TWI426102B - Metal oxide composition, hardened film, and laminated article - Google Patents
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Description
本發明係關於一種具有硬塗性之金屬氧化物組成物、及使用其之硬化膜與其積層體。The present invention relates to a metal oxide composition having a hard coat property, and a cured film using the same, and a laminate thereof.
以往,從確保資訊通訊機器之性能與安全對策之方面而言,於機器之表面,係使用光金屬氧化物組成物而形成一具有耐刮傷性、密著性、高折射率性等之硬塗性塗膜、或防止帶電性塗膜。In the past, from the aspect of ensuring the performance and safety measures of information communication equipment, a photometal oxide composition was used on the surface of the machine to form a scratch, adhesion, high refractive index, etc. Apply a coating film or prevent a charged coating film.
近年,於資訊通訊機器之發達與汎用化係有驚人之處,且尋求硬塗性塗膜、防止帶電性塗膜等的更進一步性能提昇及生產性的提高,已有使用光硬化性材料之各種提案。In recent years, the development and generalization of information communication equipment has been amazing, and the use of photocurable materials has been sought for the improvement of performance and productivity of hard coating films and antistatic coatings. Various proposals.
例如,可舉例如以下之技術提案(參照專利文獻1至3)。在專利文獻1中,揭示一種有機溶劑中,使用球磨機等而混合氧化錫等之導電性粉末與複數之單體成分,以製作導電性塗料之方法。在專利文獻2中係揭示一種製作方法,係在有機溶劑中使用球磨機而混合摻雜銻之氧化錫與具有紫外線硬化性之矽烷偶合劑,以製作導電性塗料用之分散體。進而在專利文獻3中,係使導電性氧化物粉末分散在易分散性低沸點溶劑與難分散性高沸點溶劑之混合溶劑中,製作導電性塗料之方法。For example, the following technical proposals are mentioned (refer to Patent Documents 1 to 3). Patent Document 1 discloses a method of producing a conductive paint by mixing a conductive powder such as tin oxide with a plurality of monomer components in a organic solvent using a ball mill or the like. Patent Document 2 discloses a production method in which a tantalum-doped tin oxide and a UV-curable decane coupling agent are mixed in an organic solvent using a ball mill to prepare a dispersion for a conductive coating material. Further, in Patent Document 3, a method in which a conductive coating material is prepared by dispersing a conductive oxide powder in a mixed solvent of a solvent-dispersible low-boiling solvent and a non-dispersible high-boiling solvent.
(專利文獻1)日本特開平04-172634號公報(專利文獻2)日本特開平06-264009號公報(專利文獻3)日本特開2001-131485號公報(Patent Document 1) Japanese Laid-Open Patent Publication No. Hei No. 2001-131485 (Patent Document 3)
然而藉上述方法,即使可製作於高折射率性、硬塗性、防止帶電性、耐光性等同時具有良好物性之金屬氧化物組成物,對於有機溶劑等疏水性高之媒體,無法使平均一次粒徑為100nm以下之金屬氧化物安定地以一次粒子程度分散及安定化,就塗膜之透明性或光硬化性塗料之隨時間安定性等之觀點而言易產生問題。However, by the above method, even if a metal oxide composition having high physical properties such as high refractive index, hard coating property, charge resistance, light resistance, and the like can be produced, it is impossible to make the average of the medium having high hydrophobicity such as an organic solvent. The metal oxide having a particle diameter of 100 nm or less is stably dispersed and stabilized at the primary particle level, and is liable to cause problems in terms of transparency of the coating film or stability with time of the photocurable coating material.
因此,本發明之目的在於提供一種平均一次粒徑含有100nm以下之金屬氧化物,同時可形成高折射率性、防止帶電性、硬塗性、透明性及耐光性之全部中同時具有優異之物性的塗膜,且具有隨時間安定性之金屬氧化物組成物、及使用其之硬化膜與其積層體。Therefore, an object of the present invention is to provide a metal oxide having an average primary particle diameter of 100 nm or less, and at the same time, can form a high refractive index, prevent chargeability, hard coatability, transparency, and light resistance, and have excellent physical properties. The coating film has a metal oxide composition which is stable with time, and a cured film and a laminate thereof using the same.
本發明係關於一種含有以下述通式(1)所示之分散劑(A)、及平均一次粒徑為5至100nm的金屬氧化物之金屬氧化物組成物。The present invention relates to a metal oxide composition containing a dispersant (A) represented by the following formula (1) and a metal oxide having an average primary particle diameter of 5 to 100 nm.
另外本發明係關於含有基材與上述硬化膜之積層體。Further, the present invention relates to a laminate comprising a substrate and the above-mentioned cured film.
另外本發明係關於含有上述金屬氧化物組成物之光半導體元件密封材。Further, the present invention relates to an optical semiconductor element sealing material containing the above metal oxide composition.
另外本發明係關於一種金屬氧化物分散體之製造方法,其係包含:使用以下述通式(I)所示之分散劑(A),使平均一次粒徑為5至100nm的金屬氧化物在有機溶劑存在下分散。Further, the present invention relates to a method for producing a metal oxide dispersion comprising: using a dispersing agent (A) represented by the following formula (I) to give a metal oxide having an average primary particle diameter of 5 to 100 nm at Dispersed in the presence of an organic solvent.
再者,另外本發明係關於一種硬化膜之製造方法,其係包含:使上述金屬氧化物組成物塗佈於基材上;及照射活性能量線而使金屬氧化物組成物硬化。Furthermore, the present invention relates to a method for producing a cured film comprising: applying the metal oxide composition to a substrate; and irradiating the active energy ray to cure the metal oxide composition.
本發明之金屬氧化物組成物係含有以下述通式(1)所示之分散劑(A)、及平均一次粒徑為5至100nm的金屬氧化物者,且亦可分別含有二種類以上之金屬氧化物及二種類以上之分散劑(A)。The metal oxide composition of the present invention contains a dispersant (A) represented by the following formula (1) and a metal oxide having an average primary particle diameter of 5 to 100 nm, and may contain two or more types thereof. Metal oxide and two or more kinds of dispersing agents (A).
此分散劑(A)係對於金屬氧化物具有高的分散性與光硬化性。藉由提升此分散劑(A)為平均一次粒徑5至100nm的金屬氧化物之分散性,且提高光硬化性,本發明之金屬氧化物組成物係可形成硬化性優,硬塗性、透明性、耐光性、高折射率性、防止帶電性優之硬化膜及其積層體。因此,尤其可適宜使用於塑膠光學零件、光碟、防止反射膜、觸摸面板、薄膜型液晶元件外,尚亦可適宜作為各種塑膠積層體的硬塗劑使用。This dispersant (A) has high dispersibility and photocurability to metal oxides. By increasing the dispersibility of the dispersant (A) to a metal oxide having an average primary particle diameter of 5 to 100 nm and improving photocurability, the metal oxide composition of the present invention can form excellent hardenability, hard coatability, A cured film having excellent transparency, light resistance, high refractive index, and excellent chargeability and a laminate thereof. Therefore, it can be suitably used for plastic optical parts, optical disks, antireflection films, touch panels, and film type liquid crystal elements, and can also be suitably used as a hard coating agent for various plastic laminates.
此金屬氧化物組成物係可形成折射率高之硬化膜,將此塗布於折射率同程度之基材時,所得到之積層體係不產生反射干涉條紋,而適宜使用於光學用途。進一步,因可充分地控制含有金屬氧化物之硬化物的折射率,故亦適宜作為光半導體元件密封材。The metal oxide composition can form a cured film having a high refractive index. When applied to a substrate having the same refractive index, the resulting laminated system does not cause reflection interference fringes, and is suitably used for optical applications. Further, since the refractive index of the cured product containing a metal oxide can be sufficiently controlled, it is also suitable as an optical semiconductor element sealing material.
在上述式(1)中,R9 之4價芳香族基,具體上可舉例如:苯基骨架、二苯甲酮骨架、聯苯基骨架、苯基醚骨架、二苯基碸骨架、二苯基硫醚骨架、苝骨架、芴骨架、四氫萘骨架及萘骨架等。其中,R9 宜至少一種選自聯苯基骨架、萘骨架、芴骨架及四氫萘骨架所成組群。In the above formula (1), the tetravalent aromatic group of R 9 may specifically be, for example, a phenyl skeleton, a benzophenone skeleton, a biphenyl skeleton, a phenyl ether skeleton, a diphenylfluorene skeleton or the like. a phenyl sulfide skeleton, an anthracene skeleton, an anthracene skeleton, a tetrahydronaphthalene skeleton, a naphthalene skeleton, and the like. Among them, R 9 is preferably at least one selected from the group consisting of a biphenyl skeleton, a naphthalene skeleton, an anthracene skeleton, and a tetrahydronaphthalene skeleton.
R9 之4價的脂肪族骨架係碳數4至10之烷基骨架的4價脂肪族基為適宜例,具體上可舉例如丁烷骨架、環丁烷骨架、己烷骨架、環己烷骨架、萘烷骨架等。Tetravalent aliphatic group-based aliphatic backbone carbon atoms of the alkyl group R 9 skeleton tetravalent 4-10 of favorable embodiment, for example on a concrete skeleton such as butane, cyclobutane skeleton, skeleton hexane, cyclohexane Skeleton, decalin skeleton, and the like.
在上述式(1)中,R5 至R8 之非取代或取代之直鏈或分枝鏈的伸烷基係可舉例如:亞甲基、伸乙基、C3至C10之聚亞甲基等的伸烷基。又,非取代或取代之直鏈或是分枝鏈的伸烷基氧伸烷基,係可例示如C3伸烷基-氧-C3伸烷基。此等之伸烷基或伸烷基氧伸烷基係源自於成為原料之下述第1及第2之含羥基的(甲基)丙烯酸酯化合物。In the above formula (1), the alkyl group of the unsubstituted or substituted straight or branched chain of R 5 to R 8 may, for example, be a methylene group, an ethyl group, or a C3 to C10 polymethylene group. Equivalent alkyl group. Further, an unsubstituted or substituted linear or branched alkyl alkylene oxide group is exemplified by a C3 alkyl-oxy-C3 alkylene group. These alkylene or alkylene oxide alkyl groups are derived from the following first and second hydroxyl group-containing (meth) acrylate compounds which are raw materials.
伸烷基或伸烷基氧伸烷基可取得之取代基可例示:甲基、乙基等之烷基、羥基、丙烯醯氧甲基、丙烯醯氧乙基、苯氧基等。The substituent which can be obtained by an alkyl group or an alkyloxyalkylene group is exemplified by an alkyl group such as a methyl group or an ethyl group, a hydroxyl group, an acryloxymethyl group, an acryloyloxyethyl group or a phenoxy group.
以通式(1)所示之分散劑(A)例如係藉由使具有芳香族骨架或脂肪族骨架及2個以上之羧酸酐基的化合物(x1)與具有可與羧酸酐基反應之官能基的化合物(x2)反應而構成之具有羧基的化合物(X)、與具有可與羧基反應之官能基的化合物(Y)反應所得到。此處,從光硬化性與硬塗性之觀點,上述化合物(x2)及化合物(Y)之至少一部分以具有聚合性不飽和雙鍵基者為宜。The dispersing agent (A) represented by the formula (1) is, for example, a compound (x1) having an aromatic skeleton or an aliphatic skeleton and two or more carboxylic anhydride groups, and a functional group capable of reacting with a carboxylic acid anhydride group. The compound (X) having a carboxyl group formed by reacting the compound (x2) with a group is reacted with a compound (Y) having a functional group reactive with a carboxyl group. Here, from the viewpoints of photocurability and hard coatability, at least a part of the compound (x2) and the compound (Y) is preferably a polymerizable unsaturated double bond group.
在化合物(x2)中之「可與羧酸酐基反應之官能基」雖可舉例如羥基、胺基、縮水甘油基等,但從反應控制的容易性,尤宜為羥基。因此,化合物(x2)以具有1個或2個羥基之丙烯酸酯化合物或甲基丙烯酸酯化合物為宜。In the compound (x2), the "functional group reactive with the carboxylic acid anhydride group" may, for example, be a hydroxyl group, an amine group or a glycidyl group. However, the ease of reaction control is particularly preferably a hydroxyl group. Therefore, the compound (x2) is preferably an acrylate compound or a methacrylate compound having one or two hydroxyl groups.
在化合物(Y)中之「可與羧基反應之官能基」,係可舉例如環氧基、噁唑啉基、羥基、胺基、碳二醯亞胺、異氰酸酯基、異硫氰酸酯、乙烯基醚基等。The "functional group reactive with a carboxyl group" in the compound (Y) may, for example, be an epoxy group, an oxazoline group, a hydroxyl group, an amine group, a carbodiimide, an isocyanate group or an isothiocyanate. Vinyl ether group and the like.
進一步,舉出一例而說明。具芳香族骨架或脂肪族骨架、與2個以上之羧酸酐基的化合物(x1)之下述通式(2):
此處,「丙烯酸酯基或甲基丙烯酸酯基」係包含含有或使用丙烯酸酯基及甲基丙烯酸酯基之兩者時之概念。以下,有時歸納丙烯酸酯與甲基丙烯酸酯而記載為「(甲基)丙烯酸酯」。Here, the "acrylate group or methacrylate group" includes the concept of containing or using both an acrylate group and a methacrylate group. Hereinafter, acrylate and methacrylate may be summarized and described as "(meth) acrylate".
以上述通式(2)所示之芳香族四羧酸二酐,可舉例如:均苯四甲酸二酐、二苯甲酮四羧酸二酐、具有聯苯骨架之聯苯基四羧酸二酐、氧二酞酸二酐、二苯基碸四羧酸二酐、二苯基硫醚四羧酸二酐、苝四羧酸二酐、具有萘骨架之萘四羧酸二酐、具有芴骨架之9,9-雙(3,4-二羧苯基)芴二酐、或、9,9-雙[4-(3,4-二羧苯氧基)苯基]芴二酐、具有四氫萘骨架之四氫萘羧酸二酐、乙二醇雙(偏苯三甲酸酐)、甘油雙(偏苯三甲酸酐)單乙酸酯等。Examples of the aromatic tetracarboxylic dianhydride represented by the above formula (2) include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyl tetracarboxylic acid having a biphenyl skeleton. a dianhydride, an oxydiphthalic acid dianhydride, a diphenylphosphonium tetracarboxylic dianhydride, a diphenyl sulfide tetracarboxylic dianhydride, a perylene tetracarboxylic dianhydride, a naphthalene tetracarboxylic dianhydride having a naphthalene skeleton, 9,9-bis(3,4-dicarboxyphenyl)ruthenium anhydride or 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]ruphthalic anhydride, Tetrahydronaphthalenecarboxylic acid dianhydride having a tetrahydronaphthalene skeleton, ethylene glycol bis(trimellitic anhydride), glycerol bis(trimellitic anhydride) monoacetate or the like.
市售品可舉例如新日本理化(股)製「Rikasid TMTA-C」、「Rikasid MTA-10」、「Rikasid MTA-15」、「Rikasid TMEG系列」、「Rikasid TDA」、「Rikasid DSDA」等。Commercial products such as "Rikasid TMTA-C", "Rikasid MTA-10", "Rikasid MTA-15", "Rikasid TMEG Series", "Rikasid TDA", "Rikasid DSDA", etc., manufactured by Nippon Chemical and Chemical Co., Ltd., etc. .
此等芳香族四羧酸二酐之中,聯苯基四羧酸二酐係具有聯苯基骨架者,可使聯苯基骨架有效率地導入於以式(1)所示之化合物之分子內,進一步,可一併具有硬化膜之硬塗性與金屬氧化物之良好分散性,故特佳。Among these aromatic tetracarboxylic dianhydrides, the biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton can be efficiently introduced into the molecule of the compound represented by the formula (1). Further, it is particularly preferable since it has a hard coat property of a cured film and a good dispersibility of a metal oxide.
以通式(2)所示之脂肪族四羧酸二酐,可舉例如丁烷四羧酸二酐。The aliphatic tetracarboxylic dianhydride represented by the formula (2) may, for example, be butane tetracarboxylic dianhydride.
第1及第2之含羥基的(甲基)丙烯酸酯化合物係互為相同,亦可為相異。如此之含羥基的(甲基)丙烯酸酯化合物的例可舉例如:2-羥乙基(甲基)丙烯酸酯、3-羥丙基(甲基)丙烯酸酯、4-羥丁基(甲基)丙烯酸酯、2-羥丁基(甲基)丙烯酸酯、2-羥-3-苯氧基丙基(甲基)丙烯酸酯、2-丙烯醯氧乙基-2-羥乙基酞酸、甘油單(甲基)丙烯酸酯、2-羥-3-丙烯醯氧丙基(甲基)丙烯酸酯、二羥基丙烯酸酯、甘油單(甲基)丙烯酸酯、三聚異氰酸酯EO改質二丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、二季戊四醇單(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、二季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等。提昇硬度之用途時,宜為季戊四醇三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等。The first and second hydroxyl group-containing (meth) acrylate compounds are the same or different. Examples of such a hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (methyl). Acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-propenyl oxyethyl 2-hydroxyethyl decanoic acid, Glycerol mono (meth) acrylate, 2-hydroxy-3-propenyl propyl propyl (meth) acrylate, dihydroxy acrylate, glycerol mono (meth) acrylate, trimeric isocyanate EO modified diacrylate , pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Tris(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. When the hardness is used, it is preferably pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or the like.
具體之市售品可舉例如:Biscoat #300(大阪有機化學工業(股)製)、KAYARAD PET30(日本化藥(股)製)、PETIA(Daicel UCB(股)製)、Aronix M305(東亞合成(股)製)、NK酯-A-TMM-3LMN(新中村化學工業(股)製)、Light Acrylate PE-3A(共榮社化學(股)製)、SR-444(Sartomer(股)製)、Light Acrylate DPE-6A(共榮社化學(股)製)、KAYARAD.DPHA(日本化藥(股)製)、Aronix M402(東亞合成(股)製)等。Specific commercial products include, for example, Biscoat #300 (Osaka Organic Chemical Industry Co., Ltd.), KAYARAD PET30 (manufactured by Nippon Chemical Co., Ltd.), PETIA (Daicel UCB Co., Ltd.), Aronix M305 (East Asian Synthesis) (share) system, NK ester-A-TMM-3LMN (Xinzhongcun Chemical Industry Co., Ltd.), Light Acrylate PE-3A (Kyoeisha Chemical Co., Ltd.), SR-444 (Sartomer) ), Light Acrylate DPE-6A (Kyoeisha Chemical Co., Ltd.), KAYARAD. DPHA (Nippon Chemical Co., Ltd.), Aronix M402 (East Asia Synthetic Co., Ltd.), etc.
尤其以季戊四醇三(甲基)丙烯酸酯作為主成分之KAYARAD PET30(日本化藥(股)製)係金屬氧化物之分散性良好,故更佳。In particular, the KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.)-based metal oxide having pentaerythritol tri(meth)acrylate as a main component has a good dispersibility, and therefore is more preferable.
多官能(甲基)丙烯酸酯化合物之情形,由於含有持有2個羥基之多官能(甲基)丙烯酸酯5至15重量%左右作為副成分,所得到之分散劑(A)之硬化後的重量平均分子量有高分子量化之傾向,所以金屬氧化物之分散性亦變成更良好,故佳。In the case of a polyfunctional (meth) acrylate compound, since the polyfunctional (meth) acrylate having two hydroxyl groups is contained in an amount of about 5 to 15% by weight as a by-component, the obtained dispersant (A) is cured. Since the weight average molecular weight tends to be high in molecular weight, the dispersibility of the metal oxide becomes better, which is preferable.
上述芳香族或脂肪族四羧酸二酐、與第1及第2之含羥基的(甲基)丙烯酸酯化合物之反應係芳香族或脂肪族四羧酸二酐具有之2個羧酸酐基、與第1及第2之含羥基的(甲基)丙烯酸酯化合物分別具有之羥基的反應,此為本身在該領域中者所周知之技術。例如,使芳香族四羧酸二酐與第1及第2之含羥基的(甲基)丙烯酸酯化合物,在如環己酮之有機溶劑中,如1,8-二雜氮雙環[5.4.0]-7-十一碳烯之觸媒存在下,可在50至120℃之溫度反應。此時,於反應系中可添加如甲氧基醌(methoquinone)之聚合抑制劑。The reaction of the aromatic or aliphatic tetracarboxylic dianhydride with the first and second hydroxyl group-containing (meth) acrylate compounds is two carboxylic anhydride groups of an aromatic or aliphatic tetracarboxylic dianhydride. The reaction with the hydroxyl group of each of the first and second hydroxyl group-containing (meth) acrylate compounds is a technique known per se in the art. For example, the aromatic tetracarboxylic dianhydride and the first and second hydroxyl group-containing (meth) acrylate compounds are in an organic solvent such as cyclohexanone, such as 1,8-diazabicyclo[5.4. In the presence of a catalyst of 0]-7-undecene, it can be reacted at a temperature of 50 to 120 °C. At this time, a polymerization inhibitor such as methoquinone may be added to the reaction system.
上述反應後,於含有反應生成物之式(5)化合物(X)之反應混合物中,不精製此,例如,添加化合物(Y)之下述通式(6):
於以式(6)所示之化合物的例中,係含有如縮水甘油基(甲基)丙烯酸酯、縮水甘油基丙烯酸酯之含有環氧基的(甲基)丙烯酸酯;鄰苯基酚縮水甘油基醚、對苯基酚縮水甘油基醚、單苯乙烯化酚縮水甘油基醚、4-氰-4-羥基聯苯基縮水甘油基醚、4,4’-聯酚單縮水甘油基醚、4,4’-聯酚二縮水甘油基醚之芳香族縮水甘油基醚化合物等。In the example of the compound represented by the formula (6), an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate or glycidyl acrylate; o-phenyl phenol shrinkage Glyceryl ether, p-phenylphenol glycidyl ether, monostyrenated phenol glycidyl ether, 4-cyano-4-hydroxybiphenyl glycidyl ether, 4,4'-biphenol monoglycidyl ether An aromatic glycidyl ether compound of 4,4'-biphenol diglycidyl ether.
以式(5)所示之化合物與以式(6)所示之化合物之反應,係以式(5)所示之化合物具有之羧基與以式(6)所示之化合物具有之環氧基的反應,其本身在該領域中者已為所知。例如,此反應係如在二甲基苯甲基胺等之胺觸媒存在下、在50至120℃之溫度下實施。The reaction of the compound represented by the formula (5) with the compound represented by the formula (6) is carried out by a compound represented by the formula (5) having a carboxyl group and an epoxy group having a compound represented by the formula (6). The reaction itself is known in the art. For example, the reaction is carried out at a temperature of from 50 to 120 ° C in the presence of an amine catalyst such as dimethylbenzylamine.
此等之反應可在無溶劑下實施,或亦可在對於反應為惰性的溶劑中進行。如此之溶劑可舉例如:正己烷、苯或甲苯等之烴系溶劑;丙酮、甲乙酮或甲基異丁基酮等之酮系溶劑;醋酸乙酯或醋酸丁酯等之酯系溶劑;二乙基醚、四氫呋喃或二噁烷等之醚系溶劑;二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷或四氯乙烯(perclene)等之鹵系溶劑;乙腈、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基咪唑啉二酮等之極性溶劑等。此等之溶劑即使併用2種以上亦無妨。These reactions can be carried out without a solvent or in a solvent inert to the reaction. Examples of such a solvent include a hydrocarbon solvent such as n-hexane, benzene or toluene; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as ethyl acetate or butyl acetate; An ether solvent such as an ether, tetrahydrofuran or dioxane; a halogen solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perclene; acetonitrile, N, A polar solvent such as N-dimethylformamide, N,N-dimethylacetamide or N,N-dimethylimidazolidinone. These solvents may be used in combination of two or more kinds.
其次,金屬氧化物組成物中所含有之金屬氧化物,係平均一次粒徑為5至100nm之金屬氧化物。金屬氧化物之平均一次粒徑例如係使用透過型電子顯微鏡(TEM)或掃描型電子顯微鏡(SEM)等,而藉由直接觀察粒子本身來測定。Next, the metal oxide contained in the metal oxide composition is a metal oxide having an average primary particle diameter of 5 to 100 nm. The average primary particle diameter of the metal oxide is measured by, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM), by directly observing the particles themselves.
平均一次粒徑不足5nm之金屬氧化物時,因微粒子間之凝集力非常大,故要使透明性高之一次粒子程度分散乃非常困難。另外,平均一次粒徑超過100nm之金屬氧化物時,要使一次粒子程度分散係很容易,但因粒子徑大,故對於可見光等之光易產生散射,而會產生硬化膜之透明性惡化之問題。When the metal oxide having an average primary particle diameter of less than 5 nm is used, since the cohesive force between the fine particles is extremely large, it is extremely difficult to disperse the primary particles having high transparency. Further, in the case of a metal oxide having an average primary particle diameter of more than 100 nm, it is easy to disperse the primary particles. However, since the particle diameter is large, light such as visible light is easily scattered, and the transparency of the cured film is deteriorated. problem.
金屬氧化物係宜含有至少一種選自由鈦、鋅、鋯、銻、銦、錫、鋁、矽、磷、及氟所成群組中的元素。尤其,含有銻、銦、錫之任一種的元素之金屬氧化物因導電性亦良好,故更佳。The metal oxide preferably contains at least one element selected from the group consisting of titanium, zinc, zirconium, hafnium, indium, tin, aluminum, antimony, phosphorus, and fluorine. In particular, the metal oxide containing an element of any of bismuth, indium, and tin is more preferable because it has good conductivity.
具體上,可舉例如五氧化銻、摻雜銻之氧化錫(ATO)、摻雜錫之氧化銦(ITO)、摻雜氟之氧化錫(FTO)、摻雜磷之氧化錫(PTO)、銻酸鋅(AZO)、摻雜銦之氧化鋅(IZO)、氧化錫、被覆ATO之氧化鈦、摻雜鋁之氧化鋅、氧化鈦、氧化鋅、氧化鋯、氧化矽、氧化鋁等。此等之金屬氧化物即使併用2種類以上亦無妨。Specific examples thereof include ruthenium pentoxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), and phosphorus-doped tin oxide (PTO). Zinc citrate (AZO), indium-doped zinc oxide (IZO), tin oxide, ATO-coated titanium oxide, aluminum-doped zinc oxide, titanium oxide, zinc oxide, zirconium oxide, cerium oxide, aluminum oxide, and the like. These metal oxides may be used in combination of two or more types.
金屬氧化物之販售品可舉例如:日產化學工業(股)製:Sunepoch EFR-6N、Sunepoch EFR-6NP(五氧化銻)、石原產業(股)製:SN-100P(ATO)、FS-10P(ATO)、SN-102P(ATO)、FS-12P(ATO)、ET-300W(被覆ATO之氧化鈦)、TTO-55(A)(氧化鈦)、TTO-55(B)(氧化鈦)、TTO-55(C)(氧化鈦)、TTO-55(D)(氧化鈦)、TTO-55(S)(氧化鈦)、TTO-55(N)(氧化鈦)、TTO-51(A)(氧化鈦)、TTO-51(C)(氧化鈦)、TTO-S-1(氧化鈦)、TTO-S-2(氧化鈦)、TTO-S-3(氧化鈦)、TTO-S-4(氧化鈦)、TTO-F-1(含有鐵之氧化鈦)、TTO-F-2(含有鐵之氧化鈦)、TTO-F-3(含有鐵之氧化鈦)、TTO-F-11(含有鐵之氧化鈦)、ST-01(氧化鈦)、ST-21(氧化鈦)、ST-30L(氧化鈦)、ST-31(氧化鈦)、三菱Material(股)製:T-1(ITO)、S-1200(氧化錫)、EP SP-2(摻雜磷之氧化錫)、三井金屬工業(股)製:Pastran(ITO、ATO)、CI化成(股)製:Nanotech ITO、Nanotech SnO2 、Nanotech TiO2 、Nanotech SiO2 、Nanotech Al2 O3 、Nanotech ZnO、觸媒化成工業(股)製:TL-20(ATO)、TL-30(ATO)、TL-30S(PTO)、TL-120(ITO)、TL-130(ITO)、Hakusui Tech(股)製:Pazet CK(摻雜鋁之氧化鋅)、堺化學工業(股)製:FINEX-25(氧化鋅)、FINEX-25LP(氧化鋅)、FINEX-50(氧化鋅)、FINEX-50LP(氧化鋅)、FINEX-75(氧化鋅)、NANOFINE-50A(氧化鋅)、NANOFINE-50SD(氧化鋅)、EZ-1(氧化鋅)、STR-60C(氧化鈦)、STR-60C-LP(氧化鈦)、STR-100C(氧化鈦)、STR-100C-LP(氧化鈦)、STR-100A-LP(氧化鈦)、STR-100W(氧化鈦)、住友大阪水泥(股)製:OZC-3YC(氧化鋯)、OZC-3YD(氧化鋯)、OZC-3YFA(氧化鋯)、OZC-8YC(氧化鋯)、OZC-OS100(氧化鋯)、日本電工(股)製:PCS(氧化鋯)、PCS-60(氧化鋯)、PCS-90(氧化鋯)、T-01(氧化鋯)、Tayca(股)製:MT-100S(氧化鈦)、MT-100HD(氧化鈦)、MT-100SA(氧化鈦)、MT-500HD(氧化鈦)、MT-500SA(氧化鈦)、MT-600SA(氧化鈦)、MT-700HD(氧化鈦)、MZ-303S(氧化鋅)、MZY-303S(氧化鋅)、MZ-303M(氧化鋅)、MZ-505S(氧化鋅)、MZY-505S(氧化鋅)、MZ-505M(氧化鋅)、日本AEROSIL(股)製:氧化鋁C(氧化鋁)、AEROSIL 130(氧化矽)、AEROSIL 200(氧化矽)、AEROSIL 200V(氧化矽)、AEROSIL 200CF(氧化矽)、AEROSIL 200FA(氧化矽)、AEROSIL 300(氧化矽)、AEROSIL 300CF(氧化矽)、AEROSIL 380(氧化矽)、AEROSIL R972(氧化矽)、AEROSIL R974(氧化矽)、AEROSIL R976(氧化矽)、AEROSIL R202(氧化矽)、AEROSIL R805(氧化矽)、AEROSIL R812(氧化矽)、AEROSIL 812S(氧化矽)、AEROSIL MOX50(氧化矽)、AEROSIL TT600(氧化矽)、AEROSIL MOX80(氧化矽/氧化鋁)、AEROSIL MOX170(氧化矽/氧化鋁)、AEROSIL COX84(氧化矽/氧化鋁)等。For the sale of metal oxides, for example, Nissan Chemical Industry Co., Ltd.: Sunepoch EFR-6N, Sunepoch EFR-6NP (samarium pentoxide), Ishihara Industry Co., Ltd.: SN-100P (ATO), FS- 10P (ATO), SN-102P (ATO), FS-12P (ATO), ET-300W (coated with ATO titanium oxide), TTO-55 (A) (titanium oxide), TTO-55 (B) (titanium oxide) ), TTO-55 (C) (titanium oxide), TTO-55 (D) (titanium oxide), TTO-55 (S) (titanium oxide), TTO-55 (N) (titanium oxide), TTO-51 ( A) (titanium oxide), TTO-51 (C) (titanium oxide), TTO-S-1 (titanium oxide), TTO-S-2 (titanium oxide), TTO-S-3 (titanium oxide), TTO- S-4 (titanium oxide), TTO-F-1 (titanium containing iron), TTO-F-2 (titanium containing iron), TTO-F-3 (titanium containing iron), TTO-F -11 (titanium containing iron), ST-01 (titanium oxide), ST-21 (titanium oxide), ST-30L (titanium oxide), ST-31 (titanium oxide), Mitsubishi Material: -1 (ITO), S-1200 (tin oxide), EP SP-2 (phosphorus-doped tin oxide), Mitsui Metals Co., Ltd.: Pastran (ITO, ATO), CI Huacheng (share) system: Nanotech ITO, Nanotech SnO 2 , Nanotech TiO 2 , N Anotech SiO 2 , Nanotech Al 2 O 3 , Nanotech ZnO, Catalyst Chemicals Co., Ltd.: TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), TL-120 (ITO), TL-130 (ITO), Hakusui Tech (share): Pazet CK (doped aluminum zinc oxide), 堺 chemical industry (stock): FINEX-25 (zinc oxide), FINEX-25LP (zinc oxide), FINEX -50 (zinc oxide), FINEX-50LP (zinc oxide), FINEX-75 (zinc oxide), NANOFINE-50A (zinc oxide), NANOFINE-50SD (zinc oxide), EZ-1 (zinc oxide), STR-60C (titanium oxide), STR-60C-LP (titanium oxide), STR-100C (titanium oxide), STR-100C-LP (titanium oxide), STR-100A-LP (titanium oxide), STR-100W (titanium oxide) , Sumitomo Osaka Cement Co., Ltd.: OZC-3YC (zirconia), OZC-3YD (zirconia), OZC-3YFA (zirconia), OZC-8YC (zirconia), OZC-OS100 (zirconia), Japan Electrician (stock): PCS (zirconia), PCS-60 (zirconia), PCS-90 (zirconia), T-01 (zirconia), Tayca (manufacturing): MT-100S (titanium oxide), MT-100HD (titanium oxide), MT-100SA (titanium oxide), MT-500HD (titanium oxide), MT-500SA (titanium oxide), MT-600SA ( Titanium), MT-700HD (titanium oxide), MZ-303S (zinc oxide), MZY-303S (zinc oxide), MZ-303M (zinc oxide), MZ-505S (zinc oxide), MZY-505S (zinc oxide) ), MZ-505M (zinc oxide), Japan AEROSIL (stock) system: alumina C (alumina), AEROSIL 130 (yttria), AEROSIL 200 (yttria), AEROSIL 200V (yttria), AEROSIL 200CF (oxidation)矽), AEROSIL 200FA (矽 矽), AEROSIL 300 (矽 矽), AEROSIL 300CF (矽 矽), AEROSIL 380 (矽 矽), AEROSIL R972 (矽 矽), AEROSIL R974 (矽 矽), AEROSIL R976 (矽 矽), AEROSIL R202 (cerium oxide), AEROSIL R805 (cerium oxide), AEROSIL R812 (antimony oxide), AEROSIL 812S (antimony oxide), AEROSIL MOX50 (antimony oxide), AEROSIL TT600 (antimony oxide), AEROSIL MOX80 (antimony oxide / Alumina), AEROSIL MOX170 (yttria/alumina), AEROSIL COX84 (yttria/alumina), and the like.
金屬氧化物組成物中之金屬氧化物的添加量並無特別限制,但分散劑(A)及金屬氧化物之固形分合計量100重量份中,宜為1至80重量份、更宜為10至70重量份。金屬氧化物之添加量不足1重量份時,有時源自金屬氧化物之防止帶電性差,超過80重量份時因有機成分量少,而有成膜性差之情形。The amount of the metal oxide to be added to the metal oxide composition is not particularly limited, but is preferably from 1 to 80 parts by weight, more preferably 10 parts by weight based on 100 parts by weight of the solid content of the dispersing agent (A) and the metal oxide. Up to 70 parts by weight. When the amount of the metal oxide added is less than 1 part by weight, the charge resistance from the metal oxide may be poor. When the amount is more than 80 parts by weight, the amount of the organic component may be small, and the film formability may be poor.
本發明之金屬氧化物組成物即使僅混合分散劑(A)與金屬氧化物粉末而調製,亦可得到充分作為目的之效果。但,或藉由捏合機、輥、Atraiter、超磨機、乾式粉碎處理機等機械性進行混合、或添加一於金屬氧化物粉末與有機溶劑等所產生的懸濁液系中含有分散劑(A)的溶液,於金屬氧化物表面進行使分散劑(A)沉澱等之緊密的混合系,可得到更良好的結果。When the metal oxide composition of the present invention is prepared by merely mixing the dispersant (A) and the metal oxide powder, a sufficient effect can be obtained. However, it may be mechanically mixed by a kneader, a roll, an Atraiter, an ultra-grinding machine, a dry pulverizing machine, or the like, or a suspension containing a metal oxide powder and an organic solvent may contain a dispersing agent ( The solution of A) is subjected to a close mixing system such as precipitation of the dispersing agent (A) on the surface of the metal oxide, and more excellent results can be obtained.
此金屬氧化物組成物係以金屬氧化物粉末均一地分散之金屬氧化物分散體為佳。金屬氧化物分散體係使用分散劑(A),使平均一次粒徑為5至100nm之金屬氧化物在有機溶劑存在下分散,可較佳地製造。The metal oxide composition is preferably a metal oxide dispersion in which metal oxide powder is uniformly dispersed. The metal oxide dispersion system is preferably produced by dispersing a metal oxide having an average primary particle diameter of 5 to 100 nm in the presence of an organic solvent using a dispersing agent (A).
分散之程度係以利用動態光散射法之日機裝(股)製「Nanotrack UPA」測定之情形,分散粒徑D99宜不足300nm,更宜為不足200nm。The degree of dispersion is measured by "Nanotrack UPA" manufactured by Nikkiso Co., Ltd. using a dynamic light scattering method, and the dispersed particle diameter D99 is preferably less than 300 nm, more preferably less than 200 nm.
於有機溶劑等之非水系載體(vehicle)中的分散劑(A)、金屬氧化物、或金屬氧化物組成物之分散或溶解、及此等之混合等,係可使用Paint Conditioner(Red Devil公司製)、球磨機、砂磨機(Shinmaru Enterprises公司製「Dayno mill」等)、Atraiter、珠粒研磨機(EIRICH公司製「DCP mill」等)、CoBall研磨機、均混機、均質機(M.Technical公司製「Clearmix」等)、濕式噴磨機(Genus公司製「GenusPY」、Nanomizer公司製「Nanomizer」)、微小珠粒研磨機(壽工業(股)製「Super Apec mill」、「Ultra Apec mill」)等之分散機。於分散機使用媒介質時,係宜使用玻璃珠粒、氧化鋯珠粒、氧化鋁珠粒、磁性珠粒、苯乙烯珠粒等。有關分散係分別使用2種類以上之分散機、或大小相異之2種類以上之媒介質,階段性使用亦無妨。Paint Conditioner (Red Devil) can be used for dispersion or dissolution of a dispersant (A), a metal oxide, or a metal oxide composition in a non-aqueous vehicle such as an organic solvent, and the like. (), ball mill, sand mill ("Dayno mill" by Shinmaru Enterprises, etc.), Atraiter, bead mill ("DCP mill" by EIRICH), CoBall mill, homomixer, homogenizer (M. "Clearmix" manufactured by Technical Co., Ltd.), wet jet mill ("GenusPY" manufactured by Genus, "Nanomizer" manufactured by Nanomizer), and microbead mill (Super Apec mill" manufactured by Shou Industrial Co., Ltd., "Ultra Apec mill") and other dispersing machines. When the vehicle is used in a dispersing machine, glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, and the like are preferably used. In the dispersion system, two or more types of dispersing machines or two or more types of media having different sizes are used, and it is also possible to use them in stages.
本發明之金屬氧化物組成物係至少含有分散劑(A)及金屬氧化物者,進而,在無損本發明之目的或效果的範圍內可含有溶劑或各種之添加劑。具體上可舉例如溶劑、光聚合起始劑、光硬化性化合物、聚合抑制劑、光增感劑、流平劑、界面活性劑、抗菌劑、防黏連劑、可塑劑、紫外線吸收劑、紅外線吸收劑、抗氧化劑、矽烷偶合劑、導電性聚合物、導電性界面活性劑、無機填充劑、顏料、染料等。The metal oxide composition of the present invention contains at least a dispersant (A) and a metal oxide, and further contains a solvent or various additives within a range not detracting from the object or effect of the present invention. Specific examples thereof include a solvent, a photopolymerization initiator, a photocurable compound, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an antibacterial agent, an anti-blocking agent, a plasticizer, and an ultraviolet absorber. Infrared absorber, antioxidant, decane coupling agent, conductive polymer, conductive surfactant, inorganic filler, pigment, dye, and the like.
含有分散劑(A)及金屬氧化物以外之成分的金屬氧化物組成物之製造方法,並無特別限制,可列舉一些方法。具體上係可列舉如:最先於有機溶劑中使分散劑(A)及金屬氧化物進行混合分散,得到安定之金屬氧化物分散體後,添加及調整其他之各種添加劑,進行製造之方法;從最初,以分散劑(A)、金屬氧化物、有機溶劑及其他之添加劑的全部混合之狀態,進行分散,製造之方法等。The method for producing the metal oxide composition containing the component other than the dispersing agent (A) and the metal oxide is not particularly limited, and some methods can be mentioned. Specifically, for example, a method in which a dispersing agent (A) and a metal oxide are mixed and dispersed in an organic solvent to obtain a stable metal oxide dispersion, and various other additives are added and adjusted, and the method is produced; From the beginning, a method of dispersing, manufacturing, and the like is carried out in a state in which the dispersing agent (A), the metal oxide, the organic solvent, and other additives are all mixed.
加入溶劑時,宜使溶劑揮發後再進行硬化處理。作為溶劑者並無特別限制,可使用各種習知之有機溶劑。具體上可舉例如:環己酮、甲基異丁基酮、甲乙酮、丙酮、乙醯基丙酮、甲苯、二甲苯、正丁醇、異丁醇、第三丁醇、正丙醇、異丙醇、乙醇、甲醇、3-甲氧基-1-丁醇、3-甲氧基-2-丁醇、乙二醇單甲基醚、乙二醇單正丁基醚、2-乙氧基乙醇、1-甲氧基-2-丙醇、二丙酮醇、乳酸乙酯、乳酸丁酯、丙二醇單甲基醚、乙二醇單正丁基醚乙酸酯、丙二醇單甲基醚乙酸酯、2-乙氧基乙基乙酸酯、丁基乙酸酯、異戊基乙酸酯、己二酸二甲酯、琥珀酸二甲酯、戊二酸二甲酯、四氫呋喃、甲基吡咯烷酮等。此等之有機溶劑即使併用2種類以上亦無妨。When the solvent is added, the solvent is preferably volatilized and then hardened. The solvent is not particularly limited, and various conventional organic solvents can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetyl ketone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, and isopropyl Alcohol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, 2-ethoxyl Ethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate Ester, 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, methyl Pyrrolidone and the like. These organic solvents may be used in combination of two or more types.
其中,含羥基之溶劑相對於具有親水性高的粒子表面物性之金屬氧化物因係潤濕性良好,故以在溶劑組成中含有,在金屬氧化物之分散性及其塗料(金屬氧化物組成物)的隨時間安定性之提昇上非常有效果,且塗佈步驟之流平性亦提高,故佳。全溶劑組成中之含有羥基的溶劑含量宜為10至100重量%。具體上,含有羥基的溶劑可舉例如:正丁醇、異丁醇、第三丁醇、正丙醇、異丙醇、乙醇、甲醇、3-甲氧基-1-丁醇、3-甲氧基-2-丁醇、乙二醇單甲基醚、乙二醇單正丁基醚、2-乙氧基乙醇、1-甲氧基-2-丙醇、二丙酮醇、乳酸乙酯、乳酸丁酯、丙二醇單甲基醚等。尤其3-甲氧基-1-丁醇、丙二醇單甲基醚、乙二醇單甲基醚、乙二醇單正丁基醚,因金屬氧化物之分散性與分散安定性變成更良好,故佳。Among them, the hydroxyl group-containing solvent has good wettability with respect to the metal oxide having high hydrophilicity on the surface property of the particles, so it is contained in the solvent composition, the dispersibility in the metal oxide, and the coating (metal oxide composition). The improvement of the stability of the material over time is very effective, and the leveling of the coating step is also improved, so it is good. The content of the hydroxyl group-containing solvent in the total solvent composition is preferably from 10 to 100% by weight. Specifically, the solvent containing a hydroxyl group may, for example, be n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methyl Oxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate , butyl lactate, propylene glycol monomethyl ether and the like. In particular, 3-methoxy-1-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethylene glycol mono-n-butyl ether are more excellent in dispersibility and dispersion stability of the metal oxide. So good.
光聚合起始劑係只要具有可藉由光激發而開始乙烯基聚合之功能即可,並無特別限定,例如,可使用單羰基化合物、二羰基化合物、乙醯苯化合物、苯偶因醚化合物、醯基氧化磷化合物、胺基羰基化合物等。The photopolymerization initiator is not particularly limited as long as it has a function of starting vinyl polymerization by photoexcitation, and for example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, or a benzoin ether compound can be used. , fluorenyl phosphorus oxide compounds, amine carbonyl compounds, and the like.
具體上單羰基化合物係可舉例如:二苯甲酮、4-甲基-二苯甲酮、2,4,6-三甲基二苯甲酮、甲基-鄰-苯甲醯基苯甲酸酯、4-苯基二苯甲酮、4-(4-甲基苯基硫)苯基-乙酮、3,3’-二甲基-4-甲氧基二苯甲酮、4-(1,3-丙烯醯基-1,3,3’-二甲基-4-甲氧基二苯甲酮、4-(1,3-丙烯醯基-1,4,7,10,13-五氧三癸基)二苯甲酮、3,3’,4,4’-四(第三丁過氧化羰基)二苯甲酮、4-苯甲醯基-N,N,N-三甲基-1-丙烷胺鹽酸鹽、4-苯甲醯基-N,N-二甲基-N-2-(1-氧-2-丙烯基氧乙基)偏銨草酸鹽、2-/4-異丙基硫雜蔥酮、2,4-二乙基硫雜蔥酮、2,4-二氯硫雜蔥酮、1-氯-4-丙氧基硫雜蔥酮、2-羥基-3-(3,4-二甲基-9-氧-9H硫雜蔥酮-2-基氧-N,N,N-三甲基-1-丙烷胺鹽酸鹽、苯甲醯基亞甲基-3-甲基萘(1,2-d)噻唑啉等。Specific examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, and methyl-o-benzylidenebenzophenone. Acid ester, 4-phenylbenzophenone, 4-(4-methylphenylthio)phenyl-ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-propenylmercapto-1,3,3'-dimethyl-4-methoxybenzophenone, 4-(1,3-propenylmercapto-1,4,7,10,13 -pentamethoxytrimethyl)benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4-benzylidene-N,N,N-three Methyl-1-propanamine hydrochloride, 4-benzylidene-N,N-dimethyl-N-2-(1-oxo-2-propenyloxyethyl) ammonium oxalate, 2 -/4-isopropylthioxanthene, 2,4-diethylthiane, 2,4-dichlorothiazepine, 1-chloro-4-propoxythione, 2 -hydroxy-3-(3,4-dimethyl-9-oxo-9H-thionen-2-yloxy-N,N,N-trimethyl-1-propanamine hydrochloride, benzamidine A benzylidene-3-methylnaphthalene (1,2-d) thiazoline or the like.
二羰基化合物可舉例如:1,2,2-三甲基-雙環[2.1.1]庚烷-2,3-二酮、苯偶醯(Benzil)、2-乙基蔥酮、9,10-菲醌、甲基-α-氧苯乙酸酯、4-苯基苯偶醯等。苯乙酮(Acetophenone)化合物係可舉例如:2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-二-2-甲基-1-苯基丙烷-1-酮、1-羥基-環己基苯基酮、2-羥基-2-甲基-1-苯乙烯基丙烷-1-酮聚合物、二乙氧基苯乙酮、二丁氧基苯乙酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2,2-二乙氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲基硫)苯基]-2-嗎啉基丙烷-1-酮、2-苯甲基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮、1-苯基-1,2-丙烷二酮-2-(鄰乙氧基羰基)肟、3,6-雙(2-甲基-2-嗎啉基-丙醯基)-9-丁基咔唑等。The dicarbonyl compound may, for example, be 1,2,2-trimethyl-bicyclo[2.1.1]heptane-2,3-dione, Benzil, 2-ethyl onion, 9,10 - phenanthrenequinone, methyl-α-oxyphenylacetate, 4-phenylbenzoquinone, and the like. The acetophenone compound may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-1-one or 1-(4-isopropylphenyl)-2-hydroxy-2-methyl 1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclo Hexyl phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy 1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one , 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, 3,6-bis(2-methyl-2-morpholinyl-propenyl)-9-butyl Carbazole and the like.
苯偶因醚化合物可舉例如:苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚、苯偶因異丁基醚、苯偶因正丁基醚等。Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether. Wait.
醯基氧化磷化合物可舉例如:2,4,6-三甲基苯甲醯基二苯基氧化磷、4-正丙基苯基-二(2,6-二氯苯甲醯基)氧化磷等。The fluorenylphosphorus oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 4-n-propylphenyl-bis(2,6-dichlorobenzhydryl) oxide. Phosphorus, etc.
胺基羰基化合物可舉例如:甲基-4-(二甲氧基胺基)苯甲酸酯、乙基-4-(二甲基胺基)苯甲酸酯、2-正丁氧乙基-4-(二甲基胺基)苯甲酸酯、異戊基-4-(二甲基胺基)苯甲酸酯、2-(二甲基胺基)乙基苯甲酸酯、4,4’-雙-4-二甲基胺基苯甲酸酯、4,4’-雙-4-二乙基胺基苯甲酸酯、2,5’-雙(4-二乙基胺基苯亞甲基)環戊酮等。The aminocarbonyl compound may, for example, be methyl-4-(dimethoxyamino)benzoate, ethyl-4-(dimethylamino)benzoate or 2-n-butoxyethyl -4-(Dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate, 4 , 4'-bis-4-dimethylaminobenzoate, 4,4'-bis-4-diethylaminobenzoate, 2,5'-bis(4-diethylamine) Benzomethylene)cyclopentanone and the like.
光聚合起始劑之市售品可舉例如Ciba Specialty Chemicals(股)製Irgacure 184、651、500、907、127、369、784、2959、BASF公司製Lucirin TPO、日本西貝黑格納(Nihon Siber Hegner)(股)製Esacure One等。Commercial products of the photopolymerization initiator include, for example, Irgacure 184, 651, 500, 907, 127, 369, 784, 2959 manufactured by Ciba Specialty Chemicals Co., Ltd., Lucirin TPO manufactured by BASF Corporation, and Nihon Siber Hegner (Japan). ) (share) Esacure One and so on.
光聚合起始劑係不限定於上述化合物,而只要具有藉由紫外線開始聚合之能力即可,任一者均無妨。此等之光聚合起始劑除了可以使用一種類之外,亦可混合2種類以上而使用。The photopolymerization initiator is not limited to the above compounds, and any one may have any ability to initiate polymerization by ultraviolet rays. These photopolymerization initiators may be used in combination of two or more types in addition to one type.
有關光聚合起始劑之使用量係無特別限制,但相對於含有分散劑(A)之光硬化性化合物的全量(以含有任意下述之光硬化性化合物時,係分散劑(A)與光硬化性化合物之合計量)100重量份以使用1至20重量份之範圍內為宜。The amount of the photopolymerization initiator to be used is not particularly limited, but is a total amount of the photocurable compound containing the dispersing agent (A) (in the case of containing any photocurable compound described below), the dispersing agent (A) and The total amount of the photocurable compound is preferably in the range of 1 to 20 parts by weight per 100 parts by weight.
增感劑亦可加入習知之有機胺等。The sensitizer may also be added to a conventional organic amine or the like.
進一步,除上述自由基聚合起始劑外,亦可併用陽離子聚合起始劑。Further, in addition to the above-mentioned radical polymerization initiator, a cationic polymerization initiator may be used in combination.
金屬氧化物組成物係除分散劑(A)之外,亦可含有其他之黏結劑樹脂、或光硬化性化合物。The metal oxide composition may contain other binder resins or photocurable compounds in addition to the dispersant (A).
黏結劑樹脂可舉例如:聚胺酯樹脂、聚脲樹脂、聚胺酯脲樹脂、聚酯樹脂、聚醚樹脂、聚碳酸酯樹脂、環氧基樹脂、胺基樹脂、苯乙烯樹脂、丙烯酸樹脂、三聚氰胺樹脂、聚醯胺樹脂、酚樹脂、乙烯基樹脂等。此等之樹脂可使用一種類,亦可混合2種類以上而使用。黏結劑樹脂係以金屬氧化物組成物之固形分(溶劑以外之成分。以下,相同)之全量作為基準(100重量份),使用20重量份以下之範圍內。The binder resin may, for example, be a polyurethane resin, a polyurea resin, a polyurethane urea resin, a polyester resin, a polyether resin, a polycarbonate resin, an epoxy resin, an amine resin, a styrene resin, an acrylic resin, a melamine resin, Polyamide resin, phenol resin, vinyl resin, and the like. These resins may be used in one type or in combination of two or more types. The binder resin is used in a range of 20 parts by weight or less based on the total amount of the solid content of the metal oxide composition (components other than the solvent, the same applies hereinafter).
光硬化性化合物係可使用例如:(甲基)丙烯酸系化合物、脂肪酸乙烯基酯化合物、烷基乙烯基醚化合物、α-烯烴化合物、乙烯基化合物、乙炔基化合物等具有聚合性不飽和雙鍵基之化合物。此等具有聚合性不飽和雙鍵基之化合物係進一步亦可具有羥基、烷氧基、羧基、醯胺基、矽烷醇基等之官能基。此光硬化性化合物係以金屬氧化物組成物之固形分之全量作為基準(100重量份),使用不足50重量份之範圍內尤其以使用4至40重量份之範圍內為佳。As the photocurable compound, for example, a (meth)acrylic compound, a fatty acid vinyl ester compound, an alkyl vinyl ether compound, an α-olefin compound, a vinyl compound, an ethynyl compound or the like can have a polymerizable unsaturated double bond. Base compound. The compound having a polymerizable unsaturated double bond group may further have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, a decylamino group or a stanol group. The photocurable compound is preferably used in an amount of less than 50 parts by weight, particularly preferably from 4 to 40 parts by weight, based on the total amount of the solid content of the metal oxide composition.
作為(甲基)丙烯酸系化合物係具有:苯甲基(甲基)丙烯酸酯、烷基系(甲基)丙烯酸酯、伸烷基甘醇系(甲基)丙烯酸酯、具有羧基與聚合性不飽和雙鍵之化合物、具有羥基之(甲基)丙烯酸系化合物、含氮之(甲基)丙烯酸系化合物等。又,可適宜使用單官能、多官能之化合物。從光硬化性、塗膜之硬塗性而言,宜為多官能者。The (meth)acrylic compound has a benzyl (meth) acrylate, an alkyl (meth) acrylate, an alkyl glycerol (meth) acrylate, a carboxyl group, and a polymerizable property. A compound having a saturated double bond, a (meth)acrylic compound having a hydroxyl group, a nitrogen-containing (meth)acrylic compound, or the like. Further, a monofunctional or polyfunctional compound can be suitably used. From the viewpoint of photocurability and hard coating property of the coating film, it is preferred to be a polyfunctional one.
單官能之(甲基)丙烯酸系化合物具體上,烷基系(甲基)丙烯酸酯可舉例如:甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、庚基(甲基)丙烯酸酯、己基(甲基)丙烯酸酯、辛基(甲基)丙烯酸酯、壬基(甲基)丙烯酸酯、癸基(甲基)丙烯酸酯、十一碳烷基(甲基)丙烯酸酯、十二碳烷基(甲基)丙烯酸酯、十三碳烷基(甲基)丙烯酸酯、十四碳烷基(甲基)丙烯酸酯、十五碳烷基(甲基)丙烯酸酯、十六碳烷基(甲基)丙烯酸酯、十七碳烷基(甲基)丙烯酸酯、十八烷基(甲基)丙烯酸酯、十九碳烷基(甲基)丙烯酸酯、二十碳烷基(甲基)丙烯酸酯、二十一碳烷基(甲基)丙烯酸酯、二十二碳烷基(甲基)丙烯酸酯等碳數1至22的伸烷基(甲基)丙烯酸酯。以極性之調整為目的時,係宜使用碳數2至10、更佳係具有碳數2至8之烷基的含烷基之(甲基)丙烯酸酯。又,以流平性之調節等為目的時係以使用具有碳數6以上之烷基的烷基(甲基)丙烯酸酯為佳。Specific examples of the monofunctional (meth)acrylic compound The alkyl (meth)acrylate may, for example, be methyl (meth) acrylate, ethyl (meth) acrylate or propyl (methyl). Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, Octyl (meth) acrylate, mercapto (meth) acrylate, mercapto (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate , tridecyl (meth) acrylate, tetradecyl (meth) acrylate, fifteen alkyl (meth) acrylate, hexadecyl (meth) acrylate, ten Heptacarbon (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, twenty-one carbon Alkyl (meth) acrylate having a carbon number of 1 to 22 such as an alkyl (meth) acrylate or a docosyl (meth) acrylate. For the purpose of adjusting the polarity, an alkyl group-containing (meth) acrylate having a carbon number of 2 to 10, more preferably an alkyl group having 2 to 8 carbon atoms, is preferably used. Further, in order to adjust the leveling property or the like, an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms is preferably used.
伸烷基甘醇系(甲基)丙烯酸酯可舉例如二乙二醇單(甲基)丙烯酸酯、三乙二醇單(甲基)丙烯酸酯、四乙二醇單(甲基)丙烯酸酯、六乙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、二丙二醇單(甲基)丙烯酸酯、三丙二醇單(甲基)丙烯酸酯、四丙二醇單(甲基)丙烯酸酯、聚四亞甲基甘醇(甲基)丙烯酸酯等之,於末端具有羥基且具有聚氧伸烷基鏈之單(甲基)丙烯酸酯;甲氧基乙二醇(甲基)丙烯酸酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基四乙二醇(甲基)丙烯酸酯、乙氧基四乙二醇(甲基)丙烯酸酯、丙氧基四乙二醇(甲基)丙烯酸酯、正丁氧基四乙二醇(甲基)丙烯酸酯、正戊氧基四乙二醇(甲基)丙烯酸酯、三丙二醇(甲基)丙烯酸酯、四丙二醇(甲基)丙烯酸酯、甲氧基三丙二醇(甲基)丙烯酸酯、甲氧基四丙二醇(甲基)丙烯酸酯、乙氧基四丙二醇(甲基)丙烯酸酯、丙氧基四丙二醇(甲基)丙烯酸酯、正丁氧基四丙二醇(甲基)丙烯酸酯、正戊氧基四丙二醇(甲基)丙烯酸酯、聚四亞甲基甘醇(甲基)丙烯酸酯、甲氧基聚四亞甲基甘醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯之,於末端具有烷氧基且具有聚氧伸烷基鏈之單(甲基)丙烯酸酯;苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基乙二醇(甲基)丙烯酸酯、苯氧基三乙二醇(甲基)丙烯酸酯、苯氧基四乙二醇(甲基)丙烯酸酯、苯氧基六乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、苯氧基四丙乙二醇(甲基)丙烯酸酯等之,於末端具有苯氧基或芳氧基之聚氧伸烷基系(甲基)丙烯酸酯。The alkylglycol-based (meth) acrylate may, for example, be diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate. , hexaethylene glycol mono(meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (a) Acrylate, polytetramethylene glycol (meth) acrylate, etc., mono(meth) acrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain; methoxyethylene glycol (A) Acrylate, methoxydiethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxylate Tetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-pentyloxytetraethylene glycol (A) Acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy tetrapropylene glycol (meth) acrylate, ethoxy Tetrapropanediol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentyloxy tetrapropylene glycol (meth) acrylate, polytetra Methylene glycol (meth) acrylate, methoxy polytetramethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, mono(meth) acrylate having an alkoxy group at the terminal and having a polyoxyalkylene chain; phenoxy diethylene glycol (meth) acrylate, phenoxy ethane Alcohol (meth) acrylate, phenoxy triethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, a polyoxyalkylene group having a phenoxy group or an aryloxy group at the terminal, such as phenoxy polyethylene glycol (meth) acrylate or phenoxytetrapropylene glycol (meth) acrylate (A) Base) acrylate.
具有羧基及聚合性不飽和雙鍵基之化合物係可舉例如馬來酸、富馬酸、衣康酸、中康酸、或此等之烷基或烯烴基單酯、酞酸β-(甲基)丙烯氧乙基單酯、異酞酸β-(甲基)丙烯氧乙基單酯、琥珀酸β-(甲基)丙烯氧乙基單酯、丙烯酸、甲基丙烯酸、巴豆酸、肉桂酸等。The compound having a carboxyl group and a polymerizable unsaturated double bond group may, for example, be maleic acid, fumaric acid, itaconic acid, mesaconic acid, or the like, or an alkyl or alkene monoester, or a decanoic acid β-(A) Acrylic oxyethyl monoester, isophthalic acid β-(meth) propylene oxyethyl monoester, β-(meth) propylene oxyethyl monoester succinate, acrylic acid, methacrylic acid, crotonic acid, cinnamon Acid, etc.
含羥基之(甲基)丙烯酸系化合物可舉例如:2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、4-羥基乙烯基苯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯等。Examples of the hydroxyl group-containing (meth)acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Glycerol mono (meth) acrylate, 4-hydroxyvinyl benzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
含氮之(甲基)丙烯酸系化合物有:(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基-(甲基)丙烯醯胺、N-乙氧基甲基-(甲基)丙烯醯胺、N-丙氧基甲基-(甲基)丙烯醯胺、N-丁氧基甲基-(甲基)丙烯醯胺、N-戊氧甲基-(甲基)丙烯醯胺等之單羥烷基(甲基)丙烯醯胺、N,N-二(羥甲基)丙烯醯胺、N-羥甲基-N-甲氧基甲基(甲基)丙烯醯胺、N,N-二(羥甲基)丙烯醯胺、N-乙氧基甲基-N-甲氧基甲基甲基丙烯醯胺、N,N-二(乙氧基甲基)丙烯醯氨、N-乙氧基甲基-N-丙氧基甲基甲基丙烯醯胺、N,N-二(丙氧基甲基)丙烯醯胺、N-丁氧基甲基-N-(丙氧基甲基)甲基丙烯醯胺、N,N-二(丁氧基甲基)丙烯醯胺、N-丁氧基甲基-N-(甲氧基甲基)甲基丙烯醯胺、N,N-二(戊氧基甲基)丙烯醯胺、N-甲氧基甲基-N-(戊氧基甲基)甲基丙烯醯胺等之二羥烷基(甲基)丙烯醯胺等的丙烯醯胺系不飽和化合物;二甲基胺基乙基(甲基)丙烯酸酯、二乙基胺基乙基(甲基)丙烯酸酯、甲基乙基胺基乙基(甲基)丙烯酸酯、二甲基胺基苯乙烯、二乙基胺基苯乙烯等之具有二烷基胺基的不飽和化合物;及,具有Cl- 、Br- 、I- 等之鹵素離子或QSQ3- (Q:碳數1至12之烷基)作為離子對之含二烷基胺基的不飽和化合物之4級銨鹽等。The nitrogen-containing (meth)acrylic compound is: (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl-(meth) acrylamide, N -ethoxymethyl-(meth) acrylamide, N-propoxymethyl-(meth) acrylamide, N-butoxymethyl-(meth) acrylamide, N-pentyl Monohydroxyalkyl (meth) acrylamide, N,N-bis(hydroxymethyl) acrylamide, N-hydroxymethyl-N-methoxy group such as oxymethyl-(meth) acrylamide Methyl (meth) acrylamide, N,N-bis(hydroxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) propylene hydrazine, N-ethoxymethyl-N-propoxymethyl methacrylamide, N,N-bis(propoxymethyl) acrylamide, N- Butoxymethyl-N-(propoxymethyl)methacrylamide, N,N-bis(butoxymethyl)propenylamine, N-butoxymethyl-N-(methoxy Methyl methacrylamide, N,N-bis(pentyloxymethyl)propenylamine, N-methoxymethyl-N-(pentyloxymethyl)methacrylamide, etc. Dihydroxyalkyl (meth) propylene Acrylamine-based unsaturated compound such as guanamine; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methyl ethyl amide ethyl (A) An unsaturated compound having a dialkylamino group such as acrylate, dimethylaminostyrene or diethylaminostyrene; and a halogen ion having a Cl - , Br - , I - or the like or QSQ3 - (Q: an alkyl group having 1 to 12 carbon atoms) as a quaternary ammonium salt of a dialkylamino group-containing unsaturated compound of an ion pair or the like.
其他之不飽和化合物可舉例如:全氟甲基甲基(甲基)丙烯酸酯、全氟乙基甲基(甲基)丙烯酸酯、2-全氟丁基乙基(甲基)丙烯酸酯、2-全氟己基乙基(甲基)丙烯酸酯、2-全氟辛基乙基(甲基)丙烯酸酯、2-全氟異壬基乙基(甲基)丙烯酸酯、2-全氟壬基乙基(甲基)丙烯酸酯、2-全氟癸基乙基(甲基)丙烯酸酯、全氟丙基丙基(甲基)丙烯酸酯、全氟辛基丙基(甲基)丙烯酸酯、全氟辛基戊基(甲基)丙烯酸酯、全氟辛基十一碳烷基(甲基)丙烯酸酯等之具有碳數1至20之全氟烷基的全氟烷基烷基(甲基)丙烯酸酯類。進一步,可舉例如:全氟丁基乙烯、全氟己基乙烯、全氟辛基乙烯、全氟癸基乙烯等之全氟烷基、伸烷基類等之含全氟烷基的乙烯基單體;乙烯基三氯矽烷、乙烯基三(β-甲氧基乙氧基)矽烷、乙烯基三乙氧基矽烷、γ-(甲基)丙烯氧丙基三甲氧基矽烷等之烷氧基矽烷基的乙烯基化合物及其衍生物;縮水甘油基丙烯酸酯、3,4-環氧基環己基丙烯酸酯等之含有縮水甘油基的丙烯酸酯。Examples of other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethyl methyl (meth) acrylate, and 2-perfluorobutyl ethyl (meth) acrylate. 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisodecylethyl (meth) acrylate, 2-perfluoro fluorene Ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropyl propyl (meth) acrylate, perfluorooctyl propyl (meth) acrylate a perfluoroalkylalkyl group having a perfluoroalkyl group having 1 to 20 carbon atoms such as perfluorooctylpentyl (meth) acrylate or perfluorooctyldecyl (meth) acrylate ( Methyl) acrylates. Further, for example, a perfluoroalkyl group-containing vinyl monomer such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene or the like, a perfluoroalkyl group or an alkylene group may be mentioned. Alkoxy groups such as vinyltrichloromethane, vinyltris(β-methoxyethoxy)decane, vinyltriethoxydecane, γ-(meth)acryloxypropyltrimethoxydecane a vinyl group-containing vinyl compound and a derivative thereof; a glycidyl group-containing acrylate such as glycidyl acrylate or 3,4-epoxycyclohexyl acrylate.
脂肪酸乙烯酯化合物可舉例如:醋酸乙烯酯、酪酸乙烯酯、巴豆酸乙烯酯、辛酸乙烯酯、月桂酸乙烯酯、氯醋酸乙烯酯、油酸乙烯酯、硬酯酸乙烯酯等。The fatty acid vinyl ester compound may, for example, be vinyl acetate, vinyl butyrate, vinyl crotonate, vinyl octanoate, vinyl laurate, vinyl chloroacetate, vinyl oleate or vinyl stearate.
烷基乙烯基醚化合物可舉例如丁基乙烯基醚、乙基乙烯基醚等。The alkyl vinyl ether compound may, for example, be butyl vinyl ether or ethyl vinyl ether.
α-烯烴化合物可舉例如:1-己烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯等。The α-olefin compound may, for example, be 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene or 1-hexadecene.
乙烯基化合物可舉例如:烯丙基醋酸、烯丙基醇、烯丙基苯、氰化烯丙基等之烯丙基化合物、氰化乙烯、乙烯基環己烷、乙烯基甲基酮、苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、氯苯乙烯等。Examples of the vinyl compound include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, and vinyl methyl ketone. Styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, and the like.
乙炔基化合物可舉例如:乙炔、乙炔基苯、乙炔基甲苯、1-乙炔基-1-環己醇等。Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol, and the like.
此等係可以一種使用,亦可混合2種類而使用。此等之中,分散劑(A)以外之光硬化性化合物,從塗膜強度、耐擦傷性而言,可適當使用至少具有3個官能基之聚胺酯聚(甲基)丙烯酸酯、聚環氧基聚(甲基)丙烯酸酯等之聚(甲基)丙烯酸酯類、於分子內具有3個以上之丙烯醯基的多官能丙烯酸酯類。These may be used one by one or two types may be mixed. Among these, the photocurable compound other than the dispersing agent (A) can be suitably used as a polyurethane poly(meth)acrylate or polyepoxy having at least three functional groups from the viewpoint of coating film strength and scratch resistance. A poly(meth)acrylate such as a poly(meth)acrylate or a polyfunctional acrylate having three or more acrylonitrile groups in a molecule.
聚環氧基聚(甲基)丙烯酸酯係使環氧基樹脂之環氧基以(甲基)丙烯酸進行酯化,而使官能基形成為(甲基)丙烯醯基者,有對雙酚A型環氧基樹脂之(甲基)丙烯酸加成物、對酚醛清漆型環氧基樹脂之(甲基)丙烯酸加成物等。The polyepoxy poly(meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth)acrylic acid, and forming a functional group into a (meth) acrylonitrile group, and having a bisphenol. A (meth)acrylic acid addition product of a type A epoxy resin, a (meth)acrylic acid addition product of a novolak type epoxy resin, and the like.
聚胺酯聚(甲基)丙烯酸酯例如有:使二異氰酸酯與具有羥基之(甲基)丙烯酸酯類反應所得到者;使多元醇與聚異氰酸酯在異氰酸酯基過剩的條件下反應而構成之含異氰酸酯基的胺酯聚合物、與具有羥基之(甲基)丙烯酸酯類反應所得到者。或,使多元醇與聚異氰酸酯在羥基過剩的條件下反應而構成之含羥基的胺酯聚合物、與具有異氰酸酯之(甲基)丙烯酸酯類反應所得到者。The polyurethane poly(meth) acrylate is, for example, obtained by reacting a diisocyanate with a (meth) acrylate having a hydroxyl group; and an isocyanate group formed by reacting a polyhydric alcohol with a polyisocyanate under an excess of an isocyanate group. The amine ester polymer obtained by reacting with a (meth) acrylate having a hydroxyl group. Alternatively, a hydroxyl group-containing amine ester polymer obtained by reacting a polyhydric alcohol with a polyisocyanate under conditions in which a hydroxyl group is excessively reacted with a (meth) acrylate having an isocyanate is obtained.
多元醇係可舉例如:乙二醇、丙二醇、二乙二醇、二丙二醇、丁二醇、1,6-己二醇、3-甲基-1,5-戊二醇、新戊二醇、己三醇、三羥甲基丙烷、聚四亞甲基甘醇、己二酸與乙二醇之縮聚合物等。Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and neopentyl glycol. a condensed polymer of hexanetriol, trimethylolpropane, polytetramethylene glycol, adipic acid and ethylene glycol.
聚異氰酸酯可舉例如:甲苯伸二聚異氰酸酯、異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯等。Examples of the polyisocyanate include toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
具有羥基之(甲基)丙烯酸酯類係可舉例如:2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、4-羥丁基(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、雙三羥甲基丙烷四(甲基)丙烯酸酯等。Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like.
具有異氰酸酯基之(甲基)丙烯酸酯類係可舉例如:2-(甲基)丙烯醯基氧乙基異氰酸酯、(甲基)丙烯醯基異氰酸酯等。Examples of the (meth) acrylate having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and (meth)acryl decyl isocyanate.
光硬化性化合物之市售品可例示以下者。Commercially available products of the photocurable compound are exemplified by the following.
東亞合成(股)製:Aronix M-400、Aronix M-402、Aronix M-408、Aronix M-450、Aronix M-7100、Aronix M-8030、Aronix M-8060;大阪有機化學工業(股)製:Biscoat #400;化藥Sartomer(股)製:SR-295;Daicel UCB(股)製:DPHA、Ebecry1220、Ebecryl 1290K、Ebecryl 5129、Ebecryl 2220、Ebecryl 6602、新中村化學工業(股)製:NK酯A-TMMT、NK寡聚EA-1020、NK寡聚EMA-1020、NK寡聚EA-6310、NK寡聚EA-6320、NK寡聚EA-6340、NK寡聚MA-6、NK寡聚U-4HA、NK寡聚U-6HA、NK寡聚U-324A;BASF公司製:Laromer EA81;Sannopco(股)製:Photomer 3016;荒川化學工業(股)製:Beamset 371、Beamset 575、Beamset 577、Beamset 700、Beamset 710根上工業(股)製:Artresin UN-3320HA、Artresin UN-3320HB、Artresin UN-3320HC、Artresin UN-3320HS、Artresin UN-9000H、Artresin UN-901T、Artresin HDP、Artresin HDP-3、Artresin H61;日本合成化學工業(股)製:紫外線UV-7600B、紫外線UV-7610B、紫外線UV-7620EA、紫外線UV-7630B、紫外線UV-1400B、紫外線UV-1700B、紫外線UV-6300B;共榮社化學(股)製:Light Acrylate PE-4A、Light Acrylate DPE-6A、UA-306H、UA-306T、UA-306I;日本化藥(股)製:KAYARAD DPHA、KAYARAD DPHA 2C、KAYARAD DPHA-4OH、KAYARAD DPHA D-310、KAYARAD DPHA D-330。East Asian synthetic (stock) system: Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060; Osaka Organic Chemical Industry Co., Ltd. :Biscoat #400;Chemistry Sartomer (share) system: SR-295; Daicel UCB (share) system: DPHA, Ebecry1220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602, Xinzhongcun Chemical Industry Co., Ltd.: NK Ester A-TMMT, NK oligomeric EA-1020, NK oligomeric EMA-1020, NK oligomeric EA-6310, NK oligomeric EA-6320, NK oligomeric EA-6340, NK oligomeric MA-6, NK oligomerization U-4HA, NK oligomer U-6HA, NK oligomer U-324A; BASF company: Laromer EA81; Sannopco (stock) system: Photomer 3016; Arakawa Chemical Industry Co., Ltd.: Beamset 371, Beamset 575, Beamset 577 , Beamset 700, Beamset 710 on the industrial (stock) system: Artresin UN-3320HA, Artresin UN-3320HB, Artresin UN-3320HC, Artresin UN-3320HS, Artresin UN-9000H, Artresin UN-901T, Artresin HDP, Artresin HDP-3 , Artresin H61; Japan Synthetic Chemical Industry Co., Ltd.: UV-UV-7600B, UV-UV-7610B Ultraviolet UV-7620EA, Ultraviolet UV-7630B, Ultraviolet UV-1400B, Ultraviolet UV-1700B, Ultraviolet UV-6300B; Kyoritsu Chemical Co., Ltd.: Light Acrylate PE-4A, Light Acrylate DPE-6A, UA-306H, UA-306T, UA-306I; manufactured by Nippon Kayaku Co., Ltd.: KAYARAD DPHA, KAYARAD DPHA 2C, KAYARAD DPHA-4OH, KAYARAD DPHA D-310, KAYARAD DPHA D-330.
其次,說明有關本發明之硬化膜與其積層體。Next, the cured film of the present invention and its laminate will be described.
本發明之硬化膜係使本發明之金屬氧化物組成物硬化而構成之膜。其製造方法例如包含:使金屬氧化物組成物塗佈於任意之基材上;及照射活性能量線而使基材上之金屬氧化物組成物硬化。The cured film of the present invention is a film formed by curing the metal oxide composition of the present invention. The production method includes, for example, applying a metal oxide composition onto an arbitrary substrate, and irradiating the active energy ray to cure the metal oxide composition on the substrate.
更具體地,於任意之基材上以乾燥後之膜厚較佳係成為0.1至30 μm,更宜成為0.1至20 μm塗佈金屬氧化物組成物後,進行硬化處理可形成。More specifically, it is preferable that the film thickness after drying on any of the substrates is 0.1 to 30 μm, more preferably 0.1 to 20 μm, and then a hardening treatment can be formed.
於形成時,硬化膜係可直接塗佈於基材上,亦可於硬化膜與基材之間存有1層以上之下層。At the time of formation, the cured film may be directly applied to the substrate, or one or more layers may be present between the cured film and the substrate.
此基材可舉例如:金屬、陶瓷、玻璃、塑膠、木材、石板等,無特別限制。具體之塑膠的種類可舉例如:聚酯、聚烯烴、聚碳酸酯、聚苯乙烯、聚甲基丙烯酸甲酯、三乙醯基纖維素樹脂、ABS樹脂、AS樹脂、聚醯胺、環氧基樹脂、三聚氰胺樹脂等。又,基材之形狀可舉例如:薄膜片、板狀面板、透鏡形狀、光碟形狀、纖維狀之物,但並無特別限制。The substrate may, for example, be metal, ceramic, glass, plastic, wood, slate or the like, and is not particularly limited. Specific types of plastics include, for example, polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triethyl fluorenyl cellulose resin, ABS resin, AS resin, polyamine, epoxy Base resin, melamine resin, and the like. Further, the shape of the substrate may be, for example, a film sheet, a plate-shaped panel, a lens shape, a disc shape, or a fibrous material, but is not particularly limited.
塗佈方法係可使用公知之方法,可使用例如:桿或鋼絲等之方法,或微凹板、凹板、模頭、簾式、唇式、狹縫或旋塗等之各種塗佈方法。As the coating method, a known method can be used, and for example, a method such as a rod or a steel wire, or various coating methods such as a dicavity, a concave plate, a die, a curtain, a lip, a slit, or a spin coating can be used.
硬化處理係使用公知之技術,例如:藉由照射紫外線、電子束、波長400至500nm之可見光線等的活性能量線來實施。於紫外線及波長400至500nm之可見光線的線源(光源),係可使用高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、鉀燈、氙燈、碳弧燈等。電子束源係可使用熱電子放射槍、電解放射槍等。The hardening treatment is carried out by using a known technique, for example, by irradiating an active energy ray such as ultraviolet rays, an electron beam, or a visible light having a wavelength of 400 to 500 nm. For a line source (light source) of ultraviolet light and visible light having a wavelength of 400 to 500 nm, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a potassium lamp, a xenon lamp, a carbon arc lamp or the like can be used. As the electron beam source, a thermal electron ray gun, an electrolysis lance, or the like can be used.
照設之活性能量線量宜5至2000mJ/cm2 的範圍內,進一步從步驟上易管理而言,宜為50至1000 mJ/cm2 之範圍內。The amount of active energy rays to be applied is preferably in the range of 5 to 2000 mJ/cm 2 , and further preferably in the range of 50 to 1000 mJ/cm 2 from the viewpoint of easy management in steps.
於此等之活性能量線照射,可併用以紅外線、遠紅外線、熱風、高周波加熱等之熱處理。The active energy ray irradiation of these may be used in combination with heat treatment such as infrared rays, far infrared rays, hot air, and high-frequency heating.
硬化膜係於基材上塗佈金屬氧化物組成物,自然或強制乾燥後,進行硬化處理而形成,塗佈,進行硬化處理後,亦可自然或強制乾燥,但宜自然或強制乾燥後,進行硬化處理者。The cured film is coated on the substrate with a metal oxide composition, and is naturally or forcedly dried, and then formed by hardening treatment. After coating and hardening treatment, it may be naturally or forcedly dried, but after natural or forced drying, Perform hardening treatment.
尤其,以電子束硬化時,係為防止以水所造成之硬化阻礙或有機溶劑的殘留所產生之塗膜的強度降低,更宜自然或強制乾燥後,進行硬化處理者。In particular, when it is cured by electron beam, it is preferable to prevent the hardening by water or the strength of the coating film caused by the residual of the organic solvent, and it is more preferable to perform the curing after natural or forced drying.
硬化處理之時機係可為與塗佈同時,亦可為塗佈後。所得到之硬化膜係硬塗性、透明性、耐光性、高折射率性、防止帶電性優,故可適宜作為光學材料利用。因此,本發明之硬化膜係可作為積層體,亦可作為陰極射線管、平面顯示器面板(液晶顯示器、電漿顯示器、電子發光顯示器、發光二極體顯示器等)等之各種顯示裝置之前面板或此等之輸入裝置利用。The timing of the hardening treatment may be simultaneous with coating or after coating. The obtained cured film is excellent in hard coatability, transparency, light resistance, high refractive index, and charge resistance, and therefore can be suitably used as an optical material. Therefore, the cured film of the present invention can be used as a laminate or as a front panel of various display devices such as a cathode ray tube, a flat display panel (a liquid crystal display, a plasma display, an electroluminescence display, a light-emitting diode display, etc.) or These input devices are utilized.
其他,此硬化膜係可廣泛地利用於光學用透鏡、眼鏡用鏡片、光記錄磁碟(CD、DVD光碟、藍光光碟等)、燈殼等。In addition, this cured film can be widely used for optical lenses, lenses for glasses, optical recording disks (CD, DVD, Blu-ray, etc.), lamp housings, and the like.
硬化膜之表面電阻宜為1×1012 Ω/□以下。The surface resistance of the cured film is preferably 1 × 10 12 Ω / □ or less.
硬化膜之厚度宜為0.1至30 μm。The thickness of the cured film is preferably from 0.1 to 30 μm.
進一步,硬化膜之折射率宜為1.4至2.0的範圍,更宜為1.5至1.8的範圍。Further, the refractive index of the cured film is preferably in the range of 1.4 to 2.0, more preferably in the range of 1.5 to 1.8.
本發明之積層體係含有本發明之硬化膜與基材者。基材係可任意地使用上述例示者,尤其宜為塑膠基材。基材之形狀宜為薄膜形狀、透鏡形狀、或光碟形狀。The laminated system of the present invention contains the cured film of the present invention and a substrate. The substrate may be arbitrarily used as the above-exemplified, and particularly preferably a plastic substrate. The shape of the substrate is preferably a film shape, a lens shape, or a disc shape.
此積層體係除此等以外,尚宜含有折射率相異之膜、黏着層或資訊記錄層等1層以上。In addition to these, it is preferable that the laminated system contains one or more layers of a film having a different refractive index, an adhesive layer, or an information recording layer.
含有折射率相異之膜(M)、黏着層(M)或資訊記錄層(M)之積層體,例如可形成下述(I)至(IX)等之層結構。The layered body containing the film (M) having a different refractive index, the adhesive layer (M), or the information recording layer (M) can form, for example, a layer structure of the following (I) to (IX).
(I)基材/(M)/硬化膜(II)基材/硬化膜/(M)(III)基材/(M)/硬化膜/(M)(IV)(M)/基材/硬化膜(V)(M)/基材/(M)/硬化膜(VI)(M)/基材/硬化膜/(M)(VII)(M)/基材/(M)/硬化膜/(M)(VIII)(M)/硬化膜/基材/硬化膜(IX)硬化膜/(M)/基材/硬化膜(I) Substrate/(M)/Cured film (II) Substrate/Cured film/(M)(III) Substrate/(M)/Cured film/(M)(IV)(M)/Substrate/ Hardened film (V) (M) / substrate / (M) / cured film (VI) (M) / substrate / cured film / (M) (VII) (M) / substrate / (M) / cured film /(M)(VIII)(M)/hardened film/substrate/hardened film (IX) hardened film/(M)/substrate/hardened film
折射率相異之膜或資訊記錄層係具有本發明之硬化物功能以外之功能者。其形成方法並無特別限定,可以習知之方法形成。例如蒸鍍、濺鍍等之乾塗法、使用桿、鋼絲條之方法、或可使用微凹板、凹板、模頭、簾式、唇式、狹縫或旋塗等之各種濕式塗佈方法。所使用之材料亦無限定,依需要,可使用賦予資訊記錄功能、防眩功能、防止牛頓環功能、黏着功能、特定波長之遮蔽、密着提昇、色調修正等之功能的一種類以上於積層體之任意材料。The film having a different refractive index or the information recording layer has a function other than the function of the cured product of the present invention. The method for forming the film is not particularly limited and can be formed by a conventional method. For example, a dry coating method such as vapor deposition or sputtering, a method using a rod or a wire rod, or various wet coatings such as a dicavity plate, a concave plate, a die, a curtain, a lip, a slit, or a spin coating. Cloth method. The material to be used is not limited, and any one or more of the functions of the information recording function, the anti-glare function, the prevention of the Newton's ring function, the adhesion function, the shielding of specific wavelengths, the adhesion enhancement, the color tone correction, and the like may be used as needed. Any material.
資訊記錄層係受雷射光等而產生任何的化學變化,只要藉其變化記錄資訊者即可,材料無特別限定。例如,有機系之材料可舉例如:聚甲炔色素、萘酞菁系、酞菁系、方酸(Squarylium)系、蔥醌系、氧雜蒽酮系、三苯基甲烷系金屬錯合物化合物,可使用上述的染料一種或2種以上之組合。無機系之記錄層係可使用Te、Ge、Se、In、Sb、Sn、Zn、Au、Al、Cu、Pt等之金屬、半金屬1種或組合2種以上。資訊記錄層係可為積層體等,光化學變化之態樣係可為相變化、閥型、開孔型之任一者。再者亦可為以Fe、Tb、Co為主體之光磁記錄層,亦可為螺吡喃、四烴基順己二烯二酸酐(Fulgide)系之光色材料。The information recording layer is subjected to any chemical change caused by laser light or the like, and the material is recorded by the change thereof, and the material is not particularly limited. For example, examples of the organic material include polymethine dye, naphthalocyanine, phthalocyanine, Squarylium, onion, xanthones, and triphenylmethane metal complexes. As the compound, one kind or a combination of two or more kinds of the above dyes can be used. As the inorganic recording layer, one or a combination of two or more kinds of metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, and Pt may be used. The information recording layer may be a laminate or the like, and the photochemical change state may be any one of a phase change, a valve type, and an open type. Further, it may be a magneto-optical recording layer mainly composed of Fe, Tb or Co, or a photochromic material of a spiropyran or a tetrahydrocarbyl cis-diene dihydride (Fulgide).
高折射率之硬化膜,從防止反射之觀點而言,於表層設有低折射率之被覆硬化膜,亦可作為賦予防止反射功能之積層體來利用。亦即,於薄膜等之基材上形成硬化膜,更宜將形成被覆硬化膜所得到之積層體作為防止反射膜使用。The cured film having a high refractive index is provided with a cured film having a low refractive index on the surface layer from the viewpoint of preventing reflection, and can also be used as a laminate which imparts a function of preventing reflection. That is, a cured film is formed on a substrate such as a film, and it is more preferable to use a laminate obtained by forming a cured film as an antireflection film.
在反射干涉條紋成為問題之積層體中,調整本發明之金屬氧化物組成物中的金屬氧化物之調配量,此硬化膜與基材之折射率差,或,於硬化膜與基材之間存在任意的層時,硬化膜與硬化膜相接之下層的折射率差,以形成±0.02以內之方式為宜。In the layered body in which the interference fringe is a problem, the amount of the metal oxide in the metal oxide composition of the present invention is adjusted, and the refractive index of the cured film is different from the substrate, or between the cured film and the substrate. When there is an arbitrary layer, the refractive index difference of the layer below the hardened film and the cured film is preferably within ±0.02.
本發明之金屬氧化物組成物係藉由控制金屬氧化物之種類或添加量,而可製造高折射率之硬化物。因此,為了提升光半導體元件之光輸出效率,較宜利用被要求作為使樹脂層之折射率從光半導元件側朝向最外層依序減少之光半導體元件密封材。The metal oxide composition of the present invention can produce a cured product having a high refractive index by controlling the kind or addition amount of the metal oxide. Therefore, in order to improve the light output efficiency of the optical semiconductor element, it is preferable to use an optical semiconductor element sealing material which is required to sequentially reduce the refractive index of the resin layer from the light semiconductor element side toward the outermost layer.
光半導體元件可舉例如:氮化鎵(GaN:折射率2.5)、磷化鎵(GaP:折射率2.9)、砷化鎵(GaAs:折射率3.5)等,為折射率非常高的材料。因此,成為光半導體元件密封材之硬化物的折射率,從提高光輸出效率之觀點而言,宜為1.5以上,較佳是1.5至2.1,更佳為1.7至2.1。The optical semiconductor element may be, for example, gallium nitride (GaN: refractive index: 2.5), gallium phosphide (GaP: refractive index: 2.9), gallium arsenide (GaAs: refractive index: 3.5), or the like, and has a very high refractive index. Therefore, the refractive index of the cured product of the optical semiconductor element sealing material is preferably 1.5 or more, preferably 1.5 to 2.1, and more preferably 1.7 to 2.1 from the viewpoint of improving light output efficiency.
達成硬化物之最適的折射率之方法,就所使用之金屬氧化物而言,以氧化鈦(折射率2.5至2.7)、氧化鋯(折射率2.4)、氧化鋅(折射率1.95)等為宜,於分散劑中亦要求折射率高,故以具有芳香族骨架之分散劑(A)為佳。A method for achieving an optimum refractive index of the cured product is preferably titanium oxide (refractive index of 2.5 to 2.7), zirconia (refractive index of 2.4), zinc oxide (refractive index of 1.95), and the like. The dispersant is also required to have a high refractive index, so that a dispersant (A) having an aromatic skeleton is preferred.
以下,依據製造例、實施例更詳細說明本發明,製造例、實施例中、份及%係分別表示重量份及重量%。Hereinafter, the present invention will be described in more detail based on the production examples and examples, and the production examples, examples, parts and % represent the parts by weight and % by weight, respectively.
所使用之藥品係如下。The drugs used are as follows.
聯苯基四羧酸二酐(三菱化學(股)製)9,9-雙(3,4-二羧基苯基)芴二酸酐(JFE Chemical(股)製、商品名:BPAF)四氫萘羧酸二酐(新日本理化(股)製、商品名:Rikasid TDA-100)萘四羧酸二酐(JFE Chemical(股)製、商品名:NTCDA)丁烷四羧酸二酐(新日本理化(股)製、商品名:Rikasid BT-100)季戊四醇三丙烯酸酯(1)(大阪有機化學工業(股)製、商品名:Biscoat #300)季戊四醇三丙烯酸酯(2)(日本化藥(股)製、商品名:KAYARD PET-30)二季戊四醇五丙烯酸酯(日本化藥(股)製、商品名:KAYARD DPHA)丙烯酸-2-羥乙酯(日本觸媒(股)製)氫醌(和光純藥工業(股)製)1,8-二雜氮雙環[5.4.0]-7-十一碳烯(東京化成工業(股)製)縮水甘油基甲基丙烯酸酯(Dow Chemical日本(股)製)二甲基苯甲基胺(和光純藥工業(股)製)Biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation) 9,9-bis(3,4-dicarboxyphenyl)sebacic anhydride (manufactured by JFE Chemical Co., Ltd., trade name: BPAF) tetrahydronaphthalene Carboxylic dianhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., trade name: Rikasid TDA-100) naphthalene tetracarboxylic dianhydride (manufactured by JFE Chemical Co., Ltd., trade name: NTCDA) butane tetracarboxylic dianhydride (New Japan) Physicochemical (stock) system, trade name: Rikasid BT-100) pentaerythritol triacrylate (1) (Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat #300) pentaerythritol triacrylate (2) (Japanese chemical ( Co., Ltd., trade name: KAYARD PET-30) Dipentaerythritol pentaacrylate (Nippon Chemical Co., Ltd., trade name: KAYARD DPHA) 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) (Wako Pure Chemical Industries, Ltd.) 1,8-diazabicyclo[5.4.0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) glycidyl methacrylate (Dow Chemical Japan) (share) system) dimethylbenzylamine (Wako Pure Chemical Industries Co., Ltd.)
(製造例1:分散劑(1))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中放入聯苯基四羧酸二酐80.0份、季戊四醇三丙烯酸酯(1)250.0份、氫醌0.16份、環己酮141.2份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯1.65份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯77.3份、環己酮33.9份,然後,加入二甲基苯甲基胺2.65份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分70%、數目平均分子量(MN)870、重量平均分子量(MW)2830。(Production Example 1: Dispersant (1)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride and pentaerythritol triacrylate (1) were placed. 250.0 parts, 0.16 parts of hydroquinone, and 141.2 parts of cyclohexanone were heated to 85 °C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The resulting reaction solution was light yellow transparent, solid content 70%, number average molecular weight (MN) 870, weight average molecular weight (MW) 2830.
(製造例2:分散劑(2))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入聯苯基四羧酸二酐80.0份、季戊四醇三丙烯酸酯(2)250.0份、氫醌0.16份、環己酮141.2份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯1.65份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯77.3份、環己酮33.9份,然後,加入二甲基苯甲基胺2.65份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分70%、數目平均分子量920、重量平均分子量3,130。(Production Example 2: Dispersant (2)) To a 4-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride and pentaerythritol triacrylate (2) 250.0 were added. The fraction was 0.16 parts of hydroquinone and 141.2 parts of cyclohexanone, and the temperature was raised to 85 °C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The obtained reaction solution was light yellow transparent, having a solid content of 70%, a number average molecular weight of 920, and a weight average molecular weight of 3,130.
(製造例3:分散劑(3))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入聯苯基四羧酸二酐80.0份、季戊四醇三丙烯酸酯(1)124.8份、二季戊四醇五丙烯酸酯222.8份、氫醌0.21份、環己酮430.0份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯2.14份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯77.3份、環己酮80.7份,然後,加入二甲基苯甲基胺3.42份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分50%、數目平均分子量1050、重量平均分子量3,830。(Production Example 3: Dispersant (3)) To a 4-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride and pentaerythritol triacrylate (1) 124.8 were added. 222.8 parts of dipentaerythritol pentaacrylate, 0.21 part of hydroquinone, and 430.0 parts of cyclohexanone were heated to 85 °C. Then, 2.14 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 80.7 parts of cyclohexanone were added, and then 3.42 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The obtained reaction solution was light yellow transparent, having a solid content of 50%, a number average molecular weight of 1050, and a weight average molecular weight of 3,830.
(製造例4:分散劑(4))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入9,9-雙(3,4-二羧基苯基)芴二酸酐100.0份、季戊四醇三丙烯酸酯(1)200.2份、氫醌0.15份、環己酮200.1份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯1.50份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯62.0份、環己酮42.4份,然後,加入二甲基苯甲基胺2.41份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分60%、數目平均分子量830、重量平均分子量2,310。(Production Example 4: Dispersant (4)) 9,9-bis(3,4-dicarboxyphenyl)sebacic anhydride 100.0 was placed in a 4-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. A portion, 200.2 parts of pentaerythritol triacrylate (1), 0.15 parts of hydroquinone, and 200.1 parts of cyclohexanone were heated to 85 °C. Then, 1.50 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 62.0 parts of glycidyl methacrylate and 42.4 parts of cyclohexanone were added, and then 2.41 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The resulting reaction solution was light yellow transparent, having a solid content of 60%, a number average molecular weight of 830, and a weight average molecular weight of 2,310.
(製造例5:分散劑(5))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入四氫萘羧酸二酐100.0份、季戊四醇三丙烯酸酯(2)305.7份、氫醌0.20份、環己酮405.7份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯2.03份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯94.6份、環己酮96.9份,然後,加入二甲基苯甲基胺3.26份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分50%、數目平均分子量870、重量平均分子量3,150。(Production Example 5: Dispersant (5)) 100.0 parts of tetrahydronaphthalene carboxylic acid dianhydride and 305.7 parts of pentaerythritol triacrylate (2) were placed in a 4-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. 0.20 parts of hydroquinone and 405.7 parts of cyclohexanone were heated to 85 °C. Then, 2.03 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 94.6 parts of glycidyl methacrylate and 96.9 parts of cyclohexanone were added, and then 3.26 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The resulting reaction solution was light yellow transparent, having a solid content of 50%, a number average molecular weight of 870, and a weight average molecular weight of 3,150.
(製造例6:分散劑(6))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入萘四羧酸二酐100.0份、季戊四醇三丙烯酸酯(2)342.2份、氫醌0.22份、環己酮442.2份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯2.21份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯105.9份、環己酮108.4份,然後,加入二甲基苯甲基胺3.56份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分50%、數目平均分子量820、重量平均分子量2,440。(Production Example 6: Dispersant (6)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 100.0 parts of naphthalenetetracarboxylic dianhydride and 342.2 parts of pentaerythritol triacrylate (2) were placed. 0.22 parts of hydroquinone and 442.2 parts of cyclohexanone were heated to 85 °C. Then, 2.21 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 105.9 parts of glycidyl methacrylate and 108.4 parts of cyclohexanone were added, and then 3.56 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The resulting reaction solution was light yellow transparent, having a solid content of 50%, a number average molecular weight of 820, and a weight average molecular weight of 2,440.
(製造例7:分散劑(7))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入聯苯基四羧酸二酐100.0份、二季戊四醇五丙烯酸酯556.8份、氫醌0.33份、環己酮437.8份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯3.28份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯96.6份、環己酮66.8份,然後,加入二甲基苯甲基胺5.28份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分60%、數目平均分子量820、重量平均分子量2,660。(Production Example 7: Dispersant (7)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 100.0 parts of biphenyltetracarboxylic dianhydride and 556.8 parts of dipentaerythritol pentaacrylate were added. 0.33 parts of hydroquinone and 437.8 parts of cyclohexanone were heated to 85 °C. Then, 3.28 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 96.6 parts of glycidyl methacrylate and 66.8 parts of cyclohexanone were added, and then 5.28 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The resulting reaction solution was light yellow transparent, having a solid content of 60%, a number average molecular weight of 820, and a weight average molecular weight of 2,660.
(製造例8:分散劑(8))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入9,9-雙(3,4-二羧基苯基)芴二酸酐100.0份、丙烯酸2-羥乙基酯50.7份、氫醌0.08份、環己酮100.4份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯1.51份作為觸媒,在85℃下攪拌5小時。其後,加入縮水甘油基甲基丙烯酸酯62.0份、環己酮39.7份,然後,加入二甲基苯甲基胺1.21份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分60%、數目平均分子量890、重量平均分子量1,200。(Production Example 8: Dispersant (8)) 9,9-bis(3,4-dicarboxyphenyl)sebacic anhydride 100.0 was placed in a 4-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. A solution of 50.7 parts of 2-hydroxyethyl acrylate, 0.08 parts of hydroquinone, and 100.4 parts of cyclohexanone were heated to 85 °C. Then, 1.51 part of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 5 hours. Thereafter, 62.0 parts of glycidyl methacrylate and 39.7 parts of cyclohexanone were added, and then 1.21 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The obtained reaction solution was light yellow transparent, having a solid content of 60%, a number average molecular weight of 890, and a weight average molecular weight of 1,200.
(製造例9:分散劑(9))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入丁烷四羧酸二酐100.0份、季戊四醇三丙烯酸酯(1)463.2份、氫醌0.28份、環己酮563.2份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯2.82份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯143.4份、環己酮146.5份,然後,加入二甲基苯甲基胺4.53份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分50%、數目平均分子量820、重量平均分子量2,000。(Production Example 9: Dispersant (9)) 100.0 parts of butane tetracarboxylic dianhydride and 463.2 parts of pentaerythritol triacrylate (1) were placed in a 4-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. 0.28 parts of hydroquinone and 563.2 parts of cyclohexanone were heated to 85 °C. Then, 2.82 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 146.5 parts of cyclohexanone were added, and then 4.53 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The obtained reaction solution was light yellow transparent, having a solid content of 50%, a number average molecular weight of 820, and a weight average molecular weight of 2,000.
(製造例10:分散劑(10))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入丁烷四羧酸二酐100.0份、季戊四醇三丙烯酸酯(2)463.2份、氫醌0.28份、環己酮563.2份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯2.82份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯143.4份、環己酮146.5份,然後,加入二甲基苯甲基胺4.53份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分50%、數目平均分子量920、重量平均分子量2,200。(Production Example 10: Dispersant (10)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 100.0 parts of butane tetracarboxylic dianhydride and 463.2 parts of pentaerythritol triacrylate (2) were placed. 0.28 parts of hydroquinone and 563.2 parts of cyclohexanone were heated to 85 °C. Then, 2.82 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 146.5 parts of cyclohexanone were added, and then 4.53 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The resulting reaction solution was light yellow transparent, having a solid content of 50%, a number average molecular weight of 920, and a weight average molecular weight of 2,200.
(製造例11:分散劑(11))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入丁烷四羧酸二酐80.0份、季戊四醇三丙烯酸酯(2)185.3份、二季戊四醇三丙烯酸酯330.9份、氫醌0.30份、環己酮599.5份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯2.98份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯114.8份、環己酮119.6份,然後,加入二甲基苯甲基胺4.77份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分50%、數目平均分子量950、重量平均分子量2,600。(Production Example 11: Dispersant (11)) 80.0 parts of butane tetracarboxylic dianhydride and 185.3 parts of pentaerythritol triacrylate (2) were placed in a 4-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. 330.9 parts of dipentaerythritol triacrylate, 0.30 parts of hydroquinone, 599.5 parts of cyclohexanone, and the temperature was raised to 85 °C. Then, 2.98 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 114.8 parts of glycidyl methacrylate and 119.6 parts of cyclohexanone were added, and then 4.77 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The resulting reaction solution was light yellow transparent, having a solid content of 50%, a number average molecular weight of 950, and a weight average molecular weight of 2,600.
(製造例12:分散劑(12))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入丁烷四羧酸二酐50.0份、二季戊四醇五丙烯酸酯413.4份、氫醌0.23份、環己酮463.4份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯2.32份作為觸媒,在85℃下攪拌8小時。其後,加入縮水甘油基甲基丙烯酸酯71.7份、環己酮74.3份,然後,加入二甲基苯甲基胺3.73份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分50%、數目平均分子量900、重量平均分子量2,070。(Production Example 12: Dispersant (12)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 50.0 parts of butane tetracarboxylic dianhydride, 413.4 parts of dipentaerythritol pentaacrylate, and hydrogen were placed.醌 0.23 parts, 463.4 parts of cyclohexanone, and the temperature was raised to 85 °C. Then, 2.32 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours. Thereafter, 71.7 parts of glycidyl methacrylate and 74.3 parts of cyclohexanone were added, and then 3.73 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The obtained reaction solution was light yellow transparent, having a solid content of 50%, a number average molecular weight of 900, and a weight average molecular weight of 2,070.
(製造例13:分散劑(13))於具備攪拌機、回流冷卻管、乾燥空氣導入管、溫度計之4口燒瓶中加入丁烷四羧酸二酐100.0份、丙烯酸酯2-羥基已酯117.2份、氫醌0.11份、環己酮144.8份,昇溫至85℃。然後,加入1,8-二雜氮雙環[5.4.0]-7-十一碳烯2.17份作為觸媒,在85℃下攪拌5小時。其後,加入縮水甘油基甲基丙烯酸酯143.4份、環己酮93.3份,然後,加入二甲基苯甲基胺1.74份作為觸媒,在85℃下攪拌6小時,冷卻至室溫而終止反應。所得到之反應溶液為淡黃色透明,固形分60%、數目平均分子量780、重量平均分子量1,100。(Production Example 13: Dispersant (13)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 100.0 parts of butane tetracarboxylic dianhydride and 117.2 parts of acrylate 2-hydroxyhexyl ester were placed. 0.11 parts of hydroquinone and 144.8 parts of cyclohexanone were heated to 85 °C. Then, 2.17 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C for 5 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 93.3 parts of cyclohexanone were added, and then 1.74 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours, and cooled to room temperature to terminate. reaction. The obtained reaction solution was light yellow transparent, having a solid content of 60%, a number average molecular weight of 780, and a weight average molecular weight of 1,100.
(金屬氧化物分散糊劑之製作:實施例1至22、比較例1至3)使用以上述製造例所製作之各分散劑(A),依表1所示之調配進行金屬氧化物分散,製作金屬氧化物分散糊劑(調配量表示固形分量)。分散方法係使用前分散(氧化鋯粒(1.25mm)作為媒介質,以油漆搖混器分散1小時)、使用本分散(氧化鋯粒子(0.1mm)作為媒介質,以壽工業(股)製分散機UAM-015分散)之實施2階段分散。(Production of Metal Oxide Dispersing Paste: Examples 1 to 22, Comparative Examples 1 to 3) Using the respective dispersing agents (A) prepared in the above production examples, metal oxide dispersion was carried out according to the formulation shown in Table 1. A metal oxide dispersion paste was prepared (the amount of the formulation represents a solid component). The dispersion method is dispersion before use (zirconia particles (1.25 mm) as a medium, dispersed in a paint shaker for 1 hour), and using the dispersion (zirconia particles (0.1 mm) as a medium, manufactured by Shou Industrial Co., Ltd.) The dispersion of the disperser UAM-015 was carried out in a 2-stage dispersion.
於表1中,Sb2 O5 :日產化學工業(股)製「Sunepoch EF R-6N」(平均一次粒徑:20nm)、ATO:石原產業(股)製「SN-100P」(平均一次粒徑:20nm)ITO:CI化成(股)製「Nanotech ITO」(平均一次粒徑:30nm)PTO:三菱Material(股)製「EP SP-2」(平均一次粒徑:15nm)ZrO2 :日本電工(股)製「PCS-60」(平均一次粒徑:20nm)TiO2 :石原產業(股)製「TTO-51(A)」(平均一次粒徑:20nm)ZnO:堺化學工業(股)製「FINEX-50」(平均一次粒徑:20nm)SiO2 :日本Aerosil(股)製「AEROSIL50」(平均一次粒徑:50nm)Al2 O5 :日本Aerosil(股)製「Aluminium Oxide C」(平均一次粒徑:13nm)市售分散劑:BYK Japan(股)製「DisperbyK-111」(固形分100%)市售多官能單體(1):大阪有機化學(股)製「Biscoat #400」(固形分100%)市售多官能單體(2):日本化藥(股)製「KAYARAD DPHA」(固形分100%)MIBK:甲基異丁基酮Methobuta(MB):3-甲氧基-1-丁醇In Table 1, Sb 2 O 5 : "Sunepoch EF R-6N" manufactured by Nissan Chemical Industries Co., Ltd. (average primary particle size: 20 nm), ATO: "SN-100P" manufactured by Ishihara Satoshi Co., Ltd. (average primary particle) Measure: 20 nm) ITO: "Nanotech ITO" manufactured by CI Chemical Co., Ltd. (average primary particle diameter: 30 nm) PTO: "EP SP-2" manufactured by Mitsubishi Material Co., Ltd. (average primary particle diameter: 15 nm) ZrO 2 : Japan "PCS-60" (average primary particle size: 20 nm) TiO 2 manufactured by Electrician Co., Ltd.: "TTO-51 (A)" (average primary particle diameter: 20 nm) manufactured by Ishihara Sangyo Co., Ltd. "FINEX-50" (average primary particle size: 20 nm) SiO 2 : "AEROSIL 50" manufactured by Japan Aerosil Co., Ltd. (average primary particle diameter: 50 nm) Al 2 O 5 : "Aluminium Oxide C" manufactured by Japan Aerosil Co., Ltd. (average primary particle size: 13 nm) Commercially available dispersant: "Disperby K-111" manufactured by BYK Japan Co., Ltd. (solid content: 100%) Commercially available polyfunctional monomer (1): Osaka Organic Chemical Co., Ltd. "Biscoat"#400"(solid content: 100%) Commercially available polyfunctional monomer (2): "KAYARAD DPHA" (solid content 100%) manufactured by Nippon Kayaku Co., Ltd. MIBK: Methyl isobutyl ketone Metobuta (MB): 3 -methoxy-1-butanol
使用上述所調整之金屬氧化物分散糊劑,調整表2所示之組成的金屬氧化物組成物(調配量是表示固形分量)。對100 μm厚之易接着處理PET膜(東洋紡(股)製「Cosmoshine A-4100」)以桿塗器,以乾燥後之膜厚成為5 μm之方式塗佈所得到之金屬氧化物組成物後,以金屬鹵素燈照射400mJ/cm2 之紫外線,形成硬化膜(硬塗層)。關於所得到之硬化膜,以下述之方法評估折射率、耐擦傷性、鉛筆硬度、透明性(霧度)耐光性、及表面電阻。其結果表示於表2中。The metal oxide composition having the composition shown in Table 2 was adjusted using the metal oxide dispersion paste adjusted as described above (the amount of the formulation is a solid content). After coating the obtained metal oxide composition with a 100 μm thick easy-to-treat PET film ("Cosmoshine A-4100" manufactured by Toyobo Co., Ltd.) with a bar coater so that the film thickness after drying was 5 μm The ultraviolet light of 400 mJ/cm 2 was irradiated with a metal halide lamp to form a cured film (hard coat layer). Regarding the obtained cured film, the refractive index, the scratch resistance, the pencil hardness, the transparency (haze) light resistance, and the surface resistance were evaluated by the following methods. The results are shown in Table 2.
在表2中,光硬化性化合物(1):共榮社化學(股)製「UA-306T」光硬化性化合物(2):日本化藥(股)製「KAYARAD DPHA」光聚合起始劑:Ciba Specialty Chemicals(股)製「Irgacure 184」溶劑:PGME(丙二醇單甲基醚)*1:金屬氧化物糊劑為分散不良,故未測定In Table 2, photocurable compound (1): "UA-306T" photocurable compound (2) manufactured by Kyoeisha Chemical Co., Ltd.: "KAYARAD DPHA" photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd. : "Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd. Solvent: PGME (propylene glycol monomethyl ether) *1: The metal oxide paste is poorly dispersed, so it is not determined.
(低折射率塗液之製作)混合1,2,9,10-四丙烯醯氧-4,4,5,5,6,6,7,7-八氟癸烷50重量份、氧化矽溶膠30%分散液(日產化學工業(股)製MEK-ST)120重量份、2’,2’-雙((甲基)丙烯醯氧甲基)丙酸(2-羥基)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-十九氟十一碳烷酯10重量份、丁基醇900重量份、光聚合起始劑(日本化藥(股)製KAYACURE BMS)5重量份,調整低折射率塗液。(Production of low refractive index coating liquid) 50 parts by weight of 1,2,9,10-tetrapropene oxime-4,4,5,5,6,6,7,7-octafluorodecane, cerium oxide sol 30% dispersion (MEK-ST manufactured by Nissan Chemical Industries Co., Ltd.) 120 parts by weight, 2',2'-bis((meth)acrylomethoxymethyl)propionic acid (2-hydroxy)-4,4, 10,5,6,6,7,7,8,8,9,9,10,10,11,11,11-non-dodecylundecyl ester 10 parts by weight, butyl alcohol 900 parts by weight, light 5 parts by weight of a polymerization initiator (KAYACURE BMS, manufactured by Nippon Kayaku Co., Ltd.) was adjusted to adjust the low refractive index coating liquid.
使用實施例2之金屬氧化物分散糊劑,調整以表3所示之調配所得到的組成之各金屬氧化物組成物(調配量係表示固形分量)。將此金屬氧化物組成物於100 μm厚之易接着處理PET膜(易接着處理層之折射率=1.60)的易接着處理面上,使用桿塗器而以乾燥膜厚成為6 μm之方式進行塗佈。使所得到之塗佈層在100℃下乾燥1分鐘後,以金屬鹵素燈照射400mJ/cm2 之紫外線。於所得到之硬化膜上進一步,使上述低折射塗料液以旋塗器,於乾燥膜厚顯示λ/4之光的波長成為550nm左右之方式調整層之厚度而塗布。使所得到之塗佈層在100℃下乾燥1分鐘後,以金屬鹵素燈照射400mJ/cm2 之紫外線,得到積層體。Using the metal oxide dispersion paste of Example 2, each metal oxide composition having the composition obtained by the formulation shown in Table 3 was adjusted (the amount of the formulation represents a solid component). This metal oxide composition was applied to a 100 μm-thick easy-to-handle surface of a PET film (reproducible refractive index = 1.60), using a bar coater to have a dry film thickness of 6 μm. Coating. The obtained coating layer was dried at 100 ° C for 1 minute, and then irradiated with ultraviolet rays of 400 mJ/cm 2 with a metal halide lamp. Further, the low-refractive-coating liquid is applied to the cured film by adjusting the thickness of the layer so that the wavelength of the λ/4 light is about 550 nm in a spin coater. The obtained coating layer was dried at 100 ° C for 1 minute, and then irradiated with ultraviolet rays of 400 mJ/cm 2 with a metal halide lamp to obtain a laminate.
有關所得到之積層體,以下述之方法測定硬化膜的折射率,同時並評估硬化膜之耐擦傷性、鉛筆硬度、透明性(霧度,Haze)、折射率、反射干涉條紋。其結果表示於表3中。With respect to the obtained laminate, the refractive index of the cured film was measured by the following method, and the scratch resistance, pencil hardness, transparency (haze), refractive index, and reflection interference fringe of the cured film were evaluated. The results are shown in Table 3.
在表3中,光硬化性化合物(2):日本化藥(股)製「KAYARAD DPHA」光聚合起始劑:Ciba Specialty Chemicals(股)製「Irgacure 184」基材:100 μm厚之易接着處理PET膜(東洋紡(股)製「CosmoshineA-4100」)、易接着處理面(折射率1.60)上塗佈)溶劑:PGME(丙二醇單甲基醚)In Table 3, photocurable compound (2): "KAYARAD DPHA" photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd.: "Irgacure 184" substrate manufactured by Ciba Specialty Chemicals Co., Ltd.: 100 μm thick Treatment of PET film ("Cosmoshine A-4100" manufactured by Toyobo Co., Ltd.), easy-to-handle surface (refractive index 1.60) coating) Solvent: PGME (propylene glycol monomethyl ether)
(評估方法)(1)折射率使用(股)ATAGO製Abbe折射率計而測定所得到之硬化皮膜的折射率。(Evaluation Method) (1) Refractive Index The refractive index of the obtained hardened film was measured using an Abbe refractometer made of ATAGO.
(2)耐擦傷性將塗佈物安置於學振試驗機,使用Steelwool之No.0000,而以荷重250g學振10次。有關所取出之塗佈物,依以下之5階段的目視評估判斷受刮傷之情形。顯示數值愈大,硬化膜之耐擦傷性愈良好。(2) Scratch resistance The coating material was placed on a vibration tester, and No. 0000 of Steelwool was used, and the test was carried out 10 times with a load of 250 g. Regarding the removed coating, the scratching was judged by the visual evaluation of the following five stages. The larger the display value, the better the scratch resistance of the cured film.
5:完全無刮傷4:稍刮傷3:有刮傷,但在基材看不到2:有刮傷,一部分硬化膜被剝離1:硬化膜被剝離,基材為剝離之狀態5: No scratches at all 4: Slightly scratched 3: Scratched, but not visible on the substrate 2: Scratched, part of the cured film was peeled off 1: The cured film was peeled off, and the substrate was peeled off.
(3)鉛筆硬度依據JIS-K5600,使用鉛筆硬度試驗機(HEIDON公司製Scratching Tester HEIDON-14),改變各種鉛筆芯之硬度,以荷重500g試驗5次。在5次中,1次也無刮傷,或只一次刮傷時之芯的硬度作為其硬化膜之鉛筆硬度。考慮實用上之要求物性,而判定硬化膜之鉛筆硬度為2H以上:A 1H以上:B較1H低:D(3) Pencil hardness According to JIS-K5600, the hardness of each pencil lead was changed using a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON Co., Ltd.), and the test was performed 5 times at a load of 500 g. In 5 times, the hardness of the core at the time of scratching or the scratching of only one time was taken as the pencil hardness of the cured film. Considering the practical physical properties, it is judged that the pencil hardness of the cured film is 2H or more: A 1H or more: B is lower than 1H: D
(4)透明性(霧度)使用Haze計而測定所得到之塗佈物之霧度(Haze值)。(4) Transparency (Haze) The haze (Haze value) of the obtained coating material was measured using a Haze meter.
(5)耐光性光連續照射時之隨時間的黃變,係用途展開上,非常不佳。因此,確認光連續照射時之黃變性。(5) Light-resistant yellow light change over time during continuous light irradiation, which is very unsatisfactory for use. Therefore, the yellowing of the light upon continuous irradiation was confirmed.
首先,以耐光性試驗機(光源:氙燈、照度:100W/cm2 、黑色面板溫度:60℃、60%RH)曝露塗佈物24小時。其後,將塗佈物放置於白色紙上,使用測色機(Minilta CR-300)而測定著色。測定值係以L*a*b*表示,以b*值判斷硬化膜之黃變性的標準。顯示b*值之值愈小,黃變之程度愈小,耐光性良好。考慮實用上之要求物性,硬化膜之b*值判定為不足3.5者:A 3.5以上者:DFirst, the coating was exposed to a light resistance tester (light source: xenon lamp, illuminance: 100 W/cm 2 , black panel temperature: 60 ° C, 60% RH) for 24 hours. Thereafter, the coated product was placed on a white paper, and coloring was measured using a color measuring machine (Minilta CR-300). The measured value is expressed by L*a*b*, and the standard of yellowing of the cured film is judged by the b* value. The smaller the value of the b* value is, the smaller the degree of yellowing is, and the light resistance is good. Considering the practical physical properties, the b* value of the cured film is judged to be less than 3.5: A 3.5 or more: D
(6)表面電阻依據以下之基準而評估硬化膜之表面電阻(Ω/□)。表面電阻為1×1012 以下時:A表面電阻高於1×1012 且1×1014 以下時:B表面電阻超過1×1014 時:D(6) Surface resistance The surface resistance (Ω/□) of the cured film was evaluated based on the following criteria. When the surface resistance is 1 × 10 12 or less: When the surface resistance of A is higher than 1 × 10 12 and 1 × 10 14 or less: B surface resistance exceeds 1 × 10 14 : D
(7)反射干涉條紋所得到之硬化膜的反射干涉條紋依以下之基準,以目視評估。(7) The reflection interference fringes of the cured film obtained by reflecting the interference fringes were visually evaluated on the basis of the following criteria.
無法觀察反射干涉條紋:A可觀察反射干涉條紋:DUnable to observe reflection interference fringes: A observable reflection interference fringes: D
本案之揭示係與2006年5月29日所申請之日本特願2006-148854號、及2006年5月29日所申請之日本特願2006-148855號記載之主題相關,其等之全部的揭示內容係藉由引用而在此被援用。The disclosure of the present invention is related to the subject matter described in Japanese Patent Application No. 2006-148854, filed on May 29, 2006, and the Japanese Patent Application No. 2006-148855, filed on May 29, 2006. The content is hereby incorporated by reference.
於已敘述者以外,不脫離本發明之新穎且有利之特徵,應注意亦可以於上述實施型態中加上各種修正或變更。因此,如此之全部修正或變更係暗示包含於添附之申請專利範圍中。In addition to the novel and advantageous features of the invention, it should be noted that various modifications and changes may be added to the embodiments described above. Therefore, all such modifications or variations are intended to be included in the scope of the appended claims.
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EP2305451B1 (en) * | 2008-05-13 | 2013-11-20 | Mitsubishi Gas Chemical Company, Inc. | Bendable polycarbonate resin laminate, optically transparent electromagnetic wave shield laminate, and manufacturing method thereof |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200514073A (en) * | 2003-09-17 | 2005-04-16 | Fuji Photo Film Co Ltd | Recording media |
WO2005105866A1 (en) * | 2004-04-28 | 2005-11-10 | Toyo Ink Mfg. Co., Ltd. | Photocurable composition and antireflective film using same |
TW200600823A (en) * | 2004-06-17 | 2006-01-01 | 3M Innovative Properties Co | Durable optical element |
Family Cites Families (6)
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JP4210455B2 (en) * | 2002-02-15 | 2009-01-21 | 富士フイルム株式会社 | Photocurable coloring composition and color filter |
JP2004204174A (en) * | 2002-12-26 | 2004-07-22 | Catalysts & Chem Ind Co Ltd | Coating liquid for forming transparent electeroconductive film, substrate with transparent electroconductive film and displaying device |
JP3960307B2 (en) * | 2003-05-15 | 2007-08-15 | Jsr株式会社 | Liquid resin composition, cured film and laminate |
JP4470540B2 (en) * | 2004-03-19 | 2010-06-02 | 東洋インキ製造株式会社 | Photopolymerization initiator |
JP4924425B2 (en) * | 2005-07-19 | 2012-04-25 | 東洋インキScホールディングス株式会社 | Curable composition, cured film and laminate |
-
2007
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200514073A (en) * | 2003-09-17 | 2005-04-16 | Fuji Photo Film Co Ltd | Recording media |
WO2005105866A1 (en) * | 2004-04-28 | 2005-11-10 | Toyo Ink Mfg. Co., Ltd. | Photocurable composition and antireflective film using same |
TW200600823A (en) * | 2004-06-17 | 2006-01-01 | 3M Innovative Properties Co | Durable optical element |
Also Published As
Publication number | Publication date |
---|---|
JPWO2007138946A1 (en) | 2009-10-08 |
JP4692630B2 (en) | 2011-06-01 |
CN101454351B (en) | 2013-09-04 |
KR20090023359A (en) | 2009-03-04 |
KR101051228B1 (en) | 2011-07-21 |
WO2007138946A1 (en) | 2007-12-06 |
CN101454351A (en) | 2009-06-10 |
TW200808891A (en) | 2008-02-16 |
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