is an oxirane ring or an oxetane ring.
於一實施方式中，上述含氧基為羥基或烷氧基。In one embodiment, the above-mentioned oxygen-containing group is a hydroxyl group or an alkoxy group.
於一實施方式中，R2 為可經乙烯氧基或者羥基取代之烷基、環烷基、或者烷基環烷基烷基、或-(CH2 CH2 O)y -R7 ，R7 為氫或乙烯基，y為1以上之整數。In one embodiment, R 2 is alkyl, cycloalkyl, or alkylcycloalkylalkyl which may be substituted by vinyloxy or hydroxy, or -(CH 2 CH 2 O) y -R 7 , R 7 It is hydrogen or vinyl, and y is an integer of 1 or more.
於一實施方式中，R1 為氫原子或甲基，R2 為經選自由羥基、烷氧基、環氧乙烷環及氧雜環丁烷環所組成之群中之1個至能夠取代之數量之取代基取代的烷基。In one embodiment, R 1 is a hydrogen atom or a methyl group, and R 2 is selected from the group consisting of a hydroxyl group, an alkoxy group, an oxirane ring, and an oxetane ring to be substituted The number of substituents substituted by the alkyl group.
於一實施方式中，上述經含氧基取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化26]
於一實施方式中，上述經含氧環取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化27]
於一實施方式中，R1 為氫原子或甲基，R2 為可經乙烯氧基或者羥基取代之烷基、環烷基、或者烷基環烷基烷基、或-(CH2 CH2 O)y -R7 ，R7 為氫或乙烯基，y為1至5之整數，n＝0。In one embodiment, R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group, or -(CH 2 CH 2 O) y- R 7 , R 7 is hydrogen or vinyl, y is an integer from 1 to 5, and n=0.
於一實施方式中，於n＝0時，R1 為氫原子。In one embodiment, when n=0, R 1 is a hydrogen atom.
於一實施方式中，上述第2(甲基)丙烯酸系單體由式(2)表示，
[化28]
於一實施方式中，由式(4)表示之化合物為4-羥基丁基乙烯基醚、丙烯酸2-甲氧基乙酯、丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯或甲基丙烯酸2,3-環氧丙酯。In one embodiment, the compound represented by formula (4) is 4-hydroxybutyl vinyl ether, 2-methoxyethyl acrylate, acrylic acid (3-ethyloxetan-3-yl)methyl Ester or 2,3-glycidyl methacrylate.
於一實施方式中，上述經含氧基取代之(甲基)丙烯酸烷基酯為丙烯酸2-甲氧基乙酯、丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯或甲基丙烯酸2,3-環氧丙酯。In one embodiment, the above-mentioned alkyl (meth)acrylate substituted with an oxygen-containing group is 2-methoxyethyl acrylate, (3-ethyloxetan-3-yl)methyl acrylate or 2,3-glycidyl methacrylate.
於一實施方式中，上述經含氧環取代之(甲基)丙烯酸烷基酯為丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯或甲基丙烯酸2,3-環氧丙酯。In one embodiment, the above-mentioned alkyl (meth)acrylate substituted with an oxygen-containing ring is (3-ethyloxetan-3-yl)methyl acrylate or 2,3-epoxy methacrylate Propyl ester.
於一實施方式中，由式(4)表示之化合物為4-羥基丁基乙烯基醚。In one embodiment, the compound represented by formula (4) is 4-hydroxybutyl vinyl ether.
於一實施方式中，上述第2(甲基)丙烯酸系單體為丙烯酸乙酯、丙烯酸硬脂酯、丙烯酸異硬脂酯或丙烯酸月桂酯。In one embodiment, the above-mentioned second (meth)acrylic monomer is ethyl acrylate, stearyl acrylate, isostearyl acrylate, or lauryl acrylate.
於一較佳之實施方式中，由式(4)表示之化合物為丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯或甲基丙烯酸2,3-環氧丙酯，且上述第2(甲基)丙烯酸系單體為丙烯酸異硬脂酯。於一較佳之實施方式中，由式(4)表示之化合物為丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯，且上述第2(甲基)丙烯酸系單體為丙烯酸異硬脂酯。於一較佳之實施方式中，由式(4)表示之化合物為甲基丙烯酸2,3-環氧丙酯，且上述第2(甲基)丙烯酸系單體為丙烯酸異硬脂酯。In a preferred embodiment, the compound represented by formula (4) is (3-ethyloxetan-3-yl) methyl acrylate or 2,3-glycidyl methacrylate, and the above The second (meth)acrylic monomer is isostearyl acrylate. In a preferred embodiment, the compound represented by formula (4) is (3-ethyloxetan-3-yl)methyl acrylate, and the second (meth)acrylic monomer is acrylic acid Isostearyl ester. In a preferred embodiment, the compound represented by formula (4) is 2,3-glycidyl methacrylate, and the second (meth)acrylic monomer is isostearyl acrylate.
於一較佳之實施方式中，由式(4)表示之化合物為4-羥基丁基乙烯基醚或丙烯酸2-甲氧基乙酯，且上述第2(甲基)丙烯酸系單體為丙烯酸乙酯。於一較佳之實施方式中，由式(4)表示之化合物為丙烯酸2-甲氧基乙酯，且上述第2(甲基)丙烯酸系單體為丙烯酸乙酯。於一較佳之實施方式中，由式(4)表示之化合物為4-羥基丁基乙烯基醚，且上述第2(甲基)丙烯酸系單體為丙烯酸乙酯。In a preferred embodiment, the compound represented by formula (4) is 4-hydroxybutyl vinyl ether or 2-methoxyethyl acrylate, and the second (meth)acrylic monomer is ethyl acrylate. ester. In a preferred embodiment, the compound represented by formula (4) is 2-methoxyethyl acrylate, and the second (meth)acrylic monomer is ethyl acrylate. In a preferred embodiment, the compound represented by formula (4) is 4-hydroxybutyl vinyl ether, and the second (meth)acrylic monomer is ethyl acrylate.
燒成溫度降低劑之基本使用方法如以下。The basic usage method of the firing temperature reducing agent is as follows.
(作為燒成溫度降低劑對象之導電材) 可作為本發明之燒成溫度降低劑對象之導電材為含有任意導電成分及聚合物基質之材料，較佳為任意導電成分包含金屬系成分、進而較佳為任意導電成分包含金屬成分者。(As a conductive material for the firing temperature reducer) The conductive material that can be the target of the firing temperature lowering agent of the present invention is a material containing an arbitrary conductive component and a polymer matrix, preferably the arbitrary conductive component contains a metal-based component, and more preferably the arbitrary conductive component contains a metal component.
(導電材之一般製法) (1)聚合物基質之製造方法 於代表性之實施方式中，本發明之聚合物基質可藉由將單體進行加熱、及/或藉由對單體照射特定照度之紫外線使之聚合而製備。關於此種紫外線照射，業者可任意地設定而實施。於製備聚合物基質時，於使用紫外線使之聚合而製備之情形時不需要煩雜之操作，即用以去除溶劑之乾燥操作，作業性優異。(General manufacturing method of conductive material) (1) Manufacturing method of polymer matrix In a representative embodiment, the polymer matrix of the present invention can be prepared by heating the monomer and/or by irradiating the monomer with ultraviolet light with a specific illuminance to polymerize it. Regarding such ultraviolet irradiation, the manufacturer can arbitrarily set and implement it. When preparing the polymer matrix, there is no need for complicated operations in the case of using ultraviolet rays to polymerize it, that is, the drying operation to remove the solvent, and the workability is excellent.
此處，紫外線係指波長短於可見光線且波長長於X射線之電磁波。可見光之短波長端之上限為400 nm，紫外線可定義為具有400 nm以下之波長之電磁波。紫外線之波長之下限為10 nm左右，只要為具有長於10 nm左右之波長之電磁波，則可以理解為屬於紫外線之範疇。本發明中所使用之紫外線之波長無論為何種波長均可，可視目的來選擇適當者。例如，於本發明中，只要能夠對單體發揮出初始效果，則無論何種波長均可。代表性而言，為如下波長，即，可藉由實施例中所使用之光源進行照射之波長。具體而言，可使用150 nm～400 nm左右之光源，較佳為300 nm～400 nm。Here, ultraviolet rays refer to electromagnetic waves with wavelengths shorter than visible rays and longer than X-rays. The upper limit of the short wavelength end of visible light is 400 nm, and ultraviolet rays can be defined as electromagnetic waves with a wavelength below 400 nm. The lower limit of the wavelength of ultraviolet light is about 10 nm. As long as it is an electromagnetic wave with a wavelength longer than about 10 nm, it can be understood as belonging to the category of ultraviolet light. The wavelength of the ultraviolet rays used in the present invention may be any wavelength, and an appropriate one can be selected depending on the purpose. For example, in the present invention, any wavelength may be used as long as the initial effect can be exerted on the monomer. Typically, it is a wavelength that can be irradiated by the light source used in the embodiment. Specifically, a light source of about 150 nm to 400 nm can be used, preferably 300 nm to 400 nm.
本發明中所使用之紫外線之較佳照度係根據起始物質而有所不同。紫外線照射裝置並無特別限定，例如可例舉：低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、黑光燈、UV(ultraviolet，紫外線)無電極燈、短弧燈、LED(Light Emitting Diode，發光二極體)等。The preferred illuminance of ultraviolet rays used in the present invention varies according to the starting material. The ultraviolet irradiation device is not particularly limited, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, black light lamp, UV (ultraviolet, ultraviolet) electrodeless lamp, short arc lamp, LED (Light Emitting Diode, light-emitting diode) and so on.
於使單體聚合時，較佳為使用聚合起始劑。作為聚合起始劑，例如可例舉：熱聚合起始劑、光聚合起始劑、氧化還原聚合起始劑、ATRP(Atom Transfer Radical Polymerization，原子轉移自由基聚合)起始劑、ICAR ATRP(Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization，連續再生觸媒引發劑-原子轉移自由基聚合)起始劑、ARGET ATRP(Activator ReGenerated by Electron Transfer Atom Transfer Radical Polymerization，電子轉移觸媒再生-原子轉移自由基聚合)起始劑、RAFT(Reversible Addition-Fragmentation Chain Transfer，可逆加成-斷裂鏈轉移聚合)劑、NMP(Nitroxide Mediated Polymerization，氮氧化物調控聚合作用)(經由氮氧化物之聚合)劑、高分子聚合起始劑等。該等聚合起始劑可分別單獨使用，亦可將2種以上併用。該等聚合起始劑之中，就使聚合物基質不會殘留熱歷程之觀點而言，較佳為光聚合起始劑。When polymerizing monomers, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, thermal polymerization initiator, photopolymerization initiator, redox polymerization initiator, ATRP (Atom Transfer Radical Polymerization) initiator, ICAR ATRP ( Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization, continuous regeneration catalyst initiator-atom transfer radical polymerization initiator, ARGET ATRP (Activator ReGenerated by Electron Transfer Atom Transfer Radical Polymerization, electron transfer catalyst regeneration-atom transfer radical polymerization) Polymerization) initiator, RAFT (Reversible Addition-Fragmentation Chain Transfer) agent, NMP (Nitroxide Mediated Polymerization) (polymerization via nitrogen oxide) agent, high Molecular polymerization initiators, etc. These polymerization initiators may be used alone, respectively, or two or more of them may be used in combination. Among these polymerization initiators, a photopolymerization initiator is preferred from the viewpoint of preventing the thermal history from remaining in the polymer matrix.
作為光聚合起始劑，例如可例舉：2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2'-雙(鄰氯苯基)-4,4',5,5'-四苯基-1,1'-聯咪唑、2,4,6-三(三氯甲基)-1,3,5-三𠯤、2,4-雙(三氯甲基)-6-(對甲氧基苯基乙烯基)-1,3,5-三𠯤、二苯基錪四氟硼酸鹽、二苯基錪六氟磷酸鹽、4,4'-二第三丁基二苯基錪四氟硼酸鹽、4-二乙基胺基苯基苯重氮鎓六氟磷酸鹽、安息香、2-羥基-2-甲基-1-苯基丙烷-2-酮、二苯甲酮、9-氧硫
於使用光聚合起始劑作為聚合起始劑之情形時，關於該光聚合起始劑之量，相對於全部單體100重量份，通常較佳為約0.01重量份～約20重量份。When a photopolymerization initiator is used as the polymerization initiator, the amount of the photopolymerization initiator is generally preferably about 0.01 parts by weight to about 20 parts by weight relative to 100 parts by weight of the total monomers.
作為熱聚合起始劑，例如可例舉：偶氮雙異丁腈(AIBN)、2,2'-偶氮雙(異丁酸甲酯)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2-甲基丁腈)、1,1'-偶氮雙(環己烷-1-甲腈)等偶氮系聚合起始劑、過氧化苯甲醯、過硫酸鉀、過硫酸銨等過氧化物系聚合起始劑等，但本發明並不僅限定於上述例示。該等聚合起始劑可分別單獨使用，亦可將2種以上併用。As the thermal polymerization initiator, for example, azobisisobutyronitrile (AIBN), 2,2'-azobis(methyl isobutyrate), 2,2'-azobis(2,4 -Dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile) and other azo polymerization start Agents, peroxide-based polymerization initiators such as benzoyl peroxide, potassium persulfate, and ammonium persulfate, etc., but the present invention is not limited to the above-mentioned examples. These polymerization initiators may be used alone, respectively, or two or more of them may be used in combination.
於使用熱聚合起始劑作為聚合起始劑之情形時，關於該熱聚合起始劑之量，相對於全部單體100重量份，通常較佳為約0.01重量份～約20重量份。When a thermal polymerization initiator is used as the polymerization initiator, the amount of the thermal polymerization initiator is generally preferably about 0.01 parts by weight to about 20 parts by weight relative to 100 parts by weight of the total monomers.
於使用AIBN等在聚合反應時產生氮氣(N2 )之聚合起始劑之情形時，作為結果，所產生之複合材有時包含氣泡。此種氣泡有可能成為斷裂之起點，因此可以預測，有複合材之伸長性等性質降低之虞，另一方面，衝擊吸收能有可能提昇。再者，複合材中所包含之氣泡不限定於源自聚合起始劑者，可為藉由能夠使樹脂等包含氣泡之公知方法而獲得之氣泡，例如藉由添加發泡劑而獲得者、或藉由去除溶劑而獲得者等。In the case of using a polymerization initiator such as AIBN that generates nitrogen (N 2 ) during the polymerization reaction, as a result, the resulting composite material sometimes contains bubbles. Such bubbles may become the starting point of fracture. Therefore, it can be predicted that the elongation and other properties of the composite material may decrease. On the other hand, the impact absorption energy may increase. Furthermore, the bubbles contained in the composite material are not limited to those derived from a polymerization initiator, and may be bubbles obtained by a known method capable of containing bubbles in resins, for example, those obtained by adding a foaming agent, Or obtained by removing the solvent, etc.
作為本發明中可使用之其他聚合起始劑，例如可例舉：過氧化氫與鐵(II)鹽、過硫酸鹽與亞硫酸氫鈉等氧化還原聚合起始劑、於金屬觸媒下使用鹵化烷基之ATRP(原子轉移自由基聚合)起始劑、使用金屬及含氮配位基之ICAR ATRP起始劑或ARGET ATRP起始劑、RAFT(可逆加成-斷裂鏈轉移聚合)劑、NMP(經由氮氧化物之聚合)劑、含聚二甲基矽氧烷單元之高分子偶氮聚合起始劑、含聚乙二醇單元之高分子偶氮聚合起始劑等高分子聚合起始劑等，但本發明並不僅限定於上述例示。該等聚合起始劑可分別單獨使用，亦可將2種以上併用。As other polymerization initiators that can be used in the present invention, for example, redox polymerization initiators such as hydrogen peroxide and iron (II) salt, persulfate and sodium bisulfite, etc., used under a metal catalyst ATRP (atom transfer radical polymerization) initiators of halogenated alkyl groups, ICAR ATRP initiators or ARGET ATRP initiators using metals and nitrogen-containing ligands, RAFT (reversible addition-fragmentation chain transfer polymerization) agents, Polymerization of polymers such as NMP (polymerization via nitrogen oxides) agents, polymer azo polymerization initiators containing polydimethylsiloxane units, and polymer azo polymerization initiators containing polyethylene glycol units Starting agent, etc., but the present invention is not limited to the above-mentioned examples. These polymerization initiators may be used alone, respectively, or two or more of them may be used in combination.
於使單體聚合時，亦可使用鏈轉移劑以調整分子量。鏈轉移劑通常可藉由與單體加以混合來使用。作為鏈轉移劑，例如可例舉：2-(十二烷基硫基硫代羰基硫基)-2-甲基丙酸、2-(十二烷基硫基硫代羰基硫基)丙酸、2-(十二烷基硫基硫代羰基硫基)-2-甲基丙酸甲酯、2-(十二烷基硫基硫代羰基硫基)-2-甲基丙酸3-疊氮基-1-丙醇酯、2-(十二烷基硫基硫代羰基硫基)-2-甲基丙酸五氟苯基酯、月桂硫醇、十二烷硫醇、硫代甘油等含硫醇基化合物、次磷酸鈉、亞硫酸氫鈉等無機鹽等，但本發明並不僅限定於上述例示。該等鏈轉移劑可分別單獨使用，亦可將2種以上併用。鏈轉移劑之量並無特別限定，通常只要相對於全部單體100重量份為約0.01重量份～約10重量份即可。When polymerizing monomers, a chain transfer agent can also be used to adjust the molecular weight. Chain transfer agents can usually be used by mixing with monomers. As the chain transfer agent, for example, 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid, 2-(dodecylthiothiocarbonylthio)propionic acid , 2-(Dodecylthiothiocarbonylthio)-2-methylpropionic acid methyl ester, 2-(Dodecylthiothiocarbonylthio)-2-methylpropionic acid 3- Azido-1-propanol ester, 2-(dodecylthiothiocarbonylthio)-2-methylpropionate pentafluorophenyl ester, lauryl mercaptan, dodecyl mercaptan, thio Thiol group-containing compounds such as glycerin, inorganic salts such as sodium hypophosphite and sodium bisulfite, etc., but the present invention is not limited to the above-mentioned examples. These chain transfer agents may be used individually, respectively, and may use 2 or more types together. The amount of the chain transfer agent is not particularly limited, and it may generally be about 0.01 to 10 parts by weight relative to 100 parts by weight of the total monomers.
使單體聚合時之氛圍並無特別限定，可為大氣，或者亦可為氮氣、氬氣等惰性氣體。The atmosphere when the monomer is polymerized is not particularly limited, and it may be air or an inert gas such as nitrogen and argon.
使單體聚合時之溫度並無特別限定，通常較佳為5～100℃左右之溫度。使單體聚合所需要之時間根據聚合條件而有所不同，因此無法一概而定，所以為任意，通常為1～20小時左右。The temperature when the monomer is polymerized is not particularly limited, but it is usually preferably a temperature of about 5 to 100°C. The time required to polymerize the monomers varies depending on the polymerization conditions, and therefore cannot be determined uniformly, so it is arbitrary, and is usually about 1 to 20 hours.
聚合反應可於殘存之單體之量成為20質量%以下之時點任意地結束。再者，殘存之單體之量例如可使用凝膠滲透層析法(GPC)進行測定。The polymerization reaction can be arbitrarily terminated when the amount of the remaining monomer becomes 20% by mass or less. Furthermore, the amount of remaining monomers can be measured, for example, using gel permeation chromatography (GPC).
如此使單體進行塊狀聚合，藉此可獲得聚合物基質。In this way, the monomers are polymerized in bulk, thereby obtaining a polymer matrix.
於一實施方式中，使上述單體於交聯劑之非存在下進行聚合。於另一實施方式中，使上述單體於交聯劑之存在下進行聚合。In one embodiment, the above-mentioned monomers are polymerized in the absence of a crosslinking agent. In another embodiment, the above-mentioned monomers are polymerized in the presence of a crosslinking agent.
於一實施方式中，上述聚合物基質為熱聚合或光聚合而成者。於另一實施方式中，上述聚合物基質為熱聚合而成者。於另一實施方式中，上述聚合物基質為光聚合而成者。In one embodiment, the above-mentioned polymer matrix is formed by thermal polymerization or photopolymerization. In another embodiment, the above-mentioned polymer matrix is formed by thermal polymerization. In another embodiment, the aforementioned polymer matrix is photopolymerized.
作為使單體聚合之方法，例如可例舉：塊狀聚合法、溶液聚合法、乳化聚合法、懸浮聚合法等，但本發明並不僅限定於上述例示。該等聚合法之中，較佳為塊狀聚合法及溶液聚合法。As a method of polymerizing a monomer, for example, a block polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, etc. may be mentioned, but the present invention is not limited to the above-mentioned examples. Among these polymerization methods, a bulk polymerization method and a solution polymerization method are preferable.
又，單體之聚合例如可藉由自由基聚合法、活性自由基聚合法、陰離子聚合法、陽離子聚合法、加成聚合法、縮聚法、觸媒聚合等方法來進行。In addition, the polymerization of the monomers can be carried out by methods such as radical polymerization, living radical polymerization, anionic polymerization, cationic polymerization, addition polymerization, polycondensation, and catalyst polymerization.
於藉由溶液聚合法使單體聚合之情形時，例如可藉由使單體溶解於溶劑中，一面攪拌所獲得之溶液一面向該溶液中添加聚合起始劑而使單體聚合，除此以外，還可藉由使聚合起始劑溶解於溶劑中，一面攪拌所獲得之溶液一面向該溶液中添加單體而使單體聚合。溶劑較佳為會與單體相容之有機溶劑。In the case of polymerizing monomers by the solution polymerization method, for example, the monomers can be polymerized by dissolving the monomers in a solvent, while stirring the obtained solution, and adding a polymerization initiator to the solution. In addition, it is also possible to polymerize the monomer by dissolving the polymerization initiator in the solvent and adding the monomer to the solution while stirring the obtained solution. The solvent is preferably an organic solvent that is compatible with the monomer.
本發明之導電材中所包含之共聚物亦可藉由使用過氧化物系起始劑(例如過氧化苯甲醯、及偶氮雙異丁腈、以及該等之類似物)作為聚合起始劑來進行聚合。The copolymer contained in the conductive material of the present invention can also be started by using a peroxide-based initiator (such as benzoyl peroxide, and azobisisobutyronitrile, and the like) as the polymerization starter Agent to polymerize.
於使用上述可使用之聚合起始劑作為聚合起始劑之情形時，關於該聚合起始劑之量，相對於全部單體100重量份，通常較佳為約0.01重量份～約20重量份。In the case of using the above-mentioned usable polymerization initiator as the polymerization initiator, the amount of the polymerization initiator is generally preferably about 0.01 parts by weight to about 20 parts by weight relative to 100 parts by weight of the total monomers. .
於一實施方式中，藉由對單體照射電子束而進行電子束聚合。於一實施方式中，可藉由僅照射電子束而使單體聚合。於電子束聚合中，關於電子束，於一實施方式中，係於光聚合起始劑之存在下進行照射，於另一實施方式中，係於光聚合起始劑之非存在下進行照射。任一實施方式均為本發明之範圍內。In one embodiment, electron beam polymerization is performed by irradiating the monomer with an electron beam. In one embodiment, the monomer can be polymerized by irradiating only an electron beam. In the electron beam polymerization, with regard to the electron beam, in one embodiment, irradiation is performed in the presence of a photopolymerization initiator, and in another embodiment, irradiation is performed in the absence of a photopolymerization initiator. Any embodiment is within the scope of the present invention.
關於使單體聚合時之聚合反應溫度及氛圍，並無特別限定。通常，聚合反應溫度為約50℃～約120℃。聚合反應時之氛圍例如較佳為氮氣等惰性氣體氛圍。又，單體之聚合反應時間根據聚合反應溫度等而有所不同，因此無法一概而定，但通常為約3～20小時。There are no particular limitations on the polymerization reaction temperature and atmosphere when the monomer is polymerized. Generally, the polymerization temperature is about 50°C to about 120°C. The atmosphere during the polymerization reaction is preferably, for example, an inert gas atmosphere such as nitrogen. In addition, the polymerization reaction time of the monomers differs depending on the polymerization reaction temperature and the like, and therefore cannot be determined uniformly, but it is usually about 3 to 20 hours.
(2)導電材中所包含之聚合物基質之製造方法 本發明之導電材中所包含之聚合物(或聚合物基質)可藉由如下方式來製造：將2種以上特定單體進行混合，於適當之聚合條件下，視需要使用適當之聚合起始劑等添加劑來使單體進行聚合。繼而，可藉由向該聚合物基質中混合導電成分及任意其他成分並進行加熱而製造本發明之導電材。關於聚合物，以下針對各成分或具體製造條件等進行詳細說明。(2) Manufacturing method of polymer matrix contained in conductive material The polymer (or polymer matrix) contained in the conductive material of the present invention can be manufactured by mixing two or more specific monomers, and under appropriate polymerization conditions, using appropriate polymerization starters as needed Additives such as agents to polymerize monomers. Then, the conductive material of the present invention can be manufactured by mixing conductive components and any other components into the polymer matrix and heating. Regarding the polymer, each component, specific production conditions, and the like will be described in detail below.
於一態樣中，本發明係關於一種製造由式(4)
[化29]
於一實施方式中，本發明係關於一種製造經含氧環取代之(甲基)丙烯酸烷基酯與第2(甲基)丙烯酸系單體之共聚物之方法，且
該經含氧環取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化31]
於本發明之一實施方式中，上述單體之聚合可依照選自由塊狀聚合法、溶液聚合法、乳化聚合法、及懸浮聚合法所組成之群中之聚合法來進行。本發明之單體可藉由連鎖聚合、逐次聚合、或活性聚合進行聚合，但期望不拘泥於理論。In one embodiment of the present invention, the polymerization of the above-mentioned monomers can be carried out according to a polymerization method selected from the group consisting of a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. The monomers of the present invention can be polymerized by chain polymerization, sequential polymerization, or living polymerization, but it is desirable not to be bound by theory.
(3-1)單體之製備方法 於本發明中所使用之(甲基)丙烯酸氟化烷基酯及(甲基)丙烯酸系單體可為由實施例中所例示之製造商等所市售者，亦可按照業者所周知之方法進行製備。(3-1) Preparation method of monomer The fluorinated alkyl (meth)acrylates and (meth)acrylic monomers used in the present invention may be those commercially available from the manufacturers exemplified in the examples, or they may be according to well-known in the industry. Method to prepare.
(3-2)藉由光聚合之製造方法 於一實施方式中，本發明之聚合物基質係藉由使單體(包含複數種單體)於聚合起始劑之存在下進行曝光聚合，而以1個步驟獲得。 於一實施方式中，本發明之聚合物基質可藉由對1種(甲基)丙烯酸系單體、及經含氧環取代之(甲基)丙烯酸烷基酯於聚合起始劑之存在下照射紫外線而製造。 作為聚合起始劑之較佳例，可例舉2,4,6-三甲基苯甲醯基二苯基氧化膦。 本步驟通常於室溫下進行約2小時，但並不限定於此，亦可歷時0.5～3小時、或者0.5小時～24小時或24小時以上之時間。(3-2) Manufacturing method by photopolymerization In one embodiment, the polymer matrix of the present invention is obtained in one step by subjecting monomers (including multiple monomers) to exposure polymerization in the presence of a polymerization initiator. In one embodiment, the polymer matrix of the present invention can be prepared by adding a (meth)acrylic monomer and an alkyl (meth)acrylate substituted by an oxygen-containing ring in the presence of a polymerization initiator Manufactured by irradiating ultraviolet rays. As a preferable example of the polymerization initiator, 2,4,6-trimethylbenzyldiphenylphosphine oxide can be mentioned. This step is usually carried out at room temperature for about 2 hours, but it is not limited to this, and it can also last for 0.5 to 3 hours, or 0.5 to 24 hours, or more than 24 hours.
(3-3)樹脂溶液之製備方法 於一實施方式中，使藉由使單體聚合所獲得之本發明之聚合物基質溶解於溶劑中，生成樹脂溶液。作為較佳之溶劑之例，可例舉：庚烷、辛烷、及檸檬烯等。(3-3) Preparation method of resin solution In one embodiment, the polymer matrix of the present invention obtained by polymerizing monomers is dissolved in a solvent to generate a resin solution. Examples of preferable solvents include heptane, octane, and limonene.
(3-4)導電材之製備方法 於一實施方式中，導電材係將(3-3)中所獲得之樹脂溶液與導電成分、及視需要之分散劑加以混合，並對所獲得之混合物進行加熱而獲得。業者可使用本說明書之記載及該領域中公知之任意方法來製造導電材，亦可使用除該方法以外之方法來製造導電材。(3-4) Preparation method of conductive material In one embodiment, the conductive material is obtained by mixing the resin solution obtained in (3-3) with the conductive component and, if necessary, a dispersant, and heating the obtained mixture. The industry can use the description of this specification and any method known in the field to manufacture the conductive material, and also use methods other than this method to manufacture the conductive material.
(導電成分之說明) 作為導電成分，例如可例舉：鱗片狀石墨等天然石墨、人造石墨等石墨、乙炔黑、科琴黑、煙囪黑、爐黑、燈黑、熱碳黑等碳黑、石墨烯、奈米碳管、富勒烯等碳系材料；碳纖維、金屬纖維等導電性纖維；氟化碳；銅、金、鎳、錫、鋁、鋅、鐵、銀等金屬粒子之粉末；氧化鋅、鈦酸鉀等導電性晶鬚；氧化鈦等導電性金屬氧化物；聚苯衍生物等有機導電性材料等，但本發明並不僅限定於上述例示。該等導電成分可分別單獨使用，亦可將2種以上併用。該等導電成分之中，就獲得作業性及成形性優異並且柔軟性及伸長性優異之導電膜之觀點而言，較佳為奈米碳管、碳黑、石墨烯及金屬粒子，更佳為奈米碳管、碳黑、石墨烯及銀粒子。(Description of conductive components) As the conductive component, for example, natural graphite such as flake graphite, graphite such as artificial graphite, acetylene black, Ketjen black, chimney black, furnace black, lamp black, thermal black and other carbon black, graphene, nanocarbon Carbon-based materials such as tubes and fullerenes; conductive fibers such as carbon fibers and metal fibers; carbon fluoride; powders of metal particles such as copper, gold, nickel, tin, aluminum, zinc, iron, and silver; zinc oxide, potassium titanate Conductive whiskers such as titanium oxide; conductive metal oxides such as titanium oxide; organic conductive materials such as polyphenylene derivatives, etc. However, the present invention is not limited to the above-mentioned examples. These conductive components may be used alone, or two or more of them may be used in combination. Among these conductive components, from the viewpoint of obtaining a conductive film having excellent workability and formability and excellent flexibility and elongation, carbon nanotubes, carbon black, graphene, and metal particles are preferred, and more preferred are Carbon nanotubes, carbon black, graphene and silver particles.
聚合物基質及導電成分之合計固形物成分中之導電成分之固形物成分之含有率根據該導電成分之種類等而有所不同，因此無法一概而定，通常就獲得作業性及成形性優異並且柔軟性及伸長性優異之導電膜之觀點而言，較佳為1質量%以上，就獲得作業性及成形性優異並且柔軟性及伸長性優異之導電膜之觀點而言，較佳為100質量%以下。The solid content of the conductive component in the total solid component of the polymer matrix and the conductive component differs depending on the type of the conductive component, etc., so it cannot be determined unambiguously. Usually, excellent workability and formability are obtained. From the viewpoint of a conductive film with excellent flexibility and extensibility, it is preferably 1% by mass or more, and from the viewpoint of obtaining a conductive film with excellent workability and formability and excellent flexibility and extensibility, 100 mass is preferable %the following.
作為奈米碳管，例如可例舉：將1片片狀石墨(石墨烯片)捲成筒狀而成之中空圓筒結構之單壁奈米碳管、將複數個直徑不同之單壁奈米碳管同心圓狀地積層而成之結構之多壁奈米碳管、藉由超生長法所製造之單壁奈米碳管、單壁奈米碳管之端部以圓錐狀封閉而成之形狀之奈米碳錐、內部包含富勒烯之奈米碳管等，但本發明並不僅限定於上述例示。該等奈米碳管可分別單獨使用，亦可將2種以上併用。該等奈米碳管之中，較佳為多壁奈米碳管。Examples of carbon nanotubes include: single-walled carbon nanotubes in which a sheet of graphite (graphene sheet) is rolled into a tube to form a hollow cylindrical structure, and a plurality of single-walled carbon nanotubes with different diameters Multi-walled carbon nanotubes with a concentric layered structure of carbon nanotubes, single-walled carbon nanotubes manufactured by the super-growth method, and the end of the single-walled carbon nanotubes are closed in a conical shape The shape of the carbon nanocone, the carbon nanotube containing fullerene, etc., but the present invention is not limited to the above-mentioned examples. These carbon nanotubes may be used alone, or two or more of them may be used in combination. Among these carbon nanotubes, multi-wall carbon nanotubes are preferred.
關於奈米碳管之長度，就獲得作業性及成形性優異並且柔軟性及伸長性優異之導電膜之觀點而言，較佳為0.1～1000 μm，更佳為1～500 μm，進而較佳為1～90 μm。Regarding the length of the carbon nanotube, from the viewpoint of obtaining a conductive film with excellent workability and formability and excellent flexibility and elongation, it is preferably 0.1 to 1000 μm, more preferably 1 to 500 μm, and still more preferably It is 1～90 μm.
關於奈米碳管之直徑，就獲得作業性及成形性優異並且柔軟性及伸長性優異之導電膜之觀點而言，較佳為10～50 nm，更佳為10～20 nm。Regarding the diameter of the carbon nanotube, from the viewpoint of obtaining a conductive film having excellent workability and formability and excellent flexibility and elongation, it is preferably 10-50 nm, more preferably 10-20 nm.
關於聚合物基質及奈米碳管之合計固形物成分中奈米碳管之固形物成分之含有率，就獲得作業性及成形性優異並且柔軟性及伸長性優異之導電膜之觀點而言，較佳為1質量%以上，更佳為1.5質量%以上，進而較佳為2質量%以上，就獲得作業性及成形性優異並且柔軟性及伸長性優異之導電膜之觀點而言，較佳為25質量%以下，更佳為20質量%以下，進而較佳為15質量%以下，進而更佳為3.5～10質量%。Regarding the content rate of the solid content of the carbon nanotubes in the total solid content of the polymer matrix and carbon nanotubes, from the viewpoint of obtaining a conductive film with excellent workability and formability, and excellent flexibility and elongation, It is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2% by mass or more, from the viewpoint of obtaining a conductive film excellent in workability and formability, and excellent in flexibility and elongation, it is preferred It is 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 3.5 to 10% by mass.
(導電材之用途) 本發明之導電材例如可良好地用作導電膜及該導電膜之原料，該導電膜可良好地用於致動器、產業用機器人等所使用之感測器、配線、電極、基板、發電元件、揚聲器、麥克風、噪音消除器、轉換器、人工肌肉、小型泵、醫療用器具等。(Use of conductive material) The conductive material of the present invention can be suitably used as a conductive film and a raw material of the conductive film, and the conductive film can be suitably used for sensors, wiring, electrodes, substrates, and power generation used in actuators, industrial robots, etc. Components, speakers, microphones, noise cancellers, converters, artificial muscles, small pumps, medical appliances, etc.
(較佳之實施方式) 以下說明本發明之較佳之實施方式。可以理解到，以下所提供之實施方式係為了更好地理解本發明而提供者，本發明之範圍不應限定於以下記載。因此，業者明確，可參酌本說明書中之記載，於本發明之範圍內適當進行改變。又，可以理解到，本發明之以下實施方式可單獨使用，或者亦可將該等組合使用。(Preferred implementation) The preferred embodiments of the present invention will be described below. It can be understood that the embodiments provided below are provided for a better understanding of the present invention, and the scope of the present invention should not be limited to the following description. Therefore, it is clear to the industry that they can refer to the description in this specification and make appropriate changes within the scope of the present invention. In addition, it is understood that the following embodiments of the present invention can be used alone or in combination.
(燒成溫度降低用途) 於一態樣中，本發明係關於一種燒成溫度降低用途。(For lowering the firing temperature) In one aspect, the present invention relates to an application for reducing the firing temperature.
更特定而言，於具體態樣中，本發明提供一種用於降低用以生成導電材之燒成溫度之組合物(燒成溫度降低劑)，其包含經含氧環取代之(甲基)丙烯酸烷基酯。More specifically, in a specific aspect, the present invention provides a composition for lowering the firing temperature used to generate conductive materials (the firing temperature reducer), which comprises (methyl) substituted with an oxygen-containing ring Alkyl acrylate.
於一具體實施方式中，本發明之燒成溫度降低劑係作為聚合物基質之一部分被摻入使用。該實施方式中，本發明之導電材包含經含氧環取代之(甲基)丙烯酸烷基酯之共聚物及導電成分。於較佳之實施方式中，經含氧環取代之(甲基)丙烯酸烷基酯可藉由以共聚物之形式被包含來降低用以生成導電材之燒成溫度。根據本發明，發現：藉由添加作為燒成溫度降低劑之經含氧環取代之(甲基)丙烯酸烷基酯作為單體，對藉由聚合而產生之共聚物(聚合物基質)之組成進行調整，能夠達成燒成溫度之降低，但期望不受理論所束縛。In a specific embodiment, the firing temperature reducing agent of the present invention is incorporated and used as a part of the polymer matrix. In this embodiment, the conductive material of the present invention includes a copolymer of alkyl (meth)acrylate substituted with an oxygen-containing ring and a conductive component. In a preferred embodiment, the alkyl (meth)acrylate substituted by the oxygen-containing ring can be included in the form of a copolymer to lower the firing temperature for generating the conductive material. According to the present invention, it was found that by adding an oxygen-containing ring substituted alkyl (meth)acrylate as a monomer as a firing temperature lowering agent, the composition of the copolymer (polymer matrix) produced by polymerization The adjustment can achieve a reduction in the firing temperature, but it is desirable not to be bound by theory.
於一較佳之實施方式中，較為有利的是於本發明中所使用之共聚物為經含氧基取代之(甲基)丙烯酸烷基酯與第2(甲基)丙烯酸系單體之共聚物。In a preferred embodiment, it is more advantageous that the copolymer used in the present invention is a copolymer of an oxygen-containing substituted alkyl (meth)acrylate and a second (meth)acrylic monomer .
於一較佳之實施方式中，於本發明中所使用之共聚物為經含氧環取代之(甲基)丙烯酸烷基酯與第2(甲基)丙烯酸系單體之共聚物較有利。In a preferred embodiment, the copolymer used in the present invention is a copolymer of an alkyl (meth)acrylate substituted with an oxygen-containing ring and a second (meth)acrylic monomer.
於一較佳之實施方式中，於本發明中所使用之共聚物為n為0、R1 為氫原子且R2 為作為經含氧基取代之烷基之由式(4)表示之化合物與第2(甲基)丙烯酸系單體之共聚物較有利。In a preferred embodiment, the copolymer used in the present invention is a compound represented by formula (4) in which n is 0, R 1 is a hydrogen atom, and R 2 is an alkyl group substituted with an oxygen group and The copolymer of the second (meth)acrylic monomer is more advantageous.
於一實施方式中，經含氧環取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化33]
於一實施方式中，第2(甲基)丙烯酸系單體由式(2)表示，
[化34]
於一實施方式中，R4 為具有11個或多於11個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有11個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有11個～24個碳原子之未經取代之烷基。In one embodiment, R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
於另一實施方式中，R4 為具有13個或多於13個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有13個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有13個～24個碳原子之未經取代之烷基。In another embodiment, R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
於進而另一實施方式中，R4 為具有18個或多於18個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有18個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有18個～24個碳原子之未經取代之烷基。In yet another embodiment, R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
於另一實施方式中，R4 為具有2～10個碳原子之未經取代之烷基。In another embodiment, R 4 is an unsubstituted alkyl group having 2-10 carbon atoms.
於進而另一實施方式中，經含氧環取代之(甲基)丙烯酸烷基酯為丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯或甲基丙烯酸2,3-環氧丙酯。In yet another embodiment, the alkyl (meth)acrylate substituted with an oxygen-containing ring is (3-ethyloxetan-3-yl)methyl acrylate or 2,3-ring methacrylate Oxypropyl ester.
於另一實施方式中，第2(甲基)丙烯酸系單體為丙烯酸異硬脂酯或丙烯酸月桂酯。In another embodiment, the second (meth)acrylic monomer is isostearyl acrylate or lauryl acrylate.
(導電材) 於另一態樣中，本發明提供一種導電性得到提昇之導電材。(Conductive material) In another aspect, the present invention provides a conductive material with improved conductivity.
於一具體態樣中，本發明提供一種導電材，其包含(甲基)丙烯酸氟化烷基酯之共聚物及導電成分。導電材之較佳之實施方式可利用本說明書中所記載之任意實施方式或其組合，可應用本說明書中(導電率提昇用途)之項中所記載之任意1個實施方式或將複數個實施方式加以組合來應用。In a specific aspect, the present invention provides a conductive material comprising a copolymer of fluorinated alkyl (meth)acrylate and a conductive component. The preferred embodiment of the conductive material can use any of the embodiments described in this specification or a combination thereof, and any one of the embodiments described in the item of (conductivity improvement purpose) in this specification can be applied or multiple embodiments can be used. Combine them to apply.
(製造方法) 於一態樣中，本發明亦提供一種本發明之導電材及燒成溫度降低劑之製造方法。(Production method) In one aspect, the present invention also provides a method for manufacturing the conductive material and the firing temperature reducing agent of the present invention.
於具體態樣中，本發明提供一種製造包含經含氧環取代之(甲基)丙烯酸烷基酯之共聚物及導電成分之導電材之方法。該方法包括如下步驟：藉由使上述經含氧環取代之(甲基)丙烯酸烷基酯與聚合性單體進行聚合而獲得共聚物；將該共聚物與導電成分進行混合而獲得混合物；及將該混合物進行加熱而生成導電材。製造方法之較佳之實施方式可利用本說明書中所記載之任意實施方式或其組合，可應用本說明書中(燒成溫度降低用途)之項中所記載之任意1個實施方式或將複數個實施方式加以組合來應用。In a specific aspect, the present invention provides a method of manufacturing a conductive material containing a copolymer of alkyl (meth)acrylate substituted with an oxygen-containing ring and a conductive component. The method includes the following steps: obtaining a copolymer by polymerizing the above-mentioned oxygen-containing ring-substituted alkyl (meth)acrylate and a polymerizable monomer; mixing the copolymer and a conductive component to obtain a mixture; and This mixture is heated to produce a conductive material. The preferred embodiment of the manufacturing method can utilize any of the embodiments described in this specification or a combination thereof, and can apply any one of the embodiments described in the item of (calcination temperature reduction use) in this specification or multiple implementations. Ways to be combined to apply.
本發明之製造方法中藉由使經含氧環取代之(甲基)丙烯酸烷基酯與聚合性單體進行聚合而獲得共聚物之步驟中，代表性而言，較佳為如以下之條件：大氣壓下、5℃～100℃。In the production method of the present invention, in the step of polymerizing an alkyl (meth)acrylate substituted with an oxygen-containing ring and a polymerizable monomer to obtain a copolymer, typically, the following conditions are preferred : At atmospheric pressure, 5°C to 100°C.
本發明之製造方法中將共聚物與導電成分進行混合而獲得混合物之步驟中，代表性而言，較佳為如以下之條件：於大氣壓下且於室溫下藉由行星式混合攪拌裝置進行攪拌。In the step of mixing the copolymer and the conductive component to obtain the mixture in the manufacturing method of the present invention, typically, the following conditions are preferred: at atmospheric pressure and at room temperature by a planetary mixing and stirring device Stir.
本發明之製造方法中將混合物進行加熱而生成導電材之步驟中，代表性而言，較佳為如以下之條件：大氣壓下、120℃～150℃。In the step of heating the mixture to produce the conductive material in the production method of the present invention, typically, the following conditions are preferred: 120°C to 150°C under atmospheric pressure.
(共聚物) 本發明提供一種使用本發明之技術之共聚物。(Copolymer) The present invention provides a copolymer using the technology of the present invention.
代表性之態樣中，本發明提供一種共聚物，其係由式(4)
[化35]
於一具體實施方式中，上述經含氧基取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化37]
於另一具體實施方式中，於由式(4)表示之化合物中，
[化38]
又，本發明提供一種經含氧環取代之(甲基)丙烯酸烷基酯與第2(甲基)丙烯酸系單體之共聚物，該經含氧基取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化39]
於一實施方式中，R4 為具有11個或多於11個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有11個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有11個～24個碳原子之未經取代之烷基。In one embodiment, R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
於一實施方式中，R4 為具有13個或多於13個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有13個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有13個～24個碳原子之未經取代之烷基。In one embodiment, R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
於一實施方式中，R4 為具有18個或多於18個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有18個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有18個～24個碳原子之未經取代之烷基。In one embodiment, R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
於另一實施方式中，R4 為具有2～10個碳原子之未經取代之烷基。In another embodiment, R 4 is an unsubstituted alkyl group having 2-10 carbon atoms.
本發明提供一種基質用途。 於一態樣中，本發明提供一種用於用作包含導電成分之導電材中之基質之組合物，其包含由式(1)表示之經含氧環取代之(甲基)丙烯酸烷基酯之共聚物。The invention provides a substrate use. In one aspect, the present invention provides a composition for use as a matrix in a conductive material containing a conductive component, which comprises an oxygen-containing ring substituted alkyl (meth)acrylate represented by formula (1)的copolymer.
(混合物) 又，本發明提供一種混合物。(mixture) In addition, the present invention provides a mixture.
於一態樣中，本發明提供一種作為物質之混合物(即，包含共聚物及金屬系成分之組合物)。In one aspect, the present invention provides a mixture of substances (ie, a composition containing a copolymer and a metal-based component).
於一態樣中，本發明提供一種由式(4)表示之化合物與(第2)(甲基)丙烯酸系單體之共聚物及金屬之混合物。此處，「第2」(甲基)丙烯酸系單體意指共聚物之(第1)由式(4)表示之化合物之對象單體。In one aspect, the present invention provides a mixture of a compound represented by formula (4) and a (second) (meth)acrylic monomer copolymer and a metal. Here, the "second" (meth)acrylic monomer means the (first) target monomer of the compound represented by formula (4) of the copolymer.
於一實施方式中，上述混合物為經含氧基取代之(甲基)丙烯酸烷基酯(單體)與(第2)(甲基)丙烯酸系單體之共聚物及金屬之混合物。In one embodiment, the above-mentioned mixture is a mixture of a copolymer of an alkyl (meth)acrylate (monomer) substituted by an oxygen-containing group and a (second) (meth)acrylic monomer and a metal.
於另一實施方式中，上述混合物為由式(4)表示之化合物與(第2)(甲基)丙烯酸系單體之共聚物及金屬之混合物，上述式(4)中，R1 為氫原子，R2 為可經乙烯氧基或者羥基取代之烷基、環烷基、或者烷基環烷基烷基、或-(CH2 CH2 O)y -R7 ，R7 為氫或乙烯基，y為1以上之整數且n為0。In another embodiment, the above-mentioned mixture is a mixture of the compound represented by formula (4) and (the second) (meth)acrylic monomer copolymer and metal. In the above-mentioned formula (4), R 1 is hydrogen Atom, R 2 is alkyl, cycloalkyl, or alkylcycloalkylalkyl which can be substituted by vinyloxy or hydroxy, or -(CH 2 CH 2 O) y -R 7 , R 7 is hydrogen or ethylene Base, y is an integer greater than or equal to 1 and n is 0.
又，本發明提供一種經含氧環取代之(甲基)丙烯酸烷基酯(單體)與(第2)(甲基)丙烯酸系單體之共聚物及金屬之混合物。此處，「第2」(甲基)丙烯酸系單體意指共聚物之(第1)經含氧環取代之(甲基)丙烯酸烷基酯單體之對象單體。In addition, the present invention provides a mixture of a copolymer of alkyl (meth)acrylate (monomer) and (2) (meth)acrylic monomer substituted with oxygen-containing ring, and a metal mixture. Here, the "second" (meth)acrylic monomer means the monomer of the (first) alkyl (meth)acrylate monomer substituted with an oxygen-containing ring in the copolymer.
於一實施方式中，金屬包含銀、銅、金、鋁、鋅、錫、鎳、及/或鐵。於較佳之實施方式中，金屬為銀。其原因在於銀之導電性優異，耐性亦良好，但期望不受理論所束縛。In one embodiment, the metal includes silver, copper, gold, aluminum, zinc, tin, nickel, and/or iron. In a preferred embodiment, the metal is silver. The reason is that silver has excellent electrical conductivity and good resistance, but it is expected that it is not bound by theory.
於一實施方式中，經含氧基取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化41]
於一實施方式中，經含氧環取代之(甲基)丙烯酸烷基酯由式(1)表示，
[化43]
於一實施方式中，R4 為具有11個或多於11個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有11個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有11個～24個碳原子之未經取代之烷基。In one embodiment, R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
於另一實施方式中，R4 為具有13個或多於13個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有13個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有13個～24個碳原子之未經取代之烷基。In another embodiment, R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
於另一實施方式中，R4 為具有18個或多於18個之碳原子之未經取代之烷基。於一實施方式中，R4 為具有18個～30個碳原子之未經取代之烷基。於一實施方式中，R4 為具有18個～24個碳原子之未經取代之烷基。In another embodiment, R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
於另一實施方式中，R4 為具有2～10個碳原子之未經取代之烷基。In another embodiment, R 4 is an unsubstituted alkyl group having 2-10 carbon atoms.
(註釋) 於本說明書中，「或」係於可採用文章中所例舉之事項之「至少1個以上」時所使用。「或者」亦同樣如此。於本說明書中，於明確記載為「2個值之範圍內」之情形時，該範圍亦包括2個值本身。(Comment) In this manual, "or" is used when "at least one or more" of the items listed in the article can be used. The same goes for "or". In this specification, when it is clearly stated as "within the range of two values", the range also includes the two values themselves.
關於本說明書中所引用之科學文獻、專利、專利申請等參考文獻，其整體係以參考之形式援用於本說明書中直至與各具體記載者相同之程度。Regarding references such as scientific documents, patents, and patent applications cited in this specification, the entirety is used in this specification as a reference to the same extent as each specific description.
以上，列示了較佳之實施方式對本發明進行了說明以便於理解。以下，基於實施例對本發明進行說明，但上述說明及以下之實施例係僅為了例示而提供，並非為了對本發明進行限定而提供。因此，本發明之範圍不受本說明書中具體記載之實施方式限定，亦不受實施例限定，僅由申請專利範圍所限定。 [實施例]Above, preferred embodiments are listed to illustrate the present invention for ease of understanding. Hereinafter, the present invention will be described based on examples. However, the above description and the following examples are provided for illustration only, and are not provided to limit the present invention. Therefore, the scope of the present invention is not limited by the embodiments specifically described in this specification, nor is it limited by the examples, but only by the scope of the patent application. [Example]
以下記載實施例。關於以下實施例中所使用之生物之使用，於需要之情形時遵守主管機關所規定之基準。關於試劑類，具體而言，使用實施例中所記載之製品，但亦能夠用其他製造商(Sigma-Aldrich等)之同等品來代替。Examples are described below. Regarding the use of the organisms used in the following examples, comply with the standards set by the competent authority when necessary. Regarding reagents, specifically, the products described in the examples are used, but equivalent products from other manufacturers (Sigma-Aldrich, etc.) can also be substituted.
(實施例1：聚合物基質之製備) 於本實施例中，製備聚合物基質。(Example 1: Preparation of polymer matrix) In this example, a polymer matrix was prepared.
(實施例a) 將作為單體A之丙烯酸異硬脂酯(ISTA，9.50 g)、作為單體C之丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯(4.00 g，大阪有機化學工業股份有限公司製造，商品名OXE-10)、及作為聚合起始劑之2,4,6-三甲基苯甲醯基二苯基氧化膦(0.14 g，BASF公司製造，商品名Irgacure(註冊商標)TPO)進行混合，藉此獲得含有聚合起始劑之單體成分。將所獲得之單體成分注入至透明玻璃製成形模具(縱：100 mm，橫：100 mm，深：2 mm)內後，對該單體成分以照射線量成為0.36 mW/cm2 之方式照射紫外線，使單體成分塊狀聚合2小時，藉此獲得聚合物。(Example a) Isostearyl acrylate (ISTA, 9.50 g) as monomer A and (3-ethyloxetan-3-yl) methyl acrylate as monomer C (4.00 g, Osaka Organic Chemical Industry Co., Ltd., trade name OXE-10), and 2,4,6-trimethylbenzyl diphenyl phosphine oxide (0.14 g, manufactured by BASF Corporation, product The name Irgacure (registered trademark) TPO) is mixed to obtain a monomer component containing a polymerization initiator. After injecting the obtained monomer component into a transparent glass forming mold (length: 100 mm, width: 100 mm, depth: 2 mm), the monomer component is irradiated so that the amount of irradiation becomes 0.36 mW/cm 2 Ultraviolet rays are used to polymerize the monomer components in a block form for 2 hours, thereby obtaining a polymer.
(實施例b～d、比較例1) 如表1中記載般變更單體A與單體C之比率，除此以外，以與實施例a相同之方式獲得聚合物。(Examples b to d, Comparative Example 1) Except for changing the ratio of monomer A to monomer C as described in Table 1, a polymer was obtained in the same manner as in Example a.
(實施例e～g) 同樣地，使用GMA(4.00 g，東京化成工業股份有限公司製造，商品名甲基丙烯酸縮水甘油基)代替OXE-10之作為單體C，獲得對應之聚合物。所使用之單體A與單體C之組成之重量份如表1中所記載。(Examples e～g) Similarly, GMA (4.00 g, manufactured by Tokyo Chemical Industry Co., Ltd., trade name glycidyl methacrylate) was used instead of OXE-10 as monomer C to obtain the corresponding polymer. The weight parts of the composition of monomer A and monomer C used are as described in Table 1.
(實施例h) 藉由將作為單體A之丙烯酸乙酯(EA，4.30 g)、作為單體C之丙烯酸2-甲氧基乙酯(5.60 g，大阪有機化學工業股份有限公司製造，商品名2-MTA)、及作為聚合起始劑之2,4,6-三甲基苯甲醯基二苯基氧化膦(0.14 g，BASF公司製造，商品名Irgacure(註冊商標)TPO)進行混合，而獲得含有聚合起始劑之單體成分。將所獲得之單體成分注入至透明玻璃製成形模具(縱：100 mm，橫：100 mm，深：2 mm)內，其後對該單體成分以照射線量成為0.36 mW/cm2 之方式照射紫外線，使單體成分塊狀聚合2小時，藉此獲得聚合物。(Example h) By combining ethyl acrylate (EA, 4.30 g) as monomer A and 2-methoxyethyl acrylate (5.60 g, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as monomer C as a commercial product Name 2-MTA) and 2,4,6-trimethylbenzyl diphenyl phosphine oxide (0.14 g, manufactured by BASF Corporation, trade name Irgacure (registered trademark) TPO) as a polymerization initiator. , And obtain the monomer component containing the polymerization initiator. Inject the obtained monomer component into a transparent glass forming mold (length: 100 mm, width: 100 mm, depth: 2 mm), and then irradiate the monomer component so that the amount of radiation becomes 0.36 mW/cm 2 UV rays were irradiated to polymerize the monomer components in bulk for 2 hours, thereby obtaining a polymer.
(實施例i～k、比較例2) 同樣地，使用作為單體A之丙烯酸乙酯(EA，X. XXX g)、及作為單體C之4-羥基丁基乙烯基醚(X. XX g，大阪有機化學工業股份有限公司製造，商品名 4HBVE)，獲得對應之聚合物。所使用之單體A與單體C之組成之重量份如表1中所記載。(Examples i to k, comparative example 2) Similarly, use ethyl acrylate (EA, X. XXX g) as monomer A and 4-hydroxybutyl vinyl ether (X. XX g, manufactured by Osaka Organic Chemical Industry Co., Ltd., as monomer C). Trade name 4HBVE) to obtain the corresponding polymer. The weight parts of the composition of monomer A and monomer C used are as described in Table 1.
將所獲得之各聚合物3.00 g與適當之溶劑(庚烷、辛烷、或檸檬烯)(7.00 g)混合，確認是否溶解。於已溶解之情形時，將所產生之溶液(有時亦稱為丙烯酸系樹脂溶液)用於導電膜之製備。Mix 3.00 g of each polymer obtained with an appropriate solvent (heptane, octane, or limonene) (7.00 g) to confirm whether it is dissolved. When it has been dissolved, the resulting solution (sometimes referred to as an acrylic resin solution) is used for the preparation of the conductive film.
(實施例2：導電膜之製備) 本實施例中，製備導電膜。(Example 2: Preparation of conductive film) In this embodiment, a conductive film is prepared.
(導電材前驅物) 利用倉敷紡織公司製造之Mazerustar將銀填料(7.20 g，福田金屬箔粉工業公司製造，商品名AgC-A)、及作為分散劑之2-(2-丁氧基乙氧基)乙醇(0.10 g)混合於實施例1中所獲得之各丙烯酸樹脂溶液(6.00 g)中，獲得導電材前驅物。(Precursor of conductive material) The silver filler (7.20 g, manufactured by Fukuda Metal Foil Industry Co., Ltd., trade name AgC-A) and 2-(2-butoxyethoxy)ethanol (0.10 g) as a dispersant were prepared by using Mazerustar manufactured by Kurashiki Textile Co., Ltd. ) Was mixed with each acrylic resin solution (6.00 g) obtained in Example 1 to obtain a conductive material precursor.
(塗膜形成) 將所獲得之導電材前驅物塗佈於作為剝離膜之離型聚對苯二甲酸乙二酯膜(三井化學Tohcello股份有限公司製造，商品名Separator SP-PET PET-01-Bu)，形成塗膜。(Coating film formation) The obtained conductive material precursor was coated on a release polyethylene terephthalate film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name Separator SP-PET PET-01-Bu) as a release film to form a coating membrane.
(導電膜) 針對所獲得之塗膜，用烘箱以150℃加熱60分鐘，獲得大約30 μm厚之導電膜。(Conductive film) The obtained coating film was heated at 150°C for 60 minutes in an oven to obtain an approximately 30 μm thick conductive film.
(結果)
將結果示於下述表1。
[表1-1]
根據以上，顯示：藉由增加2-MTA或4HBVE之比率，體積電阻率及電阻值變化降低。Based on the above, it is shown that by increasing the ratio of 2-MTA or 4HBVE, the volume resistivity and resistance value changes decrease.
(實施例3：體積電阻率之測定) 將實施例2中所獲得之導電膜切取成縱0.5 cm、橫2.00 cm，使用Loresta GP(Mitsubishi Chemical Analytech公司製造)並利用四端子法進行測定。(Example 3: Measurement of volume resistivity) The conductive film obtained in Example 2 was cut into a length of 0.5 cm and a width of 2.00 cm, and measured by the four-terminal method using Loresta GP (manufactured by Mitsubishi Chemical Analytech).
(結果) 將結果示於表1。(result) The results are shown in Table 1.
(實施例4：電阻值變化之確認) 本實施例中，確認到電阻值變化。(Example 4: Confirmation of resistance change) In this example, it was confirmed that the resistance value changed.
(電阻值之測定) 將上述中所獲得之導電膜切取成縱0.5 cm、橫2.00 cm，利用將電極間距離固定為1.00 cm之數位萬用錶[三和電機計器股份有限公司製造 商品名PC773]對拉伸前電阻值(ΩA)進行測定。(Determination of resistance value) Cut the conductive film obtained above into 0.5 cm in length and 2.00 cm in width, and use a digital multimeter [manufactured by Sanwa Denki Keiki Co., Ltd., trade name PC773] with the distance between electrodes fixed to 1.00 cm to determine the resistance value before stretching ( ΩA) is measured.
(電阻值變化) 繼而，於將導電膜固定於萬用錶電極上之狀態下使電極間距離成為2.00 cm，對該狀態下之電阻值(ΩB)進行測定。以如下方式算出電阻值變化。 電阻值變化＝ΩB/ΩA(Change in resistance value) Then, in the state where the conductive film was fixed on the electrodes of the multimeter, the distance between the electrodes was 2.00 cm, and the resistance value (ΩB) in this state was measured. The resistance value change is calculated as follows. Resistance value change = ΩB/ΩA
(結果) 將結果示於表1。(result) The results are shown in Table 1.
(註釋) 如以上所述，使用本發明之較佳之實施方式對本發明進行了例示，但可以理解到，本發明應僅由申請專利範圍來解釋其範圍。本申請案對日本專利申請第2019-148115號(2019年8月9日申請)主張優先權，其內容整體以參考之形式援用於本說明書中。關於本說明書中所引用之專利、專利申請及其他文獻，可以理解到，其內容應以對本說明書之參考之形式被援用，內容本身與具體記載於本說明書者相同。 [產業上之可利用性](Comment) As described above, the present invention has been exemplified using the preferred embodiments of the present invention, but it can be understood that the scope of the present invention should only be interpreted by the scope of the patent application. This application claims priority to Japanese Patent Application No. 2019-148115 (application dated August 9, 2019), and the entire content is incorporated in this specification by reference. Regarding the patents, patent applications and other documents cited in this specification, it can be understood that the content should be cited as a reference to this specification, and the content itself is the same as that specifically described in this specification. [Industrial availability]
使用本發明之導電材提昇劑能夠提供一種效率良好之導電材，可利用於需要導電材之產業中。The use of the conductive material enhancer of the present invention can provide a highly efficient conductive material, which can be used in industries that require conductive materials.
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