TWI617634B - Metal oxide film forming composition and metal oxide film - Google Patents
Metal oxide film forming composition and metal oxide film Download PDFInfo
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Abstract
本發明提供一種金屬氧化物膜形成用組成物，其係包含在表面上具有聚矽氧烷的二氧化矽粒子、與鋁化合物。 The present invention provides a metal oxide film-forming composition comprising cerium oxide particles having a polyoxyalkylene oxide on a surface thereof and an aluminum compound.
Description
本發明關於金屬氧化物膜形成用組成物及金屬氧化物膜。 The present invention relates to a composition for forming a metal oxide film and a metal oxide film.
作為如個人電腦、行動電話、電視等之資訊終端的顯示裝置，使用液晶顯示器。一般地，液晶顯示器係具有在形成有透明電極的1對基板之間封入有液晶之構造。作為此基板，使用由鈉鈣玻璃、無鹼玻璃等所形成之玻璃基板。 A liquid crystal display is used as a display device of an information terminal such as a personal computer, a mobile phone, or a television. Generally, a liquid crystal display has a structure in which a liquid crystal is sealed between a pair of substrates on which a transparent electrode is formed. As this substrate, a glass substrate formed of soda lime glass, alkali-free glass, or the like is used.
液晶顯示裝置(LCD)、電漿顯示器(PDP)、布朗恩管顯示裝置(CRT)、電致發光顯示裝置(EL)、觸控面板等為代表之顯示裝置等中所用之附透明電極的玻璃基板等之透明性基材，係在其單面上產生約4%的反射光，成為視覺辨認性及透過率降低之主要原因。因此，以減低來自基材的反射光量，提高視覺辨認性及透過率為目的，使用在基材表面上形成比基材較低折射率的被膜，即所謂防反射膜，而使反射率降低之方法。 A glass with a transparent electrode used in a representative display device, such as a liquid crystal display device (LCD), a plasma display (PDP), a Bronze display device (CRT), an electroluminescence display device (EL), a touch panel, or the like A transparent substrate such as a substrate generates about 4% of reflected light on one surface thereof, which is a cause of deterioration in visibility and transmittance. Therefore, in order to reduce the amount of reflected light from the substrate and improve visibility and transmittance, a film having a lower refractive index than the substrate, that is, an antireflection film, is formed on the surface of the substrate to reduce the reflectance. method.
為了得到低折射率之被膜，有提案一種塗佈液，其係 以一定比例含有具有5nm~30nm的粒徑之矽溶膠、與由烷氧基矽烷的水解物、金屬烷氧化物的水解物及金屬鹽所成之群選出的2種以上之成分(例如參照特開平8-122501號公報)。 In order to obtain a film having a low refractive index, a coating liquid is proposed. Two or more components selected from the group consisting of a ruthenium sol having a particle diameter of 5 nm to 30 nm, a hydrolyzate of alkoxy decane, a hydrolyzate of a metal alkoxide, and a metal salt in a certain ratio (for example, reference Kaiping No. 8-122501).
另一方面，已知藉由將低折射率被膜與高折射率被膜在基材上交替地積層而多層化，亦得到高防反射效果(例如參照特開2012-252305號公報)。 On the other hand, it is known that a high refractive index film and a high refractive index film are alternately laminated on a substrate to form a multilayer, and a high antireflection effect is also obtained (see, for example, JP-A-2012-252305).
[專利文獻1]特開平8-122501號公報 [Patent Document 1] JP-A-8-122501
[專利文獻2]特開2012-252305號公報 [Patent Document 2] JP-A-2012-252305
藉由使用特開平8-122501號公報中記載之塗佈液，雖然得到某一程度低的折射率之防反射膜，但要求具有更低折射率的防反射膜。又，於特開2012-252305號公報記載之手法中，必須分別地形成低折射率被膜與高折射率被膜，有製程效率上之問題。 An antireflection film having a lower refractive index is obtained, but an antireflection film having a lower refractive index is required, although a coating liquid described in Japanese Laid-Open Patent Publication No. Hei 8-122501 is used. Further, in the method described in Japanese Laid-Open Patent Publication No. 2012-252305, it is necessary to separately form a low refractive index film and a high refractive index film, which has a problem in process efficiency.
本發明之目的在於提供可簡便地形成低折射率的防反射膜之金屬氧化物膜形成用組成物及使用其所形成之金屬氧化物膜。 An object of the present invention is to provide a metal oxide film-forming composition which can easily form an antireflection film having a low refractive index and a metal oxide film formed using the same.
發明者們為了解決上述問題，重複專心致力的檢討，結果發現藉由使用一種包含在表面上具有聚矽氧烷的二氧化矽粒子、與至少1種的鋁化合物之金屬氧化物膜形成用組成物來形成金屬氧化物膜，可兼顧上述之課題，而完成本發明。即，本發明之要旨為以下。 In order to solve the above problems, the inventors repeated the intensive review, and found that the composition was formed by using a metal oxide film containing at least one type of cerium oxide particles having a polyoxyalkylene oxide on the surface and at least one aluminum compound. The present invention can be accomplished by forming a metal oxide film and achieving the above problems. That is, the gist of the present invention is as follows.
(1)一種金屬氧化物膜形成用組成物，其係包含：在表面上具有聚矽氧烷的二氧化矽粒子，與鋁化合物。 (1) A metal oxide film-forming composition comprising: cerium oxide particles having a polyoxyalkylene oxide on a surface thereof, and an aluminum compound.
(2)如前述(1)記載之金屬氧化物膜形成用組成物，其中鋁化合物包含含鋁之聚矽氧烷。 (2) The metal oxide film-forming composition according to the above (1), wherein the aluminum compound contains an aluminum-containing polyoxyalkylene oxide.
(3)如前述(2)記載之金屬氧化物膜形成用組成物，其中含鋁之聚矽氧烷係由鋁鹽及烷氧化鋁所成之群選出的至少1種之化合物與聚矽氧烷所成之反應物。 (3) The composition for forming a metal oxide film according to the above (2), wherein the aluminum-containing polyoxyalkylene is at least one compound selected from the group consisting of an aluminum salt and an alkane oxide, and a polyoxonium oxide. a reactant formed by an alkane.
(4)如前述(2)或(3)記載之金屬氧化物膜形成用組成物，其中含鋁之聚矽氧烷係由鹽酸鹽、硝酸鹽、硫酸鹽、乙酸鹽、胺基磺酸鹽、磺酸鹽、乙醯乙酸鹽及此等之鹼性鹽所成之群選出的至少1種之鋁鹽以及由烷氧化鋁所成之群選出的至少1種之化合物、與下述式(I)所示作為烷氧基矽烷的縮合聚合物之聚矽氧烷所成之反應物；R2 kSi(OR1)(4-k) (I) (4) The metal oxide film-forming composition according to the above (2) or (3), wherein the aluminum-containing polyoxyalkylene is a hydrochloride, a nitrate, a sulfate, an acetate or an aminosulfonic acid. At least one aluminum salt selected from the group consisting of a salt, a sulfonate, an acetamidine acetate, and a basic salt thereof, and at least one compound selected from the group consisting of an alkane alumina, and the following formula (I), the alkoxy group of the silane-condensation polymer formed by polymerization of the siloxane silicon reactant; R 2 k Si (OR 1 ) (4-k) (I)
(式中，R1各自獨立地表示碳數1~5的烷基；R2各自獨立地表示可具有取代基且可具有雜原子之碳數1~20的烴基、鹵素原子或氫原子；k表示0~3之整數)。 (Wherein, R 1 is each independently represents an alkyl group having 1 to 5 carbon atoms, a; R 2 each independently represent a hydrocarbon group, a halogen atom or a hydrogen atom may have a substituent and hetero atoms of a carbon number of 1 to 20; K Indicates an integer from 0 to 3.)
(5)如前述(2)~(4)中任一項記載之金屬氧化物膜形成用組成物，其中含鋁之聚矽氧烷，係換算成氧化 鋁(Al2O3)的鋁相對於換算成氧化矽(SiO2)的聚矽氧烷之含有比率(鋁/聚矽氧烷)，以莫耳基準計為50/50~80/20。 (5) The composition for forming a metal oxide film according to any one of the above-mentioned (2), wherein the aluminum-containing polyaluminoxane is aluminum equivalent to aluminum oxide (Al 2 O 3 ). The content ratio of polysiloxane (aluminum/polyoxyalkylene) converted to cerium oxide (SiO 2 ) is 50/50 to 80/20 on a molar basis.
(6)如前述(1)~(5)中任一項記載之金屬氧化物膜形成用組成物，其中表面上具有聚矽氧烷的二氧化矽粒子，係聚矽氧烷與二氧化矽粒子所成之反應物。 (6) The composition for forming a metal oxide film according to any one of the above aspects, wherein the cerium oxide particles having a polyoxyalkylene on the surface thereof are polyoxyalkylene oxide and cerium oxide. The reactants formed by the particles.
(7)如前述(1)~(6)中任一項記載之金屬氧化物膜形成用組成物，其中在表面上具有聚矽氧烷的二氧化矽粒子，係下述式(I)所示作為烷氧基矽烷的縮合聚合物之聚矽氧烷與二氧化矽粒子所成之反應物，R2 kSi(OR1)(4-k) (I) The composition for forming a metal oxide film according to any one of the above-mentioned (1), wherein the cerium oxide particles having a polyoxyalkylene on the surface are the following formula (I). a reaction product of a polyoxane and a cerium oxide particle as a condensation polymer of an alkoxydecane, R 2 k Si(OR 1 ) (4-k) (I)
(式中，R1各自獨立地表示碳數1~5的烷基；R2各自獨立地表示可具有取代基且可具有雜原子之碳數1~20的烴基、鹵素原子或氫原子；k表示0~3之整數)。 (wherein R 1 each independently represents an alkyl group having 1 to 5 carbon atoms; and R 2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or a hydrogen atom which may have a hetero atom; k Indicates an integer from 0 to 3.)
(8)如前述(1)~(7)中任一項記載之金屬氧化物膜形成用組成物，其中在表面上具有聚矽氧烷的二氧化矽粒子之平均粒徑為1nm~200nm。 The composition for forming a metal oxide film according to any one of the above aspects, wherein the cerium oxide particles having a polysiloxane on the surface have an average particle diameter of from 1 nm to 200 nm.
(9)如前述(1)~(8)中任一項記載之金屬氧化物膜形成用組成物，其中在表面上具有聚矽氧烷的二氧化矽粒子，係二氧化矽粒子相對於聚矽氧烷之含有比率(二氧化矽粒子/聚矽氧烷)，以莫耳基準計為50/50~80/20。 The composition for forming a metal oxide film according to any one of the above aspects, wherein the cerium oxide particles having a polysiloxane on the surface are cerium oxide particles relative to the poly The content ratio of oxoxane (cerium oxide particles/polyoxane) is 50/50 to 80/20 on a molar basis.
(10)如前述(1)~(9)中任一項記載之金屬氧化物膜形成用組成物，其中相對於換算成氧化矽(SiO2)的 聚矽氧烷及二氧化矽粒子之總量，換算成氧化鋁(Al2O3)的鋁之含有率為1莫耳%~20莫耳%。 (10) The metal oxide film-forming composition according to any one of the above-mentioned (1), wherein the total amount of the polyoxane and the cerium oxide particles converted to cerium oxide (SiO 2 ) is The amount of aluminum converted into alumina (Al 2 O 3 ) is 1 mol% to 20 mol%.
(11)如前述(1)~(10)中任一項記載之金屬氧化物膜形成用組成物，其係進一步包含沸點為170℃以上的有機溶劑。 The composition for forming a metal oxide film according to any one of the above aspects, further comprising an organic solvent having a boiling point of 170 ° C or higher.
(12)一種金屬氧化物膜，其係如前述(1)~(11)中任一項記載之金屬氧化物膜形成用組成物的硬化物。 (12) A cured product of the metal oxide film-forming composition according to any one of the above (1) to (11).
(13)一種附金屬氧化物膜之基材，其係包含：基材，與配置於基材上之如前述(1)~(11)中任一項記載之金屬氧化物膜形成用組成物的硬化物。 (13) A metal oxide film-forming substrate according to any one of the above (1) to (11), wherein the substrate is a base material, and the metal oxide film forming composition according to any one of the above (1) to (11) Hardened matter.
(14)一種附金屬氧化物膜之基材的製造方法，其係包含：於基材上，賦予如前述(1)~(11)中任一項記載之金屬氧化物膜形成用組成物，以及對於已賦予於基材上的金屬氧化物膜形成用組成物，賦予熱。 (14) A method for producing a metal oxide film according to any one of the above (1) to (11), wherein the metal oxide film-forming composition according to any one of the above (1) to (11), Further, heat is imparted to the composition for forming a metal oxide film which has been applied to the substrate.
依照本發明，可提供能簡便地形成低折射率的防反射膜之金屬氧化物膜形成用組成物及使用其所形成之金屬氧化物膜。 According to the present invention, a metal oxide film-forming composition capable of easily forming an antireflection film having a low refractive index and a metal oxide film formed using the same can be provided.
本說明書中使用「~」表示的數值範圍，係表示包含 「~」之前後所記載的數值當作各自的最小值及最大值之範圍。又，組成物中的各成分之含量，當組成物中相當於各成分的物質係複數存在時，只要沒有特別預先指明，則意指組成物中存在的該複數物質之合計量。 The range of values indicated by "~" in this manual is intended to include The values described before and after "~" are taken as the range of the minimum and maximum values. Further, when the content of each component in the composition is present in a plurality of substances corresponding to the respective components in the composition, unless otherwise specified, it means the total amount of the plural substances present in the composition.
本發明之金屬氧化物膜形成用組成物之特徵為包含：在表面上具有聚矽氧烷的二氧化矽粒子(以下稱為「A成分」)、與鋁化合物(以下稱為「B成分」)。藉由包含在表面上具有聚矽氧烷的二氧化矽粒子與鋁化合物(較佳為含鋁之聚矽氧烷)，當將其賦予基材上而形成硬化物時，可藉由簡便的手法形成折射率低、具有優異的硬度之作為金屬氧化物膜的防反射膜。再者，使用本發明之金屬氧化物膜形成用組成物，在玻璃基材上形成金屬氧化物膜時，可有效果地抑制經時所造成的玻璃基材之白化現象。 The metal oxide film-forming composition of the present invention is characterized by comprising cerium oxide particles (hereinafter referred to as "A component") having a polysiloxane, and an aluminum compound (hereinafter referred to as "B component"). ). By using a cerium oxide particle having a polyoxyalkylene on the surface and an aluminum compound (preferably an aluminum-containing polyoxyalkylene), when it is imparted to a substrate to form a cured product, it can be easily An antireflection film which is a metal oxide film having a low refractive index and excellent hardness is formed by a method. Further, when the metal oxide film forming composition of the present invention is used, when the metal oxide film is formed on the glass substrate, the whitening phenomenon of the glass substrate caused by the passage can be effectively suppressed.
由本發明之金屬氧化物膜形成用組成物所形成之金屬氧化物膜，顯示低折射率之理由的詳細係未明確，但例如判斷如以下。 The details of the reason why the metal oxide film formed of the metal oxide film-forming composition of the present invention exhibits a low refractive index are not clear, but are determined, for example, as follows.
即，茲認為由金屬氧化物膜形成用組成物所形成之金屬氧化物膜，與由以往的金屬氧化物膜形成用組成物所形成之金屬氧化物膜比較下，係金屬氧化物膜中存在的微細空隙多，藉由該空隙，可達成低折射率。 In other words, it is considered that the metal oxide film formed of the metal oxide film-forming composition is present in the metal oxide film as compared with the metal oxide film formed of the conventional metal oxide film-forming composition. There are many fine voids, and by this void, a low refractive index can be achieved.
一般地，作為形成在膜中具有空隙的金屬氧化物膜之方法，已知藉由使膜形成用之組成物中含有界面活性劑， 於製膜後加熱而自膜中去除界面活性劑，形成空隙之手法。此時，由於需要高溫下的加熱，有製程效率上之問題，有難以充分提高所得之膜的硬度之情況。 In general, as a method of forming a metal oxide film having voids in a film, it is known that a surfactant is contained in a composition for forming a film, The method of forming a void by removing the surfactant from the film after heating after film formation. At this time, since heating at a high temperature is required, there is a problem in process efficiency, and it is difficult to sufficiently increase the hardness of the obtained film.
然而，茲認為由本發明之金屬氧化物膜形成用組成物所形成的金屬氧化物膜，因為由在表面上具有聚矽氧烷的二氧化矽粒子與鋁化合物所形成，雖然保持優異的膜硬度，但在膜中形成有微細的空隙。 However, it is considered that the metal oxide film formed by the composition for forming a metal oxide film of the present invention is formed of cerium oxide particles having a polyoxyalkylene on the surface and an aluminum compound, although excellent film hardness is maintained. However, fine voids are formed in the film.
又，將本發明之金屬氧化物膜形成用組成物賦予玻璃基材而形成金屬氧化物膜時，雖然詳細的機構不明，但判斷藉由鋁化合物之作用，抑制玻璃基材的高溫高濕環境下之白化，而且可達成更低的折射率。 When a metal oxide film is formed by applying a composition for forming a metal oxide film of the present invention to a glass substrate, the detailed mechanism is not known, but it is determined that the high temperature and high humidity environment of the glass substrate is suppressed by the action of the aluminum compound. The whitening is achieved, and a lower refractive index can be achieved.
金屬氧化物膜形成用組成物包含在表面上具有聚矽氧烷的二氧化矽粒子(以下亦稱為「特定二氧化矽粒子」)之至少1種。一般地藉由包含二氧化矽粒子，可調整所形成的金屬氧化物膜之表面形狀及折射率，以及可賦予其它所欲的機能。本發明中，判斷由於二氧化矽粒子係在表面上具有聚矽氧烷，可形成折射率更低、硬度優異之金屬氧化物膜。 The metal oxide film-forming composition contains at least one of cerium oxide particles (hereinafter also referred to as "specific cerium oxide particles") having polyoxyalkylene on the surface. Generally, by including cerium oxide particles, the surface shape and refractive index of the formed metal oxide film can be adjusted, and other desired functions can be imparted. In the present invention, it is judged that the cerium oxide particles have a polyoxyalkylene oxide on the surface, and a metal oxide film having a lower refractive index and excellent hardness can be formed.
在表面上具有聚矽氧烷的二氧化矽粒子，例如可使聚矽氧烷與二氧化矽粒子接觸而得。即，在表面上具有聚矽氧烷的二氧化矽粒子較佳為聚矽氧烷與二氧化矽粒子所成之反應物，更佳為下述式(I)所示作為烷氧基矽烷的縮 合聚合物之聚矽氧烷與二氧化矽粒子所成之反應物。 The cerium oxide particles having a polyoxyalkylene on the surface can be obtained, for example, by contacting a polyoxyalkylene oxide with cerium oxide particles. That is, the cerium oxide particles having a polyoxyalkylene oxide on the surface are preferably a reaction product of a polysiloxane and a cerium oxide particle, more preferably an alkoxy decane represented by the following formula (I). Shrink A reactant of a polymer of polyoxyalkylene oxide and cerium oxide particles.
R2 kSi(OR1)(4-k) (I) R 2 k Si(OR 1 ) (4-k) (I)
式中，R1各自獨立地表示碳數1~5的烷基；R2各自獨立地表示可具有取代基且可具有雜原子之碳數1~20的烴基、鹵素原子或氫原子；k表示0~3之整數。 Formula, R 1 is each independently represents an alkyl group having 1 to 5 carbon atoms, a; R 2 each independently represent a group may have a substituent and may have a carbon number of the hydrocarbon group a hetero atom, a halogen atom or a hydrogen atom of 1 to 20; K represents An integer from 0 to 3.
R1所示之烷基係碳數較佳為1~3者，更佳為1~2者。作為R1所示之烷基，具體地可舉出甲基、乙基、丙基、異丙基、丁基、2-丁基、第二丁基、第三丁基、戊基等。 The number of carbon atoms represented by R 1 is preferably from 1 to 3, more preferably from 1 to 2. Specific examples of the alkyl group represented by R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a second butyl group, a tert-butyl group, and a pentyl group.
於式(I)所示之烷氧基矽烷中，當R1為2以上存在時，彼等可相同或相異。 In the alkoxydecane represented by the formula (I), when R 1 is 2 or more, they may be the same or different.
作為R2所示之烴基，可舉出烷基及芳基。 The hydrocarbon group represented by R 2 may, for example, be an alkyl group or an aryl group.
R2所示之烴基係可具有取代基。作為取代基，可舉出氟原子、氯原子、溴原子、碘原子等之鹵素原子；乙烯基、烯丙基等之烯基；苯基等之芳基；胺基；羥基；氫硫基(巰基)；氰基；醯胺基；脲基；丙烯醯氧基；甲基丙烯醯氧基；環氧丙基等。取代基係可更具有取代基。作為R2所示之烴基，亦可具有雜原子。作為雜原子，可舉出氧原子、硫原子、氮原子等。 The hydrocarbon group represented by R 2 may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group; an amine group; a hydroxyl group; and a thiol group ( Sulfhydryl; cyano; guanamine; ureido; propylene oxime; methacryloxy group; The substituent system may have a more substituent. The hydrocarbon group represented by R 2 may have a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
作為R2所示之烴基，具體地可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、十八基、乙烯基、氯丙基、羥基丙基、環氧丙氧基丙基、甲基丙烯醯氧基丙基、苯基、三氟丙基等。 Specific examples of the hydrocarbon group represented by R 2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an octadecyl group, a vinyl group, a chloropropyl group, and a hydroxypropyl group. , glycidoxypropyl, methacryloxypropyl, phenyl, trifluoropropyl and the like.
作為R2所示之鹵素原子，可舉出氟原子、氯原子、 溴原子、碘原子等，較佳為氯原子或溴原子。 The halogen atom represented by R 2 may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom or a bromine atom.
於式(I)所示之烷氧基矽烷中，R2為2以上存在時，彼等可相同或相異。 In the alkoxydecane represented by the formula (I), when R 2 is 2 or more, they may be the same or different.
k表示0~3之整數，較佳為0~2，更佳為0或1。 k represents an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1.
作為式(I)所示之k為0的烷氧基矽烷，具體地可舉出四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷、甲氧基三乙氧基矽烷、乙氧基三甲氧基矽烷、甲氧基三丙氧基矽烷、乙氧基三丙氧基矽烷、丙氧基三甲氧基矽烷、丙氧基三乙氧基矽烷、二甲氧基二乙氧基矽烷等。 The alkoxydecane wherein k is 0 represented by the formula (I), specifically, tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane, methoxy III Ethoxy decane, ethoxy trimethoxy decane, methoxy tripropoxy decane, ethoxy tripropoxy decane, propoxy trimethoxy decane, propoxy triethoxy decane, dimethyl Oxydiethoxydecane, and the like.
作為式(I)所示之k為1的烷氧基矽烷，具體地可舉出甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、丁基三甲氧基矽烷、丁基三乙氧基矽烷、戊基三甲氧基矽烷、戊基三乙氧基矽烷、己基三甲氧基矽烷、己基三乙氧基矽烷、庚基三甲氧基矽烷、庚基三乙氧基矽烷、辛基三甲氧基矽烷、辛基三乙氧基矽烷、十八基三甲氧基矽烷、十八基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、3-氯丙基三乙氧基矽烷、3-羥基丙基三甲氧基矽烷、3-羥基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、三氟丙基三甲氧基矽 烷、三氟丙基三乙氧基矽烷等。 The alkoxydecane wherein k is 1 represented by the formula (I) may specifically be methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane or ethyltriethoxy. Decane, propyltrimethoxydecane, propyltriethoxydecane, butyltrimethoxydecane, butyltriethoxydecane,pentyltrimethoxydecane,pentyltriethoxydecane,hexyltrimethoxy Base decane, hexyl triethoxy decane, heptyl trimethoxy decane, heptyl triethoxy decane, octyl trimethoxy decane, octyl triethoxy decane, octadecyl trimethoxy decane, eighteen Triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-chloropropyl trimethoxy decane, 3-chloropropyl triethoxy decane, 3-hydroxypropyl trimethoxy Baseline, 3-hydroxypropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-methylpropene oxime Propyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, trifluoro Trimethoxy silicon Alkane, trifluoropropyltriethoxydecane, and the like.
作為式(I)所示之k為2的烷氧基矽烷，具體地可舉出二甲基二甲氧基矽烷、二甲基二乙氧基矽烷等。 Specific examples of the alkoxydecane in which k is 2 represented by the formula (I) include dimethyldimethoxydecane, dimethyldiethoxydecane, and the like.
於此等烷氧基矽烷之中，較宜使用四甲氧基矽烷、四乙氧基矽烷等之具有碳數為1~3的烷氧基之四烷氧基矽烷。 Among the alkoxydecanes, a tetraalkoxydecane having an alkoxy group having 1 to 3 carbon atoms such as tetramethoxynonane or tetraethoxysilane is preferably used.
構成聚矽氧烷的烷氧基矽烷係可為單獨1種，也可為2種以上之組合。 The alkoxysilane of the polyoxyalkylene may be used alone or in combination of two or more.
聚矽氧烷之分子量係沒有特別的限制，可按照目的等來適宜選擇。聚矽氧烷之分子量，從保存安定性之觀點來看，數量平均分子量較佳為1000~20000，更佳為1000~8000。聚矽氧烷之數量平均分子量係使用GPC，藉由常見方法測定。 The molecular weight of the polyoxyalkylene is not particularly limited and may be appropriately selected depending on the purpose and the like. The molecular weight of the polyoxyalkylene is preferably from 1,000 to 20,000, more preferably from 1,000 to 8,000, from the viewpoint of preservation stability. The number average molecular weight of polyoxyalkylene is determined by a common method using GPC.
聚矽氧烷係以後述之製造方法製造者，也可為市售者。 The polyoxyalkylene is also a manufacturer of a production method described later, and may be a commercially available one.
調製聚矽氧烷之方法係沒有特別的限定，可自通常使用的調製方法中適宜選擇。例如，可將由上述式(I)所示之烷氧基矽烷所成之群選出的至少1種之烷氧基矽烷在溶劑中縮合聚合而調製。通常，聚矽氧烷較佳為將上述烷氧基矽烷在溶劑中縮合聚合，成為溶解於溶劑中之溶液而得。 The method of modulating the polyoxyalkylene is not particularly limited and may be appropriately selected from the usual preparation methods. For example, at least one alkoxydecane selected from the group consisting of the alkoxydecane represented by the above formula (I) can be prepared by condensation polymerization in a solvent. Usually, the polyoxyalkylene is preferably obtained by condensation-polymerizing the above alkoxydecane in a solvent to obtain a solution dissolved in a solvent.
作為將烷氧基矽烷縮合聚合之方法，具體地例如可舉 出將烷氧基矽烷在醇或二醇等之溶劑中水解、縮合聚合之方法。水解反應係可為部分水解及完全水解之任一者。完全水解時，理論上只要添加烷氧基矽烷中的全部烷氧基之0.5倍莫耳的水即可，但一般較佳為添加比0.5倍莫耳過剩量之水。 As a method of condensing and polymerizing an alkoxy decane, specifically, for example, A method of hydrolyzing and condensing and polymerizing an alkoxydecane in a solvent such as an alcohol or a diol. The hydrolysis reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add water of 0.5 times moles of all alkoxy groups in the alkoxysilane, but it is generally preferred to add water in an excess amount of 0.5 times mole.
用於上述反應之水量，係可按照所欲而適宜選擇，但一般較佳為烷氧基矽烷中的全部烷氧基之0.5~2.5倍莫耳。 The amount of water used in the above reaction can be suitably selected as desired, but it is generally preferably 0.5 to 2.5 times moles of all alkoxy groups in the alkoxydecane.
又，以促進水解反應及縮合聚合反應等為目的，亦可使用鹽酸、硫酸、硝酸等之無機酸；乙酸、甲酸、草酸、馬來酸、富馬酸等之有機酸；氨、甲胺、乙胺、乙醇胺、三乙胺等之鹼(alkali)；鹽酸鹽、硫酸鹽、硝酸鹽等之金屬鹽等觸媒。又，藉由加熱烷氧基矽烷已溶解之溶液，亦可更促進水解反應及縮合聚合反應。當時，加熱溫度及加熱時間係可按照所欲來適宜選擇。例如，於50℃加熱及攪拌24小時之方法，於回流下加熱及攪拌1~3小時之方法等。 Further, for the purpose of promoting the hydrolysis reaction, the condensation polymerization reaction, or the like, an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid; an organic acid such as acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid; ammonia or methylamine; A base such as ethylamine, ethanolamine or triethylamine; a catalyst such as a metal salt such as a hydrochloride, a sulfate or a nitrate. Further, the hydrolysis reaction and the condensation polymerization reaction can be further promoted by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and heating time can be appropriately selected as desired. For example, a method of heating and stirring at 50 ° C for 24 hours, heating and stirring under reflux for 1 to 3 hours, and the like.
又，作為其它方法，例如可舉出加熱烷氧基矽烷、溶劑及草酸之混合物而聚縮合之方法。具體地，預先在醇中加入草酸而成為草酸之醇溶液後，於已加熱該溶液之狀態下，混合烷氧基矽烷之方法。當時，所用之草酸的量，相對於烷氧基矽烷所具有的全部烷氧基之1莫耳，較佳為0.2~2莫耳。此方法中的加熱可在液溫50~180℃下進行。較佳為以不發生液之蒸發、揮散等之方式，在回流下 加熱數十分鐘~十幾小時之方法。 Further, as another method, for example, a method of heating and agglomerating a mixture of alkoxysilane, a solvent, and oxalic acid can be mentioned. Specifically, a method in which oxalic acid is added to an alcohol to form an alcohol solution of oxalic acid, and alkoxysilane is mixed in a state where the solution is heated. At that time, the amount of oxalic acid used was preferably 1 to 2 moles per 1 mole of all alkoxy groups of the alkoxydecane. The heating in this method can be carried out at a liquid temperature of 50 to 180 °C. Preferably, in the form of no evaporation, evaporation, etc. of the liquid, under reflux Heat for tens of minutes to ten hours.
於調製聚矽氧烷之際，使用複數的烷氧基矽烷時，可使用預先混合有複數種的烷氧基矽烷之混合物，也可依序混合複數種的烷氧基矽烷而使用。 When a polyoxyalkylene oxide is used, a mixture of a plurality of alkoxysilanes may be used in advance, or a plurality of alkoxysilanes may be mixed in order.
將烷氧基矽烷縮合聚合之際所使用的溶劑(以下亦稱為聚合溶劑)，只要是溶解烷氧基矽烷之溶劑，則沒有特別的限定。又，即使烷氧基矽烷不溶解之情況，也只要在烷氧基矽烷的縮合聚合反應之進行時同時溶解的溶劑即可。一般地，由於因烷氧基矽烷之縮合聚合反應而生成醇，使用與醇溶劑、二醇溶劑、二醇醚溶劑或醇溶劑之相溶性良好的有機溶劑。 The solvent (hereinafter also referred to as a polymerization solvent) to be used in the condensation polymerization of the alkoxydecane is not particularly limited as long as it is a solvent in which the alkoxysilane is dissolved. Further, even when the alkoxysilane is not dissolved, a solvent which is simultaneously dissolved in the progress of the condensation polymerization of the alkoxydecane may be used. In general, an alcohol is formed by a condensation polymerization reaction of an alkoxydecane, and an organic solvent having good compatibility with an alcohol solvent, a glycol solvent, a glycol ether solvent or an alcohol solvent is used.
作為上述聚合溶劑之具體例，可舉出甲醇、乙醇、丙醇、丁醇，二丙酮醇等之醇溶劑；乙二醇、二乙二醇、丙二醇、二丙二醇、己二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、1,5-戊二醇、2,4-戊二醇、2,3-戊二醇、1,6-己二醇等之二醇溶劑；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基醚、乙二醇二丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇 二丙基醚、丙二醇二丁基醚等之二醇醚溶劑；N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等之醯胺溶劑；γ-丁內酯、二甲亞碸、四甲基脲、六甲基磷三醯胺、間甲酚等之有機溶劑。 Specific examples of the polymerization solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, and 1,3. -propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol , diol solvent such as 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, etc.; Methyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl Ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol a glycol ether solvent such as dipropyl ether or propylene glycol dibutyl ether; N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. A decylamine solvent; an organic solvent such as γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethylphosphoric acid triamide or m-cresol.
聚合溶劑係可為單獨1種，也可混合複數種使用。 The polymerization solvent may be used singly or in combination of plural kinds.
用於在表面上具有聚矽氧烷的二氧化矽粒子之調製的二氧化矽粒子係沒有特別的限制，可自通常使用的二氧化矽粒子中適宜選擇。其中，二氧化矽粒子，從調整所形成的金屬氧化物膜之表面形狀及折射率之觀點來看，其平均粒徑較佳為1nm~200nm，更佳為1nm~100nm，尤佳為1nm~50nm，特佳為9nm~45nm。二氧化矽粒子之平均粒徑若為200nm以下，則可對所形成的金屬氧化物膜，賦予充分的透明性。又，二氧化矽粒子之平均粒徑若為1nm以上，則有抑制二氧化矽粒子的凝聚之傾向。 The cerium oxide particle used for the preparation of the cerium oxide particles having a polyoxyalkylene on the surface is not particularly limited, and can be suitably selected from the commonly used cerium oxide particles. The cerium oxide particles preferably have an average particle diameter of from 1 nm to 200 nm, more preferably from 1 nm to 100 nm, and particularly preferably from 1 nm, from the viewpoint of adjusting the surface shape and refractive index of the formed metal oxide film. 50 nm, particularly preferably 9 nm to 45 nm. When the average particle diameter of the cerium oxide particles is 200 nm or less, sufficient transparency can be imparted to the formed metal oxide film. Further, when the average particle diameter of the cerium oxide particles is 1 nm or more, aggregation of the cerium oxide particles tends to be suppressed.
二氧化矽粒子之平均粒徑係使用動態光散射法測定粒度分布，作為自小粒徑側起相當於體積累計50%之粒徑所測定的體積平均粒徑。 The average particle diameter of the cerium oxide particles is measured by a dynamic light scattering method, and the volume average particle diameter measured as a particle diameter corresponding to a volume cumulative 50% from the small particle diameter side.
二氧化矽粒子較佳為以膠體溶液(矽溶膠)之狀態使用。二氧化矽粒子之膠體溶液係可使用以通常使用的方法使二氧化矽粒子分散於分散介質中者，也可為市售的二氧化矽粒子膠體溶液(所謂的膠態二氧化矽等)。膠體溶液中的二氧化矽粒子係可為鏈狀或球狀，從更有效果地得到 本發明的效果之觀點來看，較佳為鏈狀。 The cerium oxide particles are preferably used in the form of a colloidal solution (cerium sol). The colloidal solution of the cerium oxide particles may be one in which the cerium oxide particles are dispersed in a dispersion medium by a usual method, or a commercially available cerium oxide particle colloidal solution (so-called colloidal cerium oxide or the like). The cerium oxide particles in the colloidal solution may be chain or spherical, which is obtained more effectively. From the viewpoint of the effects of the present invention, it is preferably chain-shaped.
使用膠體溶液作為二氧化矽粒子時，從金屬氧化物形成用組成物之安定性之觀點來看、pH或pKa較佳為調整至1~10，更佳為2~7。 When a colloidal solution is used as the cerium oxide particles, the pH or pKa is preferably adjusted to 1 to 10, more preferably 2 to 7, from the viewpoint of the stability of the metal oxide-forming composition.
使用膠體溶液作為二氧化矽粒子時，作為二氧化矽粒子之分散介質，可舉出水及有機溶劑。 When a colloidal solution is used as the ceria particles, water and an organic solvent are exemplified as the dispersion medium of the ceria particles.
作為用於膠體溶液之分散介質的有機溶劑，可舉出甲醇、丙醇、丁醇、乙二醇、丙二醇、丁二醇、戊二醇、己二醇、二乙二醇、二丙二醇、乙二醇單丙基醚等之醇溶劑；甲基乙基酮、甲基異丁基酮等之酮溶劑；甲苯、二甲苯等之芳香族烴溶劑；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等之醯胺溶劑；乙酸乙酯、乙酸丁酯、γ-丁內酯等之酯溶劑；四氫呋喃、1,4-二烷等之醚溶劑。於此等之中，較佳為醇溶劑及酮溶劑。此等有機溶劑係可為單獨1種或混合2種以上，作為分散介質使用。 Examples of the organic solvent used for the dispersion medium of the colloidal solution include methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, and B. Alcohol solvent such as diol monopropyl ether; ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; aromatic hydrocarbon solvent such as toluene or xylene; dimethylformamide, dimethyl a decylamine solvent such as guanamine or N-methylpyrrolidone; an ester solvent of ethyl acetate, butyl acetate, γ-butyrolactone, etc.; tetrahydrofuran, 1,4-two An ether solvent such as an alkane. Among these, an alcohol solvent and a ketone solvent are preferred. These organic solvents may be used alone or in combination of two or more kinds as a dispersion medium.
在表面上具有聚矽氧烷的二氧化矽粒子，係可藉由使聚矽氧烷與二氧化矽粒子接觸而調製。若使聚矽氧烷與二氧化矽粒子接觸，則判斷例如聚矽氧烷中之矽烷醇基或烷氧基矽烷基係與二氧化矽粒子表面上存在的羥基進行縮合反應，而形成在表面上具有聚矽氧烷的二氧化矽粒子。 The cerium oxide particles having a polyoxyalkylene on the surface can be prepared by bringing the polyoxyalkylene oxide into contact with the cerium oxide particles. When the polyoxyalkylene is brought into contact with the cerium oxide particles, it is judged that, for example, the decyl alcohol group or the alkoxy fluorenyl alkyl group in the polyoxyalkylene is condensed with the hydroxyl group present on the surface of the cerium oxide particle to form a surface. A cerium oxide particle having a polyoxyalkylene oxide.
具體地，例如藉由混合二氧化矽粒子之膠體溶液與預先準備的聚矽氧烷溶液，可調製在表面上具有聚矽氧烷的二氧化矽粒子。膠體溶液與聚矽氧烷溶液之混合係可在常溫下進行，也可邊加熱邊進行。從反應效率之觀點來看， 混合較佳為邊加熱邊進行。邊加熱邊進行混合時，其加熱溫度係可按照溶劑等來適宜選擇。加熱溫度例如可為60℃以上，較佳為溶劑之回流溫度。 Specifically, the cerium oxide particles having a polyoxyalkylene oxide on the surface can be prepared, for example, by mixing a colloidal solution of cerium oxide particles with a previously prepared polyoxyalkylene solution. The mixing of the colloidal solution and the polyoxyalkylene solution can be carried out at room temperature or with heating. From the point of view of reaction efficiency, The mixing is preferably carried out while heating. When mixing is carried out while heating, the heating temperature can be appropriately selected in accordance with a solvent or the like. The heating temperature may be, for example, 60 ° C or higher, preferably the reflux temperature of the solvent.
調製在表面上具有聚矽氧烷的二氧化矽粒子時之聚矽氧烷與二氧化矽粒子的混合比例，係可按照目的等來適宜選擇。例如，二氧化矽粒子相對於聚矽氧烷的莫耳比(二氧化矽粒子/聚矽氧烷)，較佳為50/50~80/20，更佳為50/50~70/30，尤佳為60/40~70/30。此處，聚矽氧烷之莫耳數，係以作為原料所加入的烷氧基矽烷之總莫耳數算出，二氧化矽粒子之莫耳數係將二氧化矽粒子之組成式當作SiO2而算出。 The mixing ratio of the polyoxyalkylene oxide to the cerium oxide particles in the case of cerium oxide particles having a polyoxyalkylene oxide on the surface thereof can be appropriately selected depending on the purpose and the like. For example, the molar ratio of the cerium oxide particles to the polyoxyalkylene oxide (cerium oxide particles/polyoxane) is preferably 50/50 to 80/20, more preferably 50/50 to 70/30. Especially good is 60/40~70/30. Here, the molar number of the polyoxyalkylene is calculated from the total number of moles of the alkoxysilane added as a raw material, and the molar number of the cerium oxide particles is the composition of the cerium oxide particles as SiO. 2 and calculate.
在表面上具有聚矽氧烷的二氧化矽粒子之體積平均粒徑係可按照目的等來適宜選擇。其中，從調整所形成的金屬氧化物膜之折射率的觀點來看，體積平均粒徑較佳為1nm~200nm，更佳為1nm~100nm，尤佳為9nm~60nm，特佳為9nm~45nm。 The volume average particle diameter of the cerium oxide particles having a polyoxyalkylene on the surface can be appropriately selected depending on the purpose and the like. The volume average particle diameter is preferably from 1 nm to 200 nm, more preferably from 1 nm to 100 nm, even more preferably from 9 nm to 60 nm, particularly preferably from 9 nm to 45 nm, from the viewpoint of adjusting the refractive index of the formed metal oxide film. .
再者，在表面上具有聚矽氧烷的二氧化矽粒子之體積平均粒徑，係使用動態光散射法測定。 Further, the volume average particle diameter of the cerium oxide particles having a polyoxyalkylene on the surface was measured by a dynamic light scattering method.
金屬氧化物膜形成用組成物包含鋁化合物之至少1種。金屬氧化物膜形成用組成物，係除了包含在表面上具有聚矽氧烷的二氧化矽粒子，還包含鋁化合物，而可藉由簡便的手法形成低折射率且硬度優異，更且能抑制玻璃基 材的白化之金屬氧化物膜。 The metal oxide film-forming composition contains at least one of aluminum compounds. The composition for forming a metal oxide film is not only a cerium oxide particle having a polysiloxane, but also an aluminum compound, and a low refractive index can be formed by a simple method, and the hardness is excellent, and the film can be suppressed. Glass base A whitened metal oxide film of wood.
作為B成分中的鋁化合物，可舉出鋁鹽、含鋁之聚矽氧烷等，較佳為含有含鋁之聚矽氧烷。 Examples of the aluminum compound in the component B include an aluminum salt, an aluminum-containing polysiloxane, and the like, and preferably an aluminum-containing polyoxyalkylene.
鋁鹽只要可與聚矽氧烷反應，則沒有特別的限制，可自通常使用的鋁鹽中適宜選擇而使用。作為鋁鹽，具體地較佳為由鹽酸鹽、硝酸鹽、硫酸鹽、乙酸鹽、胺基磺酸鹽、磺酸鹽、乙醯乙酸鹽及此等之鹼性鹽所成之群選出的至少1種。 The aluminum salt is not particularly limited as long as it can be reacted with polyoxyalkylene oxide, and can be appropriately selected from the commonly used aluminum salts. Specifically, the aluminum salt is preferably selected from the group consisting of hydrochloride, nitrate, sulfate, acetate, amine sulfonate, sulfonate, acetoacetate, and the like. At least one.
含鋁之聚矽氧烷例如係可藉由使由鋁鹽及烷氧化鋁選出的至少1種化合物與聚矽氧烷接觸而得。即，含鋁之聚矽氧烷較佳為由鋁鹽及烷氧化鋁選出的至少1種化合物與聚矽氧烷所成之反應物，更佳為由鹽酸鹽、硝酸鹽、硫酸鹽、乙酸鹽、胺基磺酸鹽、磺酸鹽、乙醯乙酸鹽及此等之鹼性鹽所成之群選出的至少1種之鋁鹽以及由烷氧化鋁所成之群選出的至少1種之化合物、與下述式(I)所示作為烷氧基矽烷的縮合聚合物之聚矽氧烷所成之反應物。 The aluminum-containing polyoxyalkylene can be obtained, for example, by contacting at least one compound selected from an aluminum salt and an alkane alumina with a polyoxyalkylene oxide. That is, the aluminum-containing polyoxyalkylene is preferably a reaction product of at least one compound selected from an aluminum salt and an alkane alumina and a polyoxyalkylene oxide, more preferably a hydrochloride, a nitrate or a sulfate. At least one aluminum salt selected from the group consisting of acetate, amino sulfonate, sulfonate, acetamidine acetate and the basic salt thereof, and at least one selected from the group consisting of alkane alumina The compound is a reaction product with a polyoxane which is a condensation polymer of alkoxydecane represented by the following formula (I).
R2 kSi(OR1)(4-k) (I) R 2 k Si(OR 1 ) (4-k) (I)
式中，R1各自獨立地表示碳數1~5的烷基；R2各自獨立地表示可具有取代基且可具有雜原子之碳數1~20的烴基、鹵素原子或氫原子；k表示0~3之整數。 In the formula, R 1 each independently represents an alkyl group having 1 to 5 carbon atoms; and R 2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or a hydrogen atom which may have a hetero atom; k represents An integer from 0 to 3.
式(I)所示之烷氧基矽烷的較佳態樣及作為其縮合聚合物的聚矽氧烷之較佳態樣，係與A成分中的聚矽氧烷同樣。 A preferred aspect of the alkoxydecane represented by the formula (I) and a preferred aspect of the polyoxyalkylene as the condensed polymer are the same as those of the polyoxane in the component A.
與聚矽氧烷一起形成含鋁之聚矽氧烷的化合物，較佳 為由鋁鹽及烷氧化鋁所成之群選出的至少1種。鋁鹽係如前述。 A compound which forms an aluminum-containing polyoxane together with polyoxyalkylene, preferably It is at least one selected from the group consisting of an aluminum salt and an alkane alumina. The aluminum salt is as described above.
又，烷氧化鋁只要可與聚矽氧烷反應，則沒有特別的限制，可自通常使用的烷氧化鋁中適宜選擇而使用。烷氧化鋁中的烷氧基較佳為碳數1~4者，更佳為碳數1~3者。作為烷氧化鋁，具體地可舉出三甲氧化鋁、三乙氧化鋁、三丙氧化鋁、三異丙氧化鋁等。其中，較佳為三異丙氧化鋁。 Further, the alkane alumina is not particularly limited as long as it can be reacted with polysiloxane, and can be suitably selected from alkane alumina which is usually used. The alkoxy group in the alkane oxide is preferably a carbon number of 1 to 4, more preferably a carbon number of 1 to 3. Specific examples of the alkane alumina include trimethyl alumina, triethyl alumina, tripropylene alumina, and triisopropyl alumina. Among them, preferred is triisopropyl alumina.
鋁鹽及烷氧化鋁係可為單獨1種，也可組合2種以上使用。 The aluminum salt and the alkagnelate type may be used alone or in combination of two or more.
調製含鋁之聚矽氧烷時的聚矽氧烷與由鋁鹽及烷氧化鋁所成之群選出的化合物(以下亦稱為「特定鋁化合物」)之混合比例，係可按照目的等來適宜選擇。例如，特定鋁化合物相對於聚矽氧烷之莫耳比(特定鋁化合物/聚矽氧烷)較佳為50/50~80/20，更佳為50/50~70/30，尤佳為60/40~70/30。此處，聚矽氧烷之莫耳數，係以作為原料所加入的烷氧基矽烷之總莫耳數算出。又，特定鋁化合物之莫耳數，係將作為原料所加入的特定鋁化合物之總莫耳數換算成相當於氧化鋁(Al2O3)的莫耳數而算出。即，將所加入的特定鋁化合物中所有的鋁原子之總莫耳數的1/2當作特定鋁化合物之莫耳數。 The mixing ratio of the polyoxoxane in the case of preparing the polyaluminoxane containing aluminum to the compound selected from the group consisting of the aluminum salt and the alkane alumina (hereinafter also referred to as "specific aluminum compound") can be used according to the purpose and the like. Suitable choice. For example, the molar ratio of the specific aluminum compound to the polyoxyalkylene (specific aluminum compound/polyoxane) is preferably 50/50 to 80/20, more preferably 50/50 to 70/30, and particularly preferably 60/40~70/30. Here, the molar number of polyoxyalkylene is calculated from the total number of moles of alkoxydecane added as a raw material. Further, the molar number of the specific aluminum compound is calculated by converting the total number of moles of the specific aluminum compound added as a raw material into the number of moles corresponding to alumina (Al 2 O 3 ). That is, 1/2 of the total number of moles of all aluminum atoms in the specific aluminum compound to be added is taken as the molar number of the specific aluminum compound.
作為含鋁之聚矽氧烷的調製方法，具體地可舉出藉由使預先調製的聚矽氧烷與特定鋁化合物接觸而調製之方法，於特定鋁化合物之存在下將構成聚矽氧烷的烷氧基矽 烷予以縮合聚合之方法等，較佳為於特定鋁化合物之存在下將構成聚矽氧烷的烷氧基矽烷予以縮合聚合之方法。 As a method of preparing the aluminum-containing polyoxane, specifically, a method of preparing a polysiloxane by bringing a previously prepared polysiloxane to a specific aluminum compound, and constituting the polyoxyalkylene in the presence of a specific aluminum compound Alkoxy oxime The method of condensation polymerization of an alkane, etc., is preferably a method of condensing and polymerizing an alkoxydecane constituting a polyoxyalkylene in the presence of a specific aluminum compound.
作為於特定鋁化合物之存在下將構成聚矽氧烷的烷氧基矽烷予以縮合聚合之方法，較佳為將烷氧基矽烷與特定鋁化合物之混合物予以加熱處理之方法。作為烷氧基矽烷，可合適地使用前述之聚矽氧烷的調製方法中所用之烷氧基矽烷。烷氧基矽烷與特定鋁化合物之混合物，係可按照需要亦包含有機溶劑。作為有機溶劑，可自前述的聚矽氧烷之調製方法中的聚合溶劑中適宜選擇。又，作為加熱處理之條件，可合適地使用前述的聚矽氧烷之調製方法中的加熱處理之條件。 As a method of condensing and polymerizing the alkoxy decane constituting the polyoxyalkylene in the presence of a specific aluminum compound, a method of heat-treating a mixture of an alkoxy decane and a specific aluminum compound is preferred. As the alkoxydecane, the alkoxydecane used in the above-mentioned preparation method of the polyoxyalkylene can be suitably used. A mixture of an alkoxydecane and a specific aluminum compound may also contain an organic solvent as needed. The organic solvent can be appropriately selected from the polymerization solvents in the above-mentioned preparation method of polyoxyalkylene. Further, as conditions for the heat treatment, the conditions of the heat treatment in the above-described polyoxyalkylene preparation method can be suitably used.
金屬氧化物膜形成用組成物中之在表面上具有聚矽氧烷的二氧化矽粒子及鋁化合物之含有比率係按照目的等來適宜選擇。含有比率，從所形成的金屬氧化物之折射率、硬度及對於玻璃基材的白化抑制之觀點來看，較佳為以換算成氧化鋁(Al2O3)的鋁之含有率，相對於換算成氧化矽(SiO2)的聚矽氧烷及二氧化矽粒子之總量，成為1莫耳%~20莫耳%之方式選擇，更佳以成為1莫耳%~10莫耳%之方式選擇，尤佳以成為3莫耳%~10莫耳%之方式選擇。再者，於此當鋁化合物包含聚矽氧烷時，鋁化合物中所含有的聚矽氧烷之量係不考慮。 The content ratio of the cerium oxide particles and the aluminum compound having a polyoxyalkylene on the surface in the composition for forming a metal oxide film is appropriately selected depending on the purpose and the like. The content ratio is preferably from the viewpoint of the refractive index of the metal oxide to be formed, the hardness, and the whitening inhibition of the glass substrate, in terms of the content of aluminum in terms of aluminum oxide (Al 2 O 3 ). The total amount of the polysiloxane and the cerium oxide particles converted to cerium oxide (SiO 2 ) is selected from the range of 1 mol% to 20 mol%, more preferably 1 mol% to 10 mol%. Mode selection, especially good to choose from 3 mol% ~ 10 mol%. Further, when the aluminum compound contains polyoxyalkylene, the amount of polyoxyalkylene contained in the aluminum compound is not considered.
換算成氧化鋁(Al2O3)的鋁之含有率若為1莫耳%以上，則有可達成更低折射率之傾向，而若為20莫耳%以下，則有金屬氧化物膜形成用組成物的保存安定性升高之 傾向。 In terms of aluminum oxide (Al 2 O 3) When the content of aluminum of less than 1 mole%, there tends to lower the refractive index can be achieved, while if it is 20 mole% or less, the metal oxide film is formed The tendency of the composition to be stored with increased stability.
換算成氧化鋁(Al2O3)的鋁之含有率，係可如前述地由所加入的原料算出，但也可藉由通常使用的測定方法算出鋁原子與矽原子之含有比，自該含有比求得。 The content ratio of aluminum converted to alumina (Al 2 O 3 ) can be calculated from the raw materials to be added as described above, but the ratio of the content of aluminum atoms to germanium atoms can also be calculated by a commonly used measurement method. The content ratio is obtained.
金屬氧化物膜形成用組成物，係除了在表面上具有聚矽氧烷的二氧化矽粒子、鋁化合物，視需要還可更含有其它成分。作為其它成分，可舉出有機溶劑、在表面上具有聚矽氧烷的二氧化矽粒子以外之無機粒子(以下亦僅稱「無機粒子」)等。 The composition for forming a metal oxide film is not only cerium oxide particles having a polyoxyalkylene oxide on the surface, but also an aluminum compound, and may further contain other components as necessary. Examples of the other components include an organic solvent and inorganic particles (hereinafter also referred to as "inorganic particles") other than the cerium oxide particles having a polyoxyalkylene on the surface.
金屬氧化物膜形成用組成物較佳為包含有機溶劑之至少1種。有機溶劑係可使用在表面上具有聚矽氧烷的二氧化矽粒子及含鋁之聚矽氧烷之調製時所用的有機溶劑，而且亦可為另途添加之有機溶劑。 The metal oxide film-forming composition preferably contains at least one of organic solvents. The organic solvent may be an organic solvent used in the preparation of a cerium oxide particle having a polyoxyalkylene oxide on the surface and a polyaluminoxane containing aluminum, or may be an organic solvent added in another manner.
作為有機溶劑之具體例，可舉出甲醇、乙醇、丙醇、異丙醇、丁醇、己醇、1-庚醇、1-辛醇等之醇溶劑；乙酸乙酯、乙酸丁酯等之酯溶劑；乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、己二醇等之二醇溶劑；二乙二醇二乙基醚、丙二醇單丁基醚等之二醇醚衍生物；二乙二醇單乙酸酯等之二醇酯衍生物；二乙基醚、二異丙基醚等之醚溶劑；丙酮、甲基乙基酮、環己酮等之酮溶劑；苯、甲苯等 之芳香族烴溶劑等。 Specific examples of the organic solvent include alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, 1-heptanol, and 1-octanol; ethyl acetate, butyl acetate, and the like. Ester solvent; glycol solvent such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, hexanediol, etc.; diethylene glycol diethyl ether, propylene glycol monobutyl ether, etc. a glycol ether derivative; a glycol ester derivative such as diethylene glycol monoacetate; an ether solvent such as diethyl ether or diisopropyl ether; acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvent; benzene, toluene, etc. An aromatic hydrocarbon solvent or the like.
於此等之中，從得到更低折射率之觀點來看，較佳為包含1-庚醇、1,5-戊二醇、二乙二醇二乙基醚、己二醇、丙二醇單丁基醚、1,4-丁二醇等之沸點170℃以上的有機溶劑。 Among these, from the viewpoint of obtaining a lower refractive index, it is preferred to contain 1-heptanol, 1,5-pentanediol, diethylene glycol diethyl ether, hexanediol, propylene glycol monobutylene. An organic solvent having a boiling point of 170 ° C or higher, such as a group ether or 1,4-butanediol.
此等之有機溶劑係可為單獨1種或組合2種以上使用。 These organic solvents may be used alone or in combination of two or more.
金屬氧化物膜形成用組成物包含有機溶劑時，有機溶劑之含量，較佳為使金屬氧化物膜形成用組成物之總固體成分濃度成為0.5質量%~20質量%之範圍的量，更佳成為0.5質量%~10質量%之範圍的量。金屬氧化物膜形成用組成物之總固體成分濃度若為0.5質量%以上，則容易將所形成的金屬氧化物膜之膜厚控制在所欲之範圍，金屬氧化物膜之製程係可簡略化。又，金屬氧化物膜形成用組成物之總固體成分濃度若為20質量%以下，則金屬氧化物膜形成用組成物之儲存安定性升高，更且所形成之金屬氧化物膜的膜厚控制有變容易之傾向。 When the metal oxide film-forming composition contains an organic solvent, the content of the organic solvent is preferably such that the total solid content concentration of the metal oxide film-forming composition is in the range of 0.5% by mass to 20% by mass. The amount is in the range of 0.5% by mass to 10% by mass. When the total solid content concentration of the metal oxide film-forming composition is 0.5% by mass or more, the film thickness of the formed metal oxide film is easily controlled to a desired range, and the process of the metal oxide film can be simplified. . In addition, when the total solid content concentration of the metal oxide film-forming composition is 20% by mass or less, the storage stability of the metal oxide film-forming composition is increased, and the film thickness of the formed metal oxide film is further increased. Control has a tendency to become easier.
再者，金屬氧化物膜形成用組成物之總固體成分濃度，係可將所加入的原料之聚矽氧烷及二氧化矽粒子換算成氧化矽(SiO2)，將鋁化合物換算成氧化鋁(Al2O3)而算出。又，可自金屬氧化物膜形成用組成物之不揮發性成分的總質量來算出。 Furthermore, the metal oxide film is formed with a total solid concentration of the composition, the silicon-based poly siloxane and the added silicon dioxide particles of the raw material can be converted to silicon oxide (SiO 2), aluminum is converted into aluminum oxide compound Calculated by (Al 2 O 3 ). Further, it can be calculated from the total mass of the nonvolatile components of the composition for forming a metal oxide film.
金屬氧化物膜形成用組成物，亦可更包含在表面上具有聚矽氧烷的二氧化矽粒子以外之無機粒子。作為無機粒子，例如可舉出氧化鎢、氧化鈮、氧化鉭、氧化鈦、氧化鋯、氧化錫、氧化鋁、氧化鉿、氧化鉻、氧化鈰、氧化鉬、氧化鏻等之金屬氧化物粒子。 The metal oxide film-forming composition may further contain inorganic particles other than the cerium oxide particles having a polyoxyalkylene on the surface. Examples of the inorganic particles include metal oxide particles such as tungsten oxide, cerium oxide, cerium oxide, titanium oxide, zirconium oxide, tin oxide, aluminum oxide, cerium oxide, chromium oxide, cerium oxide, molybdenum oxide, and cerium oxide.
無機粒子之平均粒徑較佳為1nm~200nm，更佳為1nm~100nm，尤佳為1nm~50nm。 The average particle diameter of the inorganic particles is preferably from 1 nm to 200 nm, more preferably from 1 nm to 100 nm, still more preferably from 1 nm to 50 nm.
金屬氧化物膜形成用組成物包含無機粒子時，其含有率較佳為總固體成分中90質量%以下，更佳為75質量%以下。含有率之下限值係沒有特別的限制，但較佳為50質量%以上。 When the metal oxide film-forming composition contains inorganic particles, the content thereof is preferably 90% by mass or less, and more preferably 75% by mass or less based on the total solid content. The lower limit of the content rate is not particularly limited, but is preferably 50% by mass or more.
含有含鋁之聚矽氧烷作為鋁化合物的金屬氧化物膜形成用組成物之製造方法，較佳為包含使聚矽氧烷與二氧化矽粒子接觸而得到在表面上具有聚矽氧烷的二氧化矽粒子；使自鋁鹽及烷氧化鋁選出的至少1種之化合物與聚矽氧烷接觸而得到含鋁之聚矽氧烷；與，混合在表面上具有聚矽氧烷的二氧化矽粒子與含鋁之聚矽氧烷。於分別調製在表面上具有聚矽氧烷的二氧化矽粒子及含鋁之聚矽氧烷後，藉由混合此等，可高效率地製造具有所欲構成之金屬氧化物膜形成用組成物。 A method for producing a composition for forming a metal oxide film containing an aluminum-containing polyoxyalkylene as an aluminum compound, preferably comprising contacting a polysiloxane with a cerium oxide particle to obtain a polyoxyalkylene on the surface. Cerium oxide particles; contacting at least one compound selected from an aluminum salt and an alkane alumina with a polyoxyalkylene to obtain an aluminum-containing polyoxyalkylene; and mixing with a polyoxane having a surface on the surface Bismuth particles and polyaluminoxanes containing aluminum. After arranging the cerium oxide particles having a polyoxy siloxane on the surface and the polysiloxane containing aluminum, the metal oxide film-forming composition having a desired structure can be efficiently produced by mixing the particles. .
使聚矽氧烷與二氧化矽粒子接觸而得到在表面上具有聚矽氧烷的二氧化矽粒子者之詳細及使由鋁鹽及烷氧化鋁 選出的至少1種化合物與聚矽氧烷接觸而得到含鋁之聚矽氧烷的詳細，係如前述。 The contact between the polyoxane and the cerium oxide particles to obtain a cerium oxide particle having a polyoxyalkylene on the surface, and the aluminum salt and the aluminosilicate The details of the at least one compound selected in contact with the polyoxyalkylene to obtain an aluminum-containing polyoxyalkylene are as described above.
混合在表面上具有聚矽氧烷的二氧化矽粒子與含鋁之聚矽氧烷的方法係沒有特別的限制，可自通常使用的混合方法中適宜選擇。又，混合時亦可使用有機溶劑。有機溶劑係可自前述的有機溶劑中適宜選擇而使用。又，混合溫度係沒有特別的限制，例如可為20~100℃。 The method of mixing the cerium oxide particles having a polyoxyalkylene on the surface with the aluminum-containing polyoxyalkylene is not particularly limited and may be appropriately selected from the usual mixing methods. Further, an organic solvent can also be used for mixing. The organic solvent can be appropriately selected from the above organic solvents and used. Further, the mixing temperature is not particularly limited and may be, for example, 20 to 100 °C.
本發明之金屬氧化物膜形成用組成物，由於可形成折射率低、硬度優異之金屬氧化物膜，而可較宜地適用在影像顯示裝置等中所使用的防反射膜、保護膜等之形成。特別地，藉由在玻璃基材(較佳為鈉鈣玻璃)上，使用本發明之金屬氧化物膜形成用組成物來形成金屬氧化物膜，可形成低折射率且高硬度，而且能有效果地抑制在高溫高濕環境下的白化之防反射膜。 The metal oxide film forming composition of the present invention can be suitably used for an antireflection film or a protective film used in an image display device or the like because it can form a metal oxide film having a low refractive index and excellent hardness. form. In particular, by forming a metal oxide film on the glass substrate (preferably soda-lime glass) using the composition for forming a metal oxide film of the present invention, a low refractive index and a high hardness can be formed, and The anti-reflection film which is whitened in a high-temperature and high-humidity environment is effectively suppressed.
本發明之金屬氧化物膜係本發明之金屬氧化物膜形成用組成物的硬化物。金屬氧化物膜例如係可藉由對金屬氧化物膜形成用組成物賦予熱，使硬化而形成。因此，本發明之態樣包含金屬氧化物膜之製造中的金屬氧化物膜形成用組成物之使用。 The metal oxide film of the present invention is a cured product of the composition for forming a metal oxide film of the present invention. The metal oxide film can be formed, for example, by applying heat to a composition for forming a metal oxide film and hardening it. Therefore, the aspect of the invention includes the use of a composition for forming a metal oxide film in the production of a metal oxide film.
賦予熱之方法、條件等之詳細係如後述。 The details of the method, conditions, and the like for imparting heat will be described later.
本發明的附金屬氧化物膜之基材，係包含基材、與配置於基材上之金屬氧化物膜形成用組成物的硬化物。本發明之金屬氧化物形成用組成物的硬化物之金屬氧化物膜，由於低折射率且高硬度，可適合作為基材之防反射膜。 The substrate with a metal oxide film of the present invention is a cured product comprising a substrate and a composition for forming a metal oxide film disposed on the substrate. The metal oxide film of the cured product of the metal oxide-forming composition of the present invention can be suitably used as an antireflection film for a substrate because of its low refractive index and high hardness.
作為基材，例如可舉出塑膠、玻璃等，較佳為液晶顯示裝置(LCD)、布朗恩管顯示裝置(CRT)等之顯示裝置的表面基材、透鏡等。 Examples of the substrate include plastic, glass, and the like, and a surface substrate, a lens, and the like of a display device such as a liquid crystal display device (LCD) or a Brownian tube display device (CRT) are preferable.
配置於基材上之金屬氧化物膜形成用組成物的硬化物之膜厚係沒有特別的限制，可按照目的等來適宜選擇。硬化物(金屬氧化物膜)之膜厚例如可成為50nm~200nm，較佳成為100nm~110nm。 The film thickness of the cured product of the metal oxide film-forming composition disposed on the substrate is not particularly limited, and can be appropriately selected according to the purpose and the like. The film thickness of the cured product (metal oxide film) can be, for example, 50 nm to 200 nm, preferably 100 nm to 110 nm.
配置於基材上之金屬氧化物膜形成用組成物的硬化物之折射率，較佳為1.45以下，更佳為1.23~1.36。配置於基材上之金屬氧化物膜形成用組成物的硬化物之硬度，以依據JIS K5400所測定的鉛筆硬度，較佳為B以上，更佳為HB以上，尤佳為H以上。 The refractive index of the cured product of the metal oxide film-forming composition disposed on the substrate is preferably 1.45 or less, more preferably 1.23 to 1.36. The hardness of the cured product of the metal oxide film-forming composition disposed on the substrate is preferably B or more, more preferably HB or more, and even more preferably H or more, based on the pencil hardness measured in accordance with JIS K5400.
附金屬氧化物膜之基材的製造方法，包含於基材上賦予金屬氧化物膜形成用組成物，以及對於已賦予基材上的金屬氧化物膜形成用組成物，賦予熱。藉由使用本發明之金屬氧化物膜形成用組成物，可以簡便的手法形成低折射率且高硬度之金屬氧化物膜。 The method for producing a substrate with a metal oxide film includes imparting a composition for forming a metal oxide film on a substrate, and imparting heat to a composition for forming a metal oxide film on the substrate. By using the metal oxide film-forming composition of the present invention, a metal oxide film having a low refractive index and a high hardness can be formed by a simple method.
因此，本發明之態樣包含附金屬氧化物膜之基材之製 造中的金屬氧化物膜形成用組成物之使用。 Therefore, the aspect of the present invention comprises a substrate made of a metal oxide film. The use of a composition for forming a metal oxide film to be formed.
金屬氧化物膜形成用組成物對基材上的賦予方法係沒有特別的限制，可按照基材、膜厚等，自通常使用的塗佈方法中適宜選擇。作為賦予方法，例如可舉出浸塗法、旋塗法、噴塗法、刷毛塗佈法、輥轉印法、網版印刷法、噴墨法、撓性印刷法等。 The method for imparting a metal oxide film-forming composition to the substrate is not particularly limited, and may be appropriately selected from usual coating methods depending on the substrate, film thickness, and the like. Examples of the method of application include a dip coating method, a spin coating method, a spray coating method, a brush coating method, a roll transfer method, a screen printing method, an inkjet method, and a flexographic printing method.
藉由對於已賦予基材上的金屬氧化物膜形成用組成物賦予熱，可形成金屬氧化物膜。對於金屬氧化物膜形成用組成物賦予熱之方法係沒有特別的限制，可按照基材之種類、目的等，自通常使用的加熱手段中適宜選擇。作為加熱手段，具體地可舉出烘烤爐、熱板等之加熱裝置。 A metal oxide film can be formed by imparting heat to the composition for forming a metal oxide film on the substrate. The method of applying heat to the metal oxide film-forming composition is not particularly limited, and may be appropriately selected from usual heating means depending on the type and purpose of the substrate. Specific examples of the heating means include a heating device such as a baking oven or a hot plate.
形成硬化物之加熱溫度，例如可為100℃以上，較佳為100~600℃。又，加熱溫度亦可為100~500℃。另外，加熱時間例如可為0.5小時~2小時。 The heating temperature at which the cured product is formed may be, for example, 100 ° C or higher, preferably 100 to 600 ° C. Further, the heating temperature may be 100 to 500 °C. Further, the heating time may be, for example, 0.5 hours to 2 hours.
附金屬氧化物膜之基材的製造方法，亦可在硬化物之形成前，包含自已賦予基材上的金屬氧化物膜形成用組成物中，去除溶劑的至少一部之乾燥步驟。乾燥步驟例如可藉由對於金屬氧化物膜形成用組成物賦予熱而進行。乾燥步驟的加熱溫度例如可為80~150℃。又，加熱時間可為30秒~10分鐘。 The method for producing a substrate with a metal oxide film may include a drying step of removing at least one portion of the solvent from the composition for forming a metal oxide film on the substrate before the formation of the cured product. The drying step can be performed, for example, by applying heat to the composition for forming a metal oxide film. The heating temperature in the drying step may be, for example, 80 to 150 °C. Moreover, the heating time can be from 30 seconds to 10 minutes.
以下，藉由實施例來更具體說明本發明，惟本發明不受此等之實施例所限定。尚且，只要沒有特別預先指明， 則「%」係以質量基準。 In the following, the invention will be more specifically described by the examples, but the invention is not limited by the examples. Still, as long as there is no special pre-specified, Then "%" is based on quality.
以下之實施例等中所用的縮寫符號等係如以下。 The abbreviations and the like used in the following examples and the like are as follows.
TEOS：四乙氧基矽烷 TEOS: tetraethoxy decane
AN：硝酸鋁．九水合物 AN: Aluminum nitrate. Nine hydrate
MeOH：甲醇(沸點64.7℃) MeOH: methanol (boiling point 64.7 ° C)
EtOH：乙醇(沸點78.4℃) EtOH: ethanol (boiling point 78.4 ° C)
PGME：丙二醇單甲基醚(沸點120℃) PGME: propylene glycol monomethyl ether (boiling point 120 ° C)
HG：己二醇(沸點198℃) HG: hexanediol (bp 198 ° C)
BCS：乙二醇單丁基醚(沸點171℃) BCS: ethylene glycol monobutyl ether (boiling point 171 ° C)
1-Hp：1-庚醇(沸點176℃) 1-Hp: 1-heptanol (boiling point 176 ° C)
1-Pen：1,5-戊二醇(沸點242℃) 1-Pen: 1,5-pentanediol (boiling point 242 ° C)
GEDME：二乙二醇二甲基醚(沸點162℃) GEDME: Diethylene glycol dimethyl ether (boiling point 162 ° C)
MeOH-ST：含有平均粒徑12nm、作為SiO2的30%之二氧化矽粒子，以甲醇作為分散介質之矽溶膠。 MeOH-ST: a cerium oxide sol having an average particle diameter of 12 nm, 30% of SiO 2 as a dispersion medium, and methanol as a dispersion medium.
MA-ST-UP：具有平均粒徑12nm、連成鏈狀之形狀。含有作為SiO2的20質量%之二氧化矽粒子，以甲醇作為分散介質之矽溶膠。 MA-ST-UP: A shape having an average particle diameter of 12 nm and connected in a chain shape. A cerium sol containing 20% by mass of cerium oxide particles as SiO 2 and methanol as a dispersion medium.
MA-ST-S：含有平均粒徑9nm、作為SiO2的20質量%之二氧化矽粒子，以甲醇作為分散介質之矽溶膠。 MA-ST-S: a cerium oxide sol having an average particle diameter of 9 nm, 20 mass% of SiO 2 , and methanol as a dispersion medium.
MA-ST-M：含有平均粒徑20nm、作為SiO2的40質量%之二氧化矽粒子，以甲醇作為分散介質之矽溶膠。 MA-ST-M: a cerium oxide sol having an average particle diameter of 20 nm, 40% by mass of SiO 2 , and methanol as a dispersion medium.
MA-ST-L：含有平均粒徑45nm、作為SiO2的40質量%之二氧化矽粒子，以甲醇作為分散介質之矽溶膠。 MA-ST-L: a cerium oxide sol having an average particle diameter of 45 nm, 40% by mass of SiO 2 , and methanol as a dispersion medium.
使用氣相層析術(以下稱為GC)，如以下地測定實施例等中所形成的反應溶液中殘留的殘留烷氧基矽烷之含量。 The content of the residual alkoxysilane remaining in the reaction solution formed in the examples and the like was measured by gas chromatography (hereinafter referred to as GC) as follows.
GC測定係使用島津製作所公司製Shimadzu GC-14B，於下述之條件下測定。 The GC measurement was carried out under the following conditions using Shimadzu GC-14B manufactured by Shimadzu Corporation.
管柱：毛細管柱CBP1-W25-100(長度25mm、直徑0.53mm、壁厚1μm) Pipe column: capillary column CBP1-W25-100 (length 25mm, diameter 0.53mm, wall thickness 1μm)
管柱溫度：自開始溫度50℃起以15℃/分鐘升溫至到達溫度290℃(保持時間3分鐘)。 Column temperature: The temperature was raised from 15 ° C / min from the starting temperature of 50 ° C to the temperature of 290 ° C (holding time 3 minutes).
樣品注入量：1μL，注射溫度：240℃，檢測器溫度：290℃，載體氣體：氮(流量30mL/分鐘)，檢測方法：FID法。 Sample injection amount: 1 μL, injection temperature: 240 ° C, detector temperature: 290 ° C, carrier gas: nitrogen (flow rate 30 mL / min), detection method: FID method.
於具備回流管的4口反應燒瓶中，投入作為溶劑的EtOH(36.36g)、作為烷氧基矽烷的TEOS(34.72g)，進行攪拌。其次，滴下作為溶劑的EtOH(18.18g)、水(9.00g)、經稀釋至十分之一的60%硝酸(1.75g)之混合物，攪拌30分鐘。攪拌後，回流3小時，放置冷卻至室溫為止。對於所得之溶液60g，添加EtOH40g進行稀釋，而調製聚矽氧烷(S1)溶液。藉由上述測定方法，以GC測定此溶液，未檢測出烷氧基矽烷。 To a four-neck reaction flask equipped with a reflux tube, EtOH (36.36 g) as a solvent and TEOS (34.72 g) as alkoxy decane were charged and stirred. Next, a mixture of EtOH (18.18 g), water (9.00 g), diluted to one tenth of 60% nitric acid (1.75 g) as a solvent was added, and the mixture was stirred for 30 minutes. After stirring, it was refluxed for 3 hours and left to cool to room temperature. To 60 g of the obtained solution, 40 g of EtOH was added and diluted to prepare a polyoxane (S1) solution. This solution was measured by GC by the above measurement method, and no alkoxydecane was detected.
於具備回流管的4口反應燒瓶中，投入作為有機溶劑(D1)的EtOH(48.45g)、水(4.05g)、作為二氧化矽粒子的矽溶膠MeOH-ST(14.00g)，攪拌後，回流2小時，滴下聚矽氧烷S1之溶液(30.00g)，回流1小時，而調製特定二氧化矽粒子T1。將作為特定二氧化矽粒子T1之各成分的聚矽氧烷、矽溶膠、有機溶劑(D1)與添加量彙總顯示於表1中。 In a four-neck reaction flask equipped with a reflux tube, EtOH (48.45 g), water (4.05 g) as an organic solvent (D1), and ruthenium MeOH-ST (14.00 g) as cerium oxide particles were placed and stirred. After refluxing for 2 hours, a solution of polyoxane S1 (30.00 g) was dropped and refluxed for 1 hour to prepare a specific cerium oxide particle T1. The polysiloxane, the cerium sol, the organic solvent (D1) and the added amount of each component of the specific cerium oxide particle T1 are collectively shown in Table 1.
除了於調製例2-1中，如表1所示地變更聚矽氧烷、矽溶膠、有機溶劑(D1)之種類及添加量以外，與調製例1同樣地，分別調製特定二氧化矽粒子T2~T13。 In the same manner as in Preparation Example 1, the specific cerium oxide particles were prepared in the same manner as in Preparation Example 1, except that the types and the amounts of the polysiloxane, the cerium sol, and the organic solvent (D1) were changed as shown in Table 1 in the preparation example 2-1. T2~T13.
於具備回流管的4口反應燒瓶中，投入作為溶劑的有機溶劑(D2)之MeOH(19.68g)、作為烷氧基矽烷的TEOS(18.75g)，進行攪拌。其次，滴下作為有機溶劑(D3)的MeOH(19.68g)、作為鋁化合物(C)的AN(33.78g)、水(1.62g)之混合物，攪拌30分鐘。攪拌後，回流1小時，放置冷卻至室溫為止。對於所得之溶液60g，添加EtOH40g進行稀釋，而調製含鋁之聚矽氧烷U1，其係作為由烷氧基矽烷之水解物及鋁鹽所成之組成物溶液。藉由上述測定方法，以GC測定此溶液，未檢測出烷氧基矽烷。 In a four-neck reaction flask equipped with a reflux tube, MeOH (19.68 g) as an organic solvent (D2) as a solvent and TEOS (18.75 g) as an alkoxy decane were added and stirred. Next, a mixture of MeOH (19.68 g) as an organic solvent (D3), AN (33.78 g) as an aluminum compound (C), and water (1.62 g) was added dropwise and stirred for 30 minutes. After stirring, it was refluxed for 1 hour and left to cool to room temperature. To 60 g of the obtained solution, 40 g of EtOH was added and diluted to prepare a polyaluminoxane U1 containing aluminum as a composition solution of a hydrolyzate of alkoxysilane and an aluminum salt. This solution was measured by GC by the above measurement method, and no alkoxydecane was detected.
除了於調製例3-1中，如表2所示地變更烷氧基矽烷、鋁化合物(C)及有機溶劑(D2、D3)之種類及添加量以外，與調製例1同樣地，分別調製含鋁之聚矽氧烷U2及U3。 In the same manner as in Preparation Example 1, except that the type and amount of the alkoxydecane, the aluminum compound (C), and the organic solvent (D2, D3) were changed as shown in Table 2, except that the preparation example 3-1 was used. Aluminum-containing polyoxanes U2 and U3.
將上述所得之特定二氧化矽粒子T1(47g)、含鋁之聚矽氧烷U1(3g)與作為有機溶劑(D4)的HG(10g) /BCS(10g)/PGME(30g)之混合溶劑，在室溫(25℃)下混合10分鐘，而成為金屬氧化物形成用組成物，調製塗覆用組成物。 The specific cerium oxide particles T1 (47 g) obtained above, aluminum-containing polyoxyalkylene oxide U1 (3 g) and HG (10 g) as an organic solvent (D4) A mixed solvent of /BCS (10 g) / PGME (30 g) was mixed at room temperature (25 ° C) for 10 minutes to form a composition for forming a metal oxide, and a coating composition was prepared.
除了於實施例1，如表3所示地變更特定二氧化矽粒子、含鋁之聚矽氧烷及有機溶劑(D4)之種類及添加量以外，與實施例1同樣地分別調製塗覆用組成物。 In the same manner as in Example 1, except that the type and the amount of the specific cerium oxide particles, the aluminum-containing polysiloxane, and the organic solvent (D4) were changed as shown in Table 1, the coating was prepared in the same manner as in Example 1. Composition.
除了於實施例1中，不使用含鋁之聚矽氧烷，如表3所示地變更特定二氧化矽粒子及有機溶劑(D4)之種類及添加量以外，與實施例1同樣地分別調製塗覆用組成物。 In the same manner as in Example 1, except that the aluminum-containing polyoxyalkylene was not used, and the types and addition amounts of the specific cerium oxide particles and the organic solvent (D4) were changed as shown in Table 3, respectively. Coating composition.
再者，表3中的「-」表示未使用該成分。 Furthermore, "-" in Table 3 indicates that the component is not used.
不使用如上述實施例1~13及比較例1~15之特定二氧化矽粒子，而代替地藉由將表4中所示的聚矽氧烷、矽溶膠、含鋁之聚矽氧烷及有機溶劑(D4)在常溫(25℃)下混合10分鐘，分別調製塗覆用組成物。 The specific cerium oxide particles as in the above Examples 1 to 13 and Comparative Examples 1 to 15 were not used, and instead, the polysiloxane, the cerium sol, the aluminum-containing polyoxy siloxane, and the aluminum-containing polyoxane shown in Table 4 were used. The organic solvent (D4) was mixed at normal temperature (25 ° C) for 10 minutes to prepare a coating composition.
使用旋塗機，將上述所得的塗覆用組成物分別塗佈在作為基材的鈉鈣玻璃(玻璃厚0.7mm)上及矽基板(厚度 0.5mm)上，而形成塗膜。然後於熱板上，在80℃乾燥處理3分鐘後，於潔淨烘箱中，在300℃熱處理30分鐘而使硬化，得到厚度100nm之金屬氧化物膜。 The coating composition obtained above was applied to a soda lime glass (glass thickness: 0.7 mm) as a substrate and a tantalum substrate (thickness) using a spin coater. 0.5 mm) to form a coating film. Then, it was dried on a hot plate at 80 ° C for 3 minutes, and then heat-treated at 300 ° C for 30 minutes in a clean oven to obtain a metal oxide film having a thickness of 100 nm.
使用股份有限公司安田精機製作所製之No.553-M、三菱鉛筆股份有限公司之Hiuni，依據JIS K5400，測定鉛筆硬度。表5中顯示其結果。 No. 553-M manufactured by Yasuda Seiki Co., Ltd., Hiuni of Mitsubishi Pencil Co., Ltd., and pencil hardness were measured in accordance with JIS K5400. The results are shown in Table 5.
對於已形成在矽基板上的金屬氧化物膜，使用股份有限公司溝尻光學工業所製之自動橢圓偏光計DVA-FLVW，測定折射率。表5中顯示其結果。 For the metal oxide film formed on the ruthenium substrate, the refractive index was measured using an automatic ellipsometer DVA-FLVW manufactured by Gynecology Optical Co., Ltd. The results are shown in Table 5.
由表5可知，使用本發明之金屬氧化物膜形成用組成物所形成的金屬氧化物膜，係折射率低且硬度高，可使低折射率與高硬度並存。 As is clear from Table 5, the metal oxide film formed using the metal oxide film-forming composition of the present invention has a low refractive index and a high hardness, and can coexist with a low refractive index and a high hardness.
使用鈉鈣玻璃基板，其形成有採用上述實施例1~實施例5及比較例1~比較例5之塗覆組成物所形成之金屬氧化物膜，如以下地進行高溫高濕下的白化評價。 A soda-lime glass substrate was used, and a metal oxide film formed by using the coating compositions of the above-described Examples 1 to 5 and Comparative Examples 1 to 5 was formed, and whitening evaluation under high temperature and high humidity was performed as follows. .
藉由ESPEC股份有限公司製小型環境試驗器SH-221，在溫度85℃、濕度85%之條件下實施1000小時的高溫高濕試驗。然後，對於該高溫高濕試驗之前及後的鈉鈣玻璃基板，分別進行霧(HAZE)值之測定。霧值之測定係使用有限公司東京電色製的分光霧度計TC-1800H進行。表6中顯示其結果。 The high-temperature and high-humidity test was carried out for 1,000 hours under the conditions of a temperature of 85 ° C and a humidity of 85% by a small environmental tester SH-221 manufactured by ESPEC Co., Ltd. Then, the haze value of each of the soda lime glass substrates before and after the high-temperature and high-humidity test was measured. The measurement of the haze value was carried out using a spectrophotometer TC-1800H manufactured by Tokyo Electrochrome Co., Ltd. The results are shown in Table 6.
由表6可知，使用本發明之金屬氧化物膜形成用組成物，在玻璃基板上形成金屬氧化物膜，可抑制玻璃基板的白化。 As is apparent from Table 6, the metal oxide film formed on the glass substrate is formed by using the metal oxide film-forming composition of the present invention, and whitening of the glass substrate can be suppressed.
日本發明專利申請案2013-128468號之揭示係藉由參照其全體而併入本說明書中。 The disclosure of Japanese Patent Application No. 2013-128468 is incorporated herein by reference in its entirety.
本說明書中記載的全部文獻、發明專利申請案及技術規格，藉由參照各個文獻、發明專利申請案及技術規格而併入者，係具體地且以與各個記載之情況相同程度，藉由參照而併入本說明書中。 All the documents, invention patent applications and technical specifications described in the specification are incorporated by reference to the respective documents, invention patent applications and technical specifications, and are specifically and in the same extent as the respective descriptions. And incorporated into this specification.
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