TWI500703B - Photo-curing coating composition, photo-curing coating film and touch panel - Google Patents
Photo-curing coating composition, photo-curing coating film and touch panel Download PDFInfo
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Description
本發明是有關於一種光硬化性塗佈組成物,且特別是有關於一種含有金屬烷氧化物經加水分解縮合反應而得光硬化性聚合物的光硬化性塗佈組成物、由所述光硬化性塗佈組成物製得的光硬化塗佈膜及包括所述光硬化塗佈膜的觸控面板。The present invention relates to a photocurable coating composition, and more particularly to a photocurable coating composition containing a photo-curable polymer obtained by subjecting a metal alkoxide to a water-condensing condensation reaction, and the light-curable coating composition A photo-curing coating film obtained by the curable coating composition and a touch panel including the photo-curing coating film.
在觸控液晶顯示裝置中,通常會在觸控面板之感測元件上設置保護層(overcoat layer)藉以保護其下的構件,進而增進觸控液晶顯示裝置的信賴性。一般而言,由於不同物質層間的折射率顯著的差異,此將導致使用者容易看見感測元件的圖案,進而降低觸控液晶顯示裝置的視別性及顯示品質。目前,相關研究是透過在保護層下方設置Nb2 O5 層來降低折射率之間的差異並提高視別性。然而,此方法雖可提高視別性,卻使得製程步驟及成本增加。因此,如何提供同時兼具有一般保 護層與Nb2 O5 層的作用,以達成高折射率、高穿透率、保護性佳與視別性佳等的效果的塗佈膜,已成為業界急切進行研究的課題。In the touch liquid crystal display device, an overcoat layer is usually disposed on the sensing element of the touch panel to protect the underlying member, thereby improving the reliability of the touch liquid crystal display device. In general, due to the significant difference in refractive index between different material layers, this will result in the user easily seeing the pattern of the sensing element, thereby reducing the visibility and display quality of the touch liquid crystal display device. At present, the related research is to reduce the difference between the refractive indexes and improve the visibility by providing a Nb 2 O 5 layer under the protective layer. However, this method can improve the visibility and increase the process steps and costs. Therefore, it has become an industry to provide a coating film which has both a general protective layer and a Nb 2 O 5 layer to achieve an effect of high refractive index, high transmittance, good protection, and good visibility. The subject of eager research.
本發明提供一種光硬化性塗佈組成物,其具有良好光硬化性,由所述光硬化性塗佈組成物所形成的光硬化塗佈膜,其具有良好折射率及穿透率,且適合應用於觸控面板中。The present invention provides a photocurable coating composition which has good photocurability, a photocurable coating film formed of the photocurable coating composition, which has a good refractive index and a transmittance, and is suitable for Applied to the touch panel.
本發明的光硬化性塗佈組成物包括光硬化性聚合物。光硬化性聚合物由至少式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物經加水分解縮合反應而得:Ra 1 Si(ORb )3 式(I);Rc 1 Si(ORd )3 式(II);Ti(ORe )4 式(III);其中Ra 表示碳數6~15的芳香基,Rb 表示碳數1~5的烷基,Rc 表示碳數2~10的烯基,Rd 表示碳數1~5的烷基,Re 表示碳數1~5的烷基,且以式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100重量份計,式(I)所示的金屬烷氧化物的含量為25重量份至50重量 份,式(II)所示的金屬烷氧化物的含量為5重量份至20重量份,式(III)所示的金屬烷氧化物的含量為45重量份至70重量份。The photocurable coating composition of the present invention includes a photocurable polymer. The photocurable polymer is obtained by subjecting at least a metal alkoxide represented by the formula (I), a metal alkoxide represented by the formula (II) and a metal alkoxide represented by the formula (III) to hydrolysis and condensation reaction: R a 1 Si(OR b ) 3 Formula (I); R c 1 Si(OR d ) 3 Formula (II); Ti(OR e ) 4 Formula (III); wherein R a represents aroma of 6-15 a group, R b represents an alkyl group having 1 to 5 carbon atoms, R c represents an alkenyl group having 2 to 10 carbon atoms, R d represents an alkyl group having 1 to 5 carbon atoms, and R e represents an alkyl group having 1 to 5 carbon atoms. And the total amount of the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II) and the metal alkoxide represented by the formula (III) is 100 parts by weight, and the formula (I) The metal alkoxide is shown in an amount of 25 parts by weight to 50 parts by weight, and the metal alkoxide represented by the formula (II) is contained in an amount of 5 parts by weight to 20 parts by weight, and the metal alkoxide is represented by the formula (III). The content of the substance is from 45 parts by weight to 70 parts by weight.
在本發明的一實施例中,以上述式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100重量份計,式(I)所示的金屬烷氧化物的含量為25重量份至45重量份。In one embodiment of the present invention, the total amount of the metal alkoxide represented by the above formula (I), the metal alkoxide represented by the formula (II), and the metal alkoxide represented by the formula (III) is The content of the metal alkoxide represented by the formula (I) is from 25 parts by weight to 45 parts by weight per 100 parts by weight.
在本發明的一實施例中,以上述式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100重量份計,式(I)所示的金屬烷氧化物的含量為30重量份至40重量份。In one embodiment of the present invention, the total amount of the metal alkoxide represented by the above formula (I), the metal alkoxide represented by the formula (II), and the metal alkoxide represented by the formula (III) is The content of the metal alkoxide represented by the formula (I) is from 30 parts by weight to 40 parts by weight per 100 parts by weight.
在本發明的一實施例中,上述的光硬化性塗佈組成物更包括溶劑。In an embodiment of the invention, the photocurable coating composition further includes a solvent.
本發明的光硬化性塗佈組成物包括光硬化性聚合物。光硬化性聚合物基本上由式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物組成經加水分解縮合反應而得:Rc 1 Si(ORd )3 式(II);Ti(ORe )4 式(III);其中Rc 表示碳數2~10的烯基,Rd 表示碳數1~5的烷基,Re 表示碳數1~5的烷基,且以式(II)所示的金屬烷氧化物及式(III) 所示的金屬烷氧化物的總量為100重量份計,式(III)所示的金屬烷氧化物的含量為55重量份至70重量份。The photocurable coating composition of the present invention includes a photocurable polymer. The photocurable polymer is obtained by substantially hydrolyzing a condensation reaction of a metal alkoxide represented by the formula (II) and a metal alkoxide represented by the formula (III): R c 1 Si(OR d ) 3 (II); Ti(OR e ) 4 Formula (III); wherein R c represents an alkenyl group having 2 to 10 carbon atoms, R d represents an alkyl group having 1 to 5 carbon atoms, and R e represents an alkane having 1 to 5 carbon atoms; And the content of the metal alkoxide represented by the formula (III) is 100 parts by weight based on 100 parts by weight of the total amount of the metal alkoxide represented by the formula (II) and the metal alkoxide represented by the formula (III). 55 parts by weight to 70 parts by weight.
在本發明的一實施例中,上述的光硬化性塗佈組成物更包括溶劑。In an embodiment of the invention, the photocurable coating composition further includes a solvent.
本發明的光硬化塗佈膜是由如上所述的光硬化性塗佈組成物所製得。The photo-curing coating film of the present invention is produced from the photocurable coating composition as described above.
在本發明的一實施例中,上述光硬化塗佈膜的膜厚度為80nm至120nm,且折射率為1.60至1.70。In an embodiment of the invention, the photo-curing coating film has a film thickness of 80 nm to 120 nm and a refractive index of 1.60 to 1.70.
在本發明的一實施例中,在波長380nm至450nm的範圍內,上述光硬化塗佈膜的穿透率大於95%。In an embodiment of the invention, the light-curing coating film has a transmittance of more than 95% in a wavelength range of 380 nm to 450 nm.
本發明的觸控面板包括如上所述的光硬化塗佈膜。The touch panel of the present invention includes the photo-curing coating film as described above.
基於上述,本發明所提出的光硬化性塗佈組成物,其包括由至少式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物反應而得的光硬化性聚合物。藉由式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的含量在上述範圍內,本發明的光硬化性塗佈組成物具有良好光硬化性,且可製得具有良好折射率及穿透率的光硬化塗佈膜。本發明所提出的另一光硬化性塗佈組成物,其包括基本上由式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物組成反應而得的光硬化性聚合 物。藉由式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的含量在上述範圍內,本發明的光硬化性塗佈組成物具有良好光硬化性,且可製得具有良好折射率的光硬化塗佈膜。如此一來,使用本發明的光硬化塗佈膜的觸控面板可具備良好的視別性及顯示品質。Based on the above, the photocurable coating composition of the present invention comprises at least a metal alkoxide represented by the formula (I), a metal alkoxide represented by the formula (II), and a formula (III). A photocurable polymer obtained by reacting a metal alkoxide. The photocurability of the present invention is attained by the content of the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II), and the metal alkoxide represented by the formula (III) within the above range. The coating composition has good photocurability, and a light-curing coating film having a good refractive index and transmittance can be obtained. Another photocurable coating composition according to the present invention, which comprises a photohardening reaction consisting essentially of a metal alkoxide represented by the formula (II) and a metal alkoxide represented by the formula (III) Sexual aggregation Things. When the content of the metal alkoxide represented by the formula (II) and the metal alkoxide represented by the formula (III) is within the above range, the photocurable coating composition of the present invention has good photocurability and can be A photo-curing coating film having a good refractive index was obtained. As a result, the touch panel using the photo-curing coating film of the present invention can have good visibility and display quality.
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。The above described features and advantages of the invention will be apparent from the following description.
100‧‧‧觸控面板100‧‧‧ touch panel
102‧‧‧基板102‧‧‧Substrate
104‧‧‧觸控元件104‧‧‧Touch components
106‧‧‧保護層106‧‧‧Protective layer
110、120‧‧‧觸控串列110, 120‧‧‧ Touch series
112、122‧‧‧觸控電極112, 122‧‧‧ touch electrodes
114、124‧‧‧連接部114, 124‧‧‧ Connections
130‧‧‧絕緣圖案130‧‧‧Insulation pattern
D1、D2‧‧‧方向D1, D2‧‧‧ direction
圖1是本發明一實施方式的觸控面板的上視示意圖。1 is a top plan view of a touch panel according to an embodiment of the present invention.
圖2是圖1的觸控面板沿剖線I-I’的剖面示意圖。2 is a cross-sectional view of the touch panel of FIG. 1 taken along line I-I'.
在本文中,由「一數值至另一數值」表示的範圍,是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此,某一特定數值範圍的記載,涵蓋該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍,如同在說明書中明文寫出該任意數值和該較小數值範圍一樣。In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, the recitation of a particular range of values is intended to include any value in the range of values and the range of values defined by any value in the range of values, as in the specification. The scope is the same.
為了製備出具有良好折射率及穿透率的光硬化塗佈 膜,且適合應用於觸控面板中,本發明提出一種具有良好光硬化性的光硬化性塗佈組成物,其可達到上述優點。以下,特舉實施方式作為本發明確實能夠據以實施的範例。In order to prepare a photoharden coating with good refractive index and transmittance The film is suitable for use in a touch panel, and the present invention proposes a photocurable coating composition having good photocurability which can attain the above advantages. Hereinafter, the specific embodiments are described as examples in which the present invention can be implemented.
本發明之一實施方式提供的光硬化性塗佈組成物包括光硬化性聚合物。光硬化性聚合物由至少式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物經加水分解縮合反應而得:Ra 1 Si(ORb )3 式(I);Rc 1 Si(ORd )3 式(II);Ti(ORe )4 式(III);其中Ra 表示碳數6~15的芳香基,Rb 表示碳數1~5的烷基,Rc 表示碳數2~10的烯基,Rd 表示碳數1~5的烷基,Re 表示碳數1~5的烷基。A photocurable coating composition according to an embodiment of the present invention includes a photocurable polymer. The photocurable polymer is obtained by subjecting at least a metal alkoxide represented by the formula (I), a metal alkoxide represented by the formula (II) and a metal alkoxide represented by the formula (III) to hydrolysis and condensation reaction: R a 1 Si(OR b ) 3 Formula (I); R c 1 Si(OR d ) 3 Formula (II); Ti(OR e ) 4 Formula (III); wherein R a represents aroma of 6-15 Further, R b represents an alkyl group having 1 to 5 carbon atoms, R c represents an alkenyl group having 2 to 10 carbon atoms, R d represents an alkyl group having 1 to 5 carbon atoms, and R e represents an alkyl group having 1 to 5 carbon atoms.
詳細而言,在Ra 的定義中,芳香基例如但不限於苯基、甲苯基(tolyl)、對-羥基苯基、1-(對-羥基苯基)乙基、2-(對-羥基苯基)乙基、4-羥基-5-(對-羥基苯基羰氧基)戊基(4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl)或萘基(naphthyl);在Rb 的定義中,烷基例如但不限於甲基、乙基、正丙基、異丙基或正丁基;在Rc 的定義中,烯基例如但不限於乙烯基、3-丙烯醯氧基丙基或3-甲基丙烯醯氧基丙基;在 Rd 的定義中,烷基例如但不限於甲基、乙基、正丙基、異丙基或正丁基;及在Re 的定義中,烷基例如但不限於甲基、乙基、正丙基、異丙基或正丁基。In detail, in the definition of R a , the aryl group is, for example but not limited to, phenyl, tolyl, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyl) Phenyl)ethyl, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl or naphthyl; definition of R b In the alkyl group, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl or n-butyl; in the definition of R c , alkenyl group such as, but not limited to, vinyl, 3-propenyloxypropyl Or 3-methacryloxypropyl; in the definition of Rd , alkyl is, for example but not limited to, methyl, ethyl, n-propyl, isopropyl or n-butyl; and in the definition of R e Alkyl groups are, for example but not limited to, methyl, ethyl, n-propyl, isopropyl or n-butyl.
式(I)所示的金屬烷氧化物的實例包括但不限於苯基三甲氧基矽烷(phenyl trimethoxysilane)、苯基三乙氧基矽烷(phenyl triethoxysilane)、對-羥基苯基三甲氧基矽烷(p-hydroxyphenyl trimethoxysilane)、1-(對-羥基苯基)乙基三甲氧基矽烷(1-(p-hydroxyphenyl)ethyl trimethoxysilane)、2-(對-羥基苯基)乙基三甲氧基矽烷(2-(p-hydroxyphenyl)ethyl trimethoxysilane)、4-羥基-5-(對-羥基苯基羰氧基)戊基三甲氧基矽烷(4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl trimethoxysilane)。另外,適合用作式(I)所示的金屬烷氧化物的市售產品的實例包括:KBM-103或KBE-103(由信越化學工業製造)。在一實施例中,式(I)所示的金屬烷氧化物為苯基三甲氧基矽烷。Examples of the metal alkoxide represented by the formula (I) include, but are not limited to, phenyl trimethoxysilane, phenyl triethoxysilane, p-hydroxyphenyltrimethoxydecane ( P-hydroxyphenyl trimethoxysilane), 1-(p-hydroxyphenyl)ethyl trimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxydecane (2) -(p-hydroxyphenyl)ethyl trimethoxysilane), 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl trimethoxysilane. Further, examples of commercially available products suitable for use as the metal alkoxide represented by the formula (I) include: KBM-103 or KBE-103 (manufactured by Shin-Etsu Chemical Co., Ltd.). In one embodiment, the metal alkoxide of formula (I) is phenyltrimethoxydecane.
式(II)所示的金屬烷氧化物的實例包括但不限於乙烯基三甲氧基矽烷(vinyl trimethoxysilane)、乙烯基三乙氧基矽烷(vinyl triethoxysilane)、3-丙烯醯氧基丙基三甲氧基矽烷(3-acryoyloxypropyl trimethoxysilane)、3-甲基丙烯醯氧基丙基三甲氧基矽烷(3-methylacryloyloxypropyl trimethoxysilane) 或3-甲基丙烯醯氧基丙基三乙氧基矽烷(3-methylacryloyloxypropyl triethoxysilane)。另外,適合用作式(II)所示的金屬烷氧化物的市售產品的實例包括:KBM-1003、KBE-1003、KBM-503、KBE-503和KBM-5103(由信越化學工業製造)。在一實施例中,式(II)所示的金屬烷氧化物為3-甲基丙烯醯氧基丙基三甲氧基矽烷。Examples of the metal alkoxide represented by the formula (II) include, but are not limited to, vinyl trimethoxysilane, vinyl triethoxysilane, 3-propenyloxypropyltrimethoxysilane. 3-acryoyloxypropyl trimethoxysilane, 3-methylacryloyloxypropyl trimethoxysilane Or 3-methylacryloyloxypropyl triethoxysilane. Further, examples of commercially available products suitable for use as the metal alkoxide represented by the formula (II) include: KBM-1003, KBE-1003, KBM-503, KBE-503, and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) . In one embodiment, the metal alkoxide of formula (II) is 3-methylpropenyloxypropyltrimethoxydecane.
式(III)所示的金屬烷氧化物的實例包括但不限於四甲氧基鈦、四乙氧基鈦、四正丙氧基鈦、四異丙氧基鈦或四正丁氧基鈦。另外,適合用作式(III)所示的金屬烷氧化物的市售產品的實例包括:TPT或TBT(由日本曹達株式會社製造)。在一實施例中,式(III)所示的金屬烷氧化物為四正丁氧基鈦。Examples of the metal alkoxide represented by the formula (III) include, but are not limited to, titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide or titanium tetra-n-butoxide. Further, examples of commercially available products suitable for use as the metal alkoxide represented by the formula (III) include: TPT or TBT (manufactured by Nippon Soda Co., Ltd.). In one embodiment, the metal alkoxide of formula (III) is tetra-n-butoxytitanium.
在本實施方式中,以式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100重量份計,式(I)所示的金屬烷氧化物的含量為25重量份至50重量份,較佳為25重量份至45重量份,更佳為30重量份至40重量份。當式(I)所示的金屬烷氧化物的含量小於25重量份時,在波長380nm至450nm的範圍內,由光硬化性塗佈組成物所製得的光硬化塗佈膜的穿透率差。當式(I)所示的金屬烷氧化物的含量大於50重量份時,在波長380nm至450nm的範圍內,雖然由光硬化性塗佈組成物所製得的光硬化塗佈膜 的穿透率佳,但會有嚴重黃化的問題。In the present embodiment, the total amount of the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II), and the metal alkoxide represented by the formula (III) is 100 parts by weight. The content of the metal alkoxide represented by the formula (I) is from 25 parts by weight to 50 parts by weight, preferably from 25 parts by weight to 45 parts by weight, more preferably from 30 parts by weight to 40 parts by weight. When the content of the metal alkoxide represented by the formula (I) is less than 25 parts by weight, the transmittance of the photohardenable coating film prepared from the photocurable coating composition in the wavelength range of 380 nm to 450 nm difference. When the content of the metal alkoxide represented by the formula (I) is more than 50 parts by weight, the photocurable coating film obtained from the photocurable coating composition is in the range of the wavelength of 380 nm to 450 nm. The penetration rate is good, but there will be serious yellowing problems.
在本實施方式中,以式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100重量份計,式(II)所示的金屬烷氧化物的含量為5重量份至20重量份。當式(II)所示的金屬烷氧化物的含量小於5重量份時,光硬化性塗佈組成物的光硬化性差。當式(II)所示的金屬烷氧化物的含量大於20重量份時,雖然光硬化性塗佈組成物的光硬化性佳,但由光硬化性塗佈組成物所製得的光硬化塗佈膜的折射率不佳,或在波長380nm至450nm的範圍內,所述光硬化塗佈膜的穿透率不佳。In the present embodiment, the total amount of the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II), and the metal alkoxide represented by the formula (III) is 100 parts by weight. The metal alkoxide represented by the formula (II) is contained in an amount of from 5 parts by weight to 20 parts by weight. When the content of the metal alkoxide represented by the formula (II) is less than 5 parts by weight, the photocurable coating composition is inferior in photocurability. When the content of the metal alkoxide represented by the formula (II) is more than 20 parts by weight, although the photocurable coating composition has good photocurability, the photohardenable coating prepared from the photocurable coating composition is used. The refractive index of the film is not good, or the transmittance of the photo-curing coating film is not good in the range of 380 nm to 450 nm.
在本實施方式中,以式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100重量份計,式(III)所示的金屬烷氧化物的含量為45重量份至70重量份。當式(III)所示的金屬烷氧化物的含量小於45重量份時,由光硬化性塗佈組成物所製得的光硬化塗佈膜的折射率太小。當式(III)所示的金屬烷氧化物的含量大於70重量份時,光硬化性塗佈組成物的光硬化性不佳、由光硬化性塗佈組成物所製得的光硬化塗佈膜的折射率太大,或在波長380nm至450nm的範圍內,所述光硬化塗佈膜的穿透率不佳。In the present embodiment, the total amount of the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II), and the metal alkoxide represented by the formula (III) is 100 parts by weight. The metal alkoxide represented by the formula (III) is contained in an amount of from 45 parts by weight to 70 parts by weight. When the content of the metal alkoxide represented by the formula (III) is less than 45 parts by weight, the refractive index of the photohardenable coating film produced from the photocurable coating composition is too small. When the content of the metal alkoxide represented by the formula (III) is more than 70 parts by weight, the photocurable coating composition is inferior in photocurability, and photoharden coating by the photocurable coating composition is obtained. The refractive index of the film is too large, or in the range of wavelengths of 380 nm to 450 nm, the transmittance of the photo-curing coating film is not good.
在不損及本發明的光硬化性塗佈組成物的效果範圍 內,光硬化性塗佈組成物中光硬化性聚合物除了上述式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物之外,亦可以含有其他金屬烷氧化物經加水分解縮合反應而得。所述其他金屬烷氧化物包含但不限於3-環氧丙氧基丙基三甲氧基矽烷(3-glycidoxypropyl trimethoxysilane)、3-環氧丙氧基丙基三乙氧基矽烷(3-glycidoxypropyl triethoxysilane)、2-(3,4-環氧環己基)乙基三甲氧基矽烷(2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane)、3-乙基-3-((3-(三苯氧基矽基)丙氧基)甲基)環氧丙烷(3-ethyl-3-((3-(triphenoxysilyl)propoxy)methyl)oxetane)、3-乙基-3-((3-(三甲氧基矽基)丙氧基)甲基)環氧丙烷(3-ethyl-3-((3-(trimethoxysilyl)propoxy)methyl)oxetane)、3-乙基-3-((3-(三乙氧基矽基)丙氧基)甲基)環氧丙烷(3-ethyl-3-((3-(triethoxysilyl)propoxy)methyl)oxetane)、2-(三甲氧基矽基)乙基丁二酸酐(2-(trimethoxysilyl)ethyl succinic anhydride)、3-(三苯氧基矽基)丙基丁二酸酐(3-(triphenoxysilyl)propyl succinic anhydride)、3-(三甲氧基矽基)丙基丁二酸酐(3-(trimethoxysilyl)propyl succinic anhydride)、3-(三乙氧基矽基)丙基丁二酸酐(3-(triethoxysilyl)propyl succinic anhydride)、3-(三甲氧基矽 基)丙基戊二酸酐(3-(trimethoxysilyl)propyl glutaric anhydride)、3-(三乙氧基矽基)丙基戊二酸酐(3-(triethoxysilyl)propyl glutaric anhydride)、3-(三苯氧基矽基)丙基戊二酸酐(3-(triphenoxysilyl)propyl glutaric anhydride)、二異丙氧基-二(2-環氧丙烷基丁氧基丙基)矽烷(diisopropoxy-di(2-oxetanylpropylbutoxypropyl)silane)、二(3-環氧丙烷基戊基)二甲氧基矽烷(di(3-oxetanylpentyl)dimethoxy silane)、(二正丁氧基矽基)二(丙基丁二酸酐)((di-n-butoxysilyl)di(propyl succinic anhydride))、(二甲氧基矽基)二(乙基丁二酸酐)((dimethoxysilyl)di(ethyl succinic anhydride))、3-環氧丙氧基二甲基甲氧基矽烷(3-glycidoxydimethylmethoxysilane)、3-環氧丙氧基二甲基乙氧基矽(3-glycidoxydimethylethoxysilane)、二(2-環氧丙烷基丁氧基戊基)-2-環氧丙烷基戊基乙氧基矽(di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxy silane)、三(2-環氧丙烷基戊基)甲氧基矽烷(tri(2-oxetanylpentyl)methoxy silane)、(苯氧基矽基)三(丙基丁二酸酐)((phenoxysilyl)tri(propyl succinic anhydride))、(甲基甲氧基矽基)二(乙基丁二酸酐)((methylmethoxysilyl) di(ethyl succinic anhydride))、四甲氧基矽烷(tetramethoxysilane)、四乙氧基矽烷(tetraethoxysilane)、四乙醯氧基矽烷(tetraacetoxysilane)、四苯氧基矽烷(tetraphenoxysilane)、甲基三甲氧基矽烷(methyltrimethoxysilane)、甲基三乙氧基矽烷(methyltriethoxysilane)、甲基三異丙氧基矽烷(methyltriisopropoxysilane)、甲基三正丁氧基矽烷(methyltri-n-butoxysilane)、乙基三甲氧基矽烷(ethyltrimethoxysilane)、乙基三乙氧基矽烷(ethyltriethoxysilane)、乙基三異丙氧基矽烷(ethyltriisopropoxysilane)、乙基三正丁氧基矽烷(ethyltri-n-butoxysilane)、正丙基三甲氧基矽烷(n-propyltrimethoxysilane)、正丙基三乙氧基矽烷(n-propyltriethoxysilane)、正丁基三甲氧基矽烷(n-butyltrimethoxysilane)、正丁基三乙氧基矽烷(n-butyltriethoxysilane)、正己基三甲氧基矽烷(n-hexyltrimethoxysilane)、正己基三乙氧基矽烷(n-hexyltriethoxysilane)、癸基三甲氧基矽烷(decyltrimethoxysilane)、三氟甲基三甲氧基矽烷(trifluoromethyltrimethoxysilane)、三氟甲基三乙氧基矽烷 (trifluoromethyltriethoxysilane)、3,3,3-三氟丙基三甲氧基矽烷(3,3,3-trifluoropropyltrimethoxysilane)、3-胺丙基三甲氧基矽烷(3-aminopropyltrimethoxysilane)、3-胺丙基三乙氧基矽烷(3-aminopropyltriethoxysilane)、二甲基二甲氧基矽烷(dimethyldimethoxysilane)、二甲基二乙氧基矽烷(dimethyldiethoxysilane)、二甲基二乙醯氧基矽烷(dimethyldiacetyloxysilane)、二正丁基二甲氧基矽烷(di-n-butyldimethoxysilane)、二苯基二甲氧基矽烷(diphenyldimethoxysilane)、三甲基甲氧基矽烷(trimethylmethoxysilane)、三正丁基乙氧基矽烷(tri-n-butylethoxysilane)、3-巰丙基三甲氧基矽烷(3-mercaptopropyltrimethoxysilane)。The effect range of the photocurable coating composition of the present invention is not impaired In the photocurable coating composition, the photocurable polymer is a metal alkoxide represented by the above formula (I), a metal alkoxide represented by the formula (II), and a metal alkane represented by the formula (III). In addition to the oxide, other metal alkoxides may also be obtained by hydrolysis and condensation reaction. The other metal alkoxides include, but are not limited to, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane , 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-ethyl-3-((3-(triphenyloxy)) 3-ethyl-3-((3-(triphenoxysilyl)propoxy)methyl)oxetane), 3-ethyl-3-((3-(trimethoxy) oxime) 3-ethyl-3-((3-(trimethoxysilyl)propoxy)methyl)oxetane), 3-ethyl-3-((3-(triethoxy) oxime) 3-ethyl-3-((3-(triethoxysilyl)propoxy)methyl)oxetane), 2-(trimethoxyindenyl)ethyl succinic anhydride (2- (trimethoxysilyl)ethyl succinic anhydride), 3-(triphenoxysilyl)propyl succinic anhydride, 3-(trimethoxyindolyl)propyl succinic anhydride (3) -(trimethoxysilyl)propyl succinic anhydride), 3-(triethoxysilyl)propyl succinic anhydride (3-(triethoxysilyl) propyl Succinic anhydride), 3-(trimethoxyanthracene) 3-(trimethoxysilyl)propyl glutaric anhydride, 3-(triethoxysilyl)propyl glutaric anhydride, 3-(triphenyloxy) 3-(triphenoxysilyl)propyl glutaric anhydride, diisopropoxy-di(2-oxetanylpropylbutoxypropyl) Silane), di(3-oxetanylpentyl)dimethoxy silane, (di-n-butoxycarbonyl)di(propyl succinic anhydride) (di -n-butoxysilyl)di(propyl succinic anhydride), (dimethoxysilyl) di(ethyl succinic anhydride), 3-epoxypropoxy dimethyl 3-glycidoxydimethylmethoxysilane, 3-glycidoxydimethylethoxysilane, bis(2-propylene oxide-butoxypentyl)-2-epoxy Di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxy silane, tri(2-oxetanylpentyl)methoxy s Ilane), (phenoxysilyl) tri(propyl succinic anhydride), (methylmethoxyindolyl) di(ethyl succinic anhydride) ((methylmethoxysilyl) ) Di(ethyl succinic anhydride)), tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, methyltrimethoxy Methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxydecane (ethyltrimethoxysilane), ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxydecane (n-propyltrimethoxysilane), n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethyl N-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane Trifluoromethyl trimethoxy Silane (trifluoromethyltrimethoxysilane), trifluoromethyl triethoxy silane- (trifluoromethyltriethoxysilane), 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetyloxysilane, di-n-butyl Di-n-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, tri-n-butylethoxysilane , 3-mercaptopropyltrimethoxysilane.
本發明之另一實施方式提供的光硬化性塗佈組成物包括光硬化性聚合物。光硬化性聚合物基本上由式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物組成經加水分解縮合反應而得:Rc 1 Si(ORd )3 式(II);Ti(ORe )4 式(III);其中Rc 表示碳數2~10的烯基,Rd 表示碳數1~5的烷基,Re 表示碳數1~5的烷基。A photocurable coating composition provided by another embodiment of the present invention includes a photocurable polymer. The photocurable polymer is obtained by substantially hydrolyzing a condensation reaction of a metal alkoxide represented by the formula (II) and a metal alkoxide represented by the formula (III): R c 1 Si(OR d ) 3 (II); Ti(OR e ) 4 Formula (III); wherein R c represents an alkenyl group having 2 to 10 carbon atoms, R d represents an alkyl group having 1 to 5 carbon atoms, and R e represents an alkane having 1 to 5 carbon atoms; base.
式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的實例包括如同前述所列舉的實例。Examples of the metal alkoxide represented by the formula (II) and the metal alkoxide represented by the formula (III) include the examples as exemplified above.
在本實施方式中,以式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100重量份計,式(III)所示的金屬烷氧化物的含量為55重量份至70重量份。當式(III)所示的金屬烷氧化物的含量小於55重量份時,由光硬化性塗佈組成物所製得的光硬化塗佈膜的折射率太小。當式(III)所示的金屬烷氧化物的含量大於70重量份時,光硬化性塗佈組成物的光硬化性不佳、由光硬化性塗佈組成物所製得的光硬化塗佈膜的折射率太大。In the present embodiment, the metal alkoxide represented by the formula (III) is a total amount of the metal alkoxide represented by the formula (II) and the metal alkoxide represented by the formula (III) in an amount of 100 parts by weight. The content is from 55 parts by weight to 70 parts by weight. When the content of the metal alkoxide represented by the formula (III) is less than 55 parts by weight, the refractive index of the photohardenable coating film produced from the photocurable coating composition is too small. When the content of the metal alkoxide represented by the formula (III) is more than 70 parts by weight, the photocurable coating composition is inferior in photocurability, and photoharden coating by the photocurable coating composition is obtained. The refractive index of the film is too large.
在前述實施方式中,所述加水分解縮合反應可使用一般的方法。舉例而言,將式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物與溶劑、水或選擇性添加的觸媒於30℃~150℃下加熱攪拌0.5小時~120小時。另外,在攪拌時,進一步地可藉由蒸餾除去副產物(醇類、水等)。In the foregoing embodiment, the hydrolysis method can be carried out by a general method. For example, a metal alkoxide represented by the formula (I), a metal alkoxide represented by the formula (II), and a metal alkoxide represented by the formula (III) are contacted with a solvent, water or a selective addition. The medium is heated and stirred at 30 ° C to 150 ° C for 0.5 hour to 120 hours. Further, by stirring, by-products (alcohols, water, etc.) can be further removed by distillation.
上述溶劑並沒有特別限制,可與本發明光硬化性塗佈組成物中所使用的溶劑(相關描述將於下文中說明)相同或不同。以式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100克計,溶劑的使用 量較佳為100克至1,200克,更佳為300克至1,000克。The above solvent is not particularly limited and may be the same as or different from the solvent used in the photocurable coating composition of the present invention (the related description will be described later). The total amount of the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II) and the metal alkoxide represented by the formula (III) is 100 g, and the solvent is used. The amount is preferably from 100 g to 1,200 g, more preferably from 300 g to 1,000 g.
以式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物中所含的可水解基團為1莫耳計,用於水解的水的使用量為0.5莫耳至2莫耳。The hydrolyzable group contained in the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II) and the metal alkoxide represented by the formula (III) is 1 mol. The amount of water used for hydrolysis is from 0.5 moles to 2 moles.
上述觸媒並沒有特別的限制。在一實施例中,觸媒是選自於酸觸媒或鹼觸媒。所述酸觸媒包含但不限於草酸、鹽酸、硝酸、硫酸、氟酸、磷酸、醋酸、三氟醋酸、蟻酸、多元羧酸或其酐、離子交換樹脂等。所述鹼觸媒包含但不限於二乙胺、三乙胺、三丙胺、三丁胺、三戊胺、三己胺、三庚胺、三辛胺、二乙醇胺、三乙醇胺、氫氧化鈉、氫氧化鉀、含有胺基的烷氧基矽烷、離子交換樹脂等。以式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100克計,觸媒的使用量較佳為0.005克至15克,更佳為0.01克至12克,又更佳為0.05克至10克。The above catalyst is not particularly limited. In one embodiment, the catalyst is selected from an acid catalyst or a base catalyst. The acid catalyst includes, but is not limited to, oxalic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, ion exchange resin, and the like. The base catalyst includes, but is not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide, Potassium hydroxide, an alkoxysilane containing an amine group, an ion exchange resin, and the like. The total amount of the catalyst is compared with the total amount of the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II) and the metal alkoxide represented by the formula (III). Preferably, it is from 0.005 g to 15 g, more preferably from 0.01 g to 12 g, still more preferably from 0.05 g to 10 g.
基於安定性的觀點,經加水分解縮合反應而得的光硬化性聚合物以不含副產物(如醇類或水)、觸媒為佳,因此可選擇性地對經加水分解縮合反應而得的光硬化性聚合物進行純化。純化方法並無特別限制。在一實施例中,可以疏水性溶劑稀釋光硬化性聚合物,接著以蒸發器濃縮經水洗滌數回的有機層,以除去醇類或水。另外,可使用離子交換樹脂除去觸媒。From the viewpoint of stability, the photocurable polymer obtained by the hydrolysis reaction is preferably free from by-products (such as alcohols or water) and a catalyst, so that it can be selectively hydrolyzed and condensed. The photohardenable polymer is purified. The purification method is not particularly limited. In one embodiment, the photocurable polymer may be diluted with a hydrophobic solvent, followed by concentration of the organic layer washed several times with water by an evaporator to remove the alcohol or water. Alternatively, the catalyst can be removed using an ion exchange resin.
另外,在本實施方式中,光硬化性塗佈組成物可更包括溶劑。溶劑的種類並沒有特別限制。詳細而言,溶劑包括但不限於含醇式羥基(alcoholic hydroxyl)的化合物或含羰基的環狀化合物。另外,溶劑可單獨或混合使用。Further, in the present embodiment, the photocurable coating composition may further include a solvent. The kind of the solvent is not particularly limited. In detail, the solvent includes, but is not limited to, a compound containing an alcoholic hydroxyl group or a cyclic compound containing a carbonyl group. Further, the solvent may be used singly or in combination.
所述含醇式羥基的化合物包含但不限於丙酮醇(acetol)、3-羥基-3-甲基-2-丁酮、4-羥基-3-甲基-2-丁酮、5-羥基-2-戊酮、4-羥基-4-甲基-2-戊酮(又稱二丙酮醇,diacetone alcohol)、乳酸乙酯、乳酸丁酯、丙二醇單甲醚、丙二醇單乙醚(propylene glycol monoethyl ether)、丙二醇甲醚醋酸酯(propylene glycol monomethylether acetate)、丙二醇單正丙醚、丙二醇單正丁醚、丙二醇單第三丁醚、3-甲氧基-1-丁醇、3-甲基-3-甲氧基-1-丁醇或此等一組合。含醇式羥基的化合物較佳是擇自於二丙酮醇、乳酸乙酯、丙二醇單乙醚、丙二醇甲醚醋酸酯,或此等一組合。The alcoholic hydroxyl group-containing compound includes, but is not limited to, acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy- 2-pentanone, 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether ), propylene glycol monomethylether acetate, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, 3-methoxy-1-butanol, 3-methyl-3 -Methoxy-1-butanol or a combination of these. The alcoholic hydroxyl group-containing compound is preferably selected from the group consisting of diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, or a combination thereof.
所述含羰基的環狀化合物包含但不限於γ-丁內酯、γ-戊內酯、δ-戊內酯、碳酸丙烯酯、氮-甲基吡咯烷酮、環己酮或環庚酮等。含羰基的環狀化合物較佳是擇自於γ-丁內酯、氮-甲基吡咯烷酮、環己酮,或此等一組合。The carbonyl group-containing cyclic compound includes, but is not limited to, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, nitrogen-methylpyrrolidone, cyclohexanone or cycloheptanone. The carbonyl-containing cyclic compound is preferably selected from the group consisting of γ-butyrolactone, nitrogen-methylpyrrolidone, cyclohexanone, or a combination thereof.
當含醇式羥基的化合物與含羰基的環狀化合物混合使用時,其重量比率並沒有特別限制。在一實施例中,含醇式 羥基的化合物與含羰基的環狀化合物的重量比較佳為99/1至50/50,更佳為95/5至60/40。When the compound having an alcoholic hydroxyl group is used in combination with a cyclic compound containing a carbonyl group, the weight ratio thereof is not particularly limited. In one embodiment, the alcoholic form The weight of the hydroxy compound and the carbonyl group-containing cyclic compound is preferably from 99/1 to 50/50, more preferably from 95/5 to 60/40.
在不損及本發明的光硬化性塗佈組成物的效果範圍內,光硬化性塗佈組成物亦可以含有其他溶劑。所述其他溶劑包含但不限於(1)酯類:醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、丙二醇甲醚醋酸酯、3-甲氧基-1-醋酸丁酯、3-甲基-3-甲氧基-1-醋酸丁酯等;(2)酮類:甲基異丁酮、二異丙酮、二異丁酮等;(3)醚類:二乙醚、二異丙醚、二正丁醚、二苯醚等。The photocurable coating composition may contain other solvents within the range of the effect of not impairing the photocurable coating composition of the present invention. The other solvents include, but are not limited to, (1) esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, 3-methoxy- 1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, etc.; (2) ketones: methyl isobutyl ketone, diisopropanone, diisobutyl ketone, etc.; (3) ether Class: diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether and the like.
另外,以光硬化性聚合物的總量為100重量份計,溶劑的使用量為500重量份至20,000重量份,較佳為800重量份至10,000重量份,更佳為1,000重量份至6,000重量份。Further, the solvent is used in an amount of from 500 parts by weight to 20,000 parts by weight, based on the total amount of the photocurable polymer, preferably from 800 parts by weight to 10,000 parts by weight, more preferably from 1,000 parts by weight to 6,000 parts by weight. Share.
在不損及本發明的光硬化性塗佈組成物的效果範圍內,光硬化性塗佈組成物可依需要添加使用其他的添加劑。添加劑可單獨或混合使用,且添加劑包含但不限於增感劑、密著助劑、界面活性劑、溶解促進劑、消泡劑,或此等一組合。The photocurable coating composition may be added with other additives as needed within the range of the effect of not impairing the photocurable coating composition of the present invention. The additives may be used singly or in combination, and the additives include, but are not limited to, sensitizers, adhesion promoters, surfactants, dissolution promoters, antifoaming agents, or a combination thereof.
本發明之一實施方式提供的光硬化塗佈膜由任一種前述實施方式中的光硬化性塗佈組成物所製得。詳細而言,光硬化塗佈膜的製備方法依序包括:將光硬化性塗佈組成物塗佈於一基材上、進行預烤(pre-bake)處理以形成預烤塗膜、對 預烤塗膜進行光硬化處理以及進行後烤(post-bake)處理。A photo-curing coating film according to an embodiment of the present invention is produced by the photocurable coating composition of any of the above embodiments. In detail, the method for preparing the photo-curable coating film includes sequentially applying a photo-curable coating composition onto a substrate, performing a pre-bake treatment to form a pre-baked coating film, and The prebaked coating film is subjected to photohardening treatment and post-bake treatment.
塗佈光硬化性塗佈組成物的方法可使用一般所進行的塗佈法,例如浸漬塗佈法、旋塗法、噴塗法、刷毛塗佈法、輥轉印法、網版印刷法、噴墨法或膠版印刷法。所述基材可以是無鹼玻璃、鈉鈣玻璃、硬質玻璃(派勒斯玻璃)、石英玻璃或附著有透明導電膜的上述玻璃。在一實施例中,前述透明導電膜例如是觸控面板的觸控元件。The method of applying the photocurable coating composition can be carried out by a coating method generally performed, for example, a dip coating method, a spin coating method, a spray coating method, a brush coating method, a roll transfer method, a screen printing method, or a spray method. Ink method or offset printing method. The substrate may be alkali-free glass, soda-lime glass, hard glass (Pyrus glass), quartz glass, or the above-described glass to which a transparent conductive film is attached. In one embodiment, the transparent conductive film is, for example, a touch element of a touch panel.
所述預烤處理的溫度條件較佳為室溫至150℃,更佳為40℃至120℃。預烤處理的時間條件較佳為30秒至10分鐘左右,更佳為1分鐘至8分鐘左右。預烤處理的方法例如可使用加熱板或熱風循環式烘箱等。The temperature condition of the pre-baking treatment is preferably from room temperature to 150 ° C, more preferably from 40 ° C to 120 ° C. The time condition of the pre-baking treatment is preferably from about 30 seconds to about 10 minutes, more preferably from about 1 minute to about 8 minutes. As the method of the pre-baking treatment, for example, a hot plate or a hot air circulation type oven or the like can be used.
所述光硬化處理所使用的光線以g線、b線、i線等紫外線為佳,並且用來提供紫外線的設備可為(超)高壓水銀燈或金屬鹵素燈。The light used in the photohardening treatment is preferably ultraviolet rays such as g-line, b-line, or i-line, and the device for providing ultraviolet rays may be a (ultra) high pressure mercury lamp or a metal halide lamp.
所述後烤處理的溫度條件較佳為100℃至300℃,更佳為150℃至250℃。後烤處理的時間條件較佳為5分鐘以上,更佳為15分鐘以上。後烤處理的方法例如可使用加熱板、熱風循環式烘箱或紅外線烘箱等。The temperature condition of the post-baking treatment is preferably from 100 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C. The time condition of the post-baking treatment is preferably 5 minutes or longer, more preferably 15 minutes or longer. For the post-baking treatment, for example, a hot plate, a hot air circulating oven, an infrared oven, or the like can be used.
在一實施例中,本發明的光硬化塗佈膜的膜厚度為80nm至120nm,且折射率為1.60至1.70。In one embodiment, the photohardenable coating film of the present invention has a film thickness of from 80 nm to 120 nm and a refractive index of from 1.60 to 1.70.
在一實施例中,在波長380nm至450nm的範圍內,本發明的光硬化塗佈膜的穿透率大於95%。In one embodiment, the light-curable coating film of the present invention has a transmittance of greater than 95% in the range of wavelengths of 380 nm to 450 nm.
另外,與一般由有機材料所構成的塗佈膜相比,以金屬烷氧化物(無機材料)作為主要成分的本發明的光硬化塗佈膜具有較優異的機械強度,藉此適用於後述之本發明的觸控面板。In addition, the photocurable coating film of the present invention containing a metal alkoxide (inorganic material) as a main component has superior mechanical strength as compared with a coating film which is generally composed of an organic material, and is suitable for use in the following description. The touch panel of the present invention.
本發明之一實施方式提供的觸控面板包括任一種前述實施方式中的光硬化塗佈膜。以下,將參照圖1及圖2詳細說明本發明的觸控面板。A touch panel according to an embodiment of the present invention includes the photo-curing coating film according to any of the foregoing embodiments. Hereinafter, the touch panel of the present invention will be described in detail with reference to FIGS. 1 and 2.
圖1是本發明一實施方式的觸控面板的上視示意圖。圖2是圖1的觸控面板沿剖線I-I’的剖面示意圖。請同時參照圖1及圖2,觸控面板100包括基板102、觸控元件104及保護層106。1 is a top plan view of a touch panel according to an embodiment of the present invention. 2 is a cross-sectional view of the touch panel of FIG. 1 taken along line I-I'. Referring to FIG. 1 and FIG. 2 , the touch panel 100 includes a substrate 102 , a touch element 104 , and a protective layer 106 .
基板102可以是所屬領域中具有通常知識者所周知的任一基板,例如矽基板、玻璃基板、塑膠基板或是其他軟性基板。Substrate 102 can be any substrate known in the art, such as a germanium substrate, a glass substrate, a plastic substrate, or other flexible substrate.
觸控元件104配置在基板102上。在本實施方式中,觸控元件104包括多個觸控串列110及多個觸控串列120,其中觸控串列110沿著方向D1延伸,觸控串列120沿著與方向D1相交的方向D2延伸,以及觸控串列110與觸控串列120 彼此電性絕緣。詳細而言,各觸控串列110包括多個觸控電極112以及多條連接部114,其中各連接部114連接相鄰兩個觸控電極112,以及各觸控串列120包括多個觸控電極122以及多條連接部124,其中各連接部124連接相鄰兩個觸控電極122。另外,觸控串列110與觸控串列120的交錯處設置有絕緣圖案130,以使兩者彼此電性絕緣。The touch element 104 is disposed on the substrate 102. In this embodiment, the touch component 104 includes a plurality of touch strings 110 and a plurality of touch strings 120, wherein the touch string 110 extends along the direction D1, and the touch string 120 intersects the direction D1. The direction D2 extends, and the touch string 110 and the touch string 120 Electrically insulated from each other. In detail, each touch string 110 includes a plurality of touch electrodes 112 and a plurality of connecting portions 114. Each of the connecting portions 114 connects two adjacent touch electrodes 112, and each touch string 120 includes multiple touches. The control electrode 122 and the plurality of connecting portions 124 are connected to the adjacent two touch electrodes 122. In addition, an insulation pattern 130 is disposed at the intersection of the touch string 110 and the touch string 120 to electrically insulate the two.
觸控串列110之觸控電極112與連接部114以及觸控串列120之觸控電極122與連接部124的材質可以相同或是不同,且例如是透明導電材料或其他適合的導電材料,其中透明導電材料例如是銦錫氧化物、銦鋅氧化物、鋁鋅氧化物等,以及其混合物或是疊層。The material of the touch electrode 112 and the connecting portion 114 of the touch string 110 and the touch electrode 122 and the connecting portion 124 of the touch string 120 may be the same or different, and is, for example, a transparent conductive material or other suitable conductive material. The transparent conductive material is, for example, indium tin oxide, indium zinc oxide, aluminum zinc oxide, or the like, and a mixture or laminate thereof.
此外,雖然在本實施方式中是以具有圖1及圖2所示之結構的觸控元件104為例來進行說明,但本發明不以此為限。觸控元件104可以是所屬領域具有通常知識者所周知的任一觸控元件。也就是說,觸控元件104可以具有所熟知的其他構形。In addition, in the present embodiment, the touch element 104 having the structure shown in FIGS. 1 and 2 is taken as an example, but the invention is not limited thereto. Touch element 104 can be any touch element known to those of ordinary skill in the art. That is, touch element 104 can have other configurations as are well known.
保護層106配置在基板102上且覆蓋觸控元件104,用以保護觸控元件104免於外力按壓而破壞。在本實施方式中,保護層106是由任一種前述實施方式中的光硬化塗佈膜實現。也就是說,保護層106是透過將本發明的光硬化性塗佈組 成物塗佈於觸控元件104上後,進行預烤處理、光硬化處理以及後烤處理而形成。然而,光硬化塗佈膜的相關描述及製備方法已於前述實施方式中進行詳盡地說明,故於此不再贅述。The protective layer 106 is disposed on the substrate 102 and covers the touch element 104 for protecting the touch element 104 from external force. In the present embodiment, the protective layer 106 is realized by the photo-curing coating film of any of the above embodiments. That is, the protective layer 106 is transmitted through the photocurable coating group of the present invention. After the application is applied to the touch element 104, it is formed by prebaking, photohardening, and post-baking. However, the related description and preparation method of the photo-curing coating film have been described in detail in the foregoing embodiments, and thus will not be described herein.
值得說明的是,如前文所述,本發明的光硬化塗佈膜的折射率介於1.60至1.70之間,且在波長380nm至450nm的範圍內,穿透率大於95%,藉此使得以本發明的光硬化塗佈膜作為保護層的觸控面板可擁有良好的視別性及顯示品質。It is to be noted that, as described above, the photo-curing coating film of the present invention has a refractive index of between 1.60 and 1.70, and a transmittance of more than 95% in the wavelength range of 380 nm to 450 nm, thereby The light-curing coating film of the present invention can have good visibility and display quality as a touch panel of a protective layer.
下文將參照實驗例,更具體地描述本發明的光硬化性塗佈組成物。雖然描述了以下實驗,但是在不逾越本發明範疇的情況下,可適當地改變所用材料、其量及比率、處理細節以及處理流程等等。因此,不應根據下文所述的實驗對本發明作出限制性的解釋。The photocurable coating composition of the present invention will be more specifically described below with reference to experimental examples. Although the following experiments are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively based on the experiments described below.
在容積為1,000毫升的三頸燒瓶中,加入25重量份的苯基三甲氧基矽烷(以下簡稱PTMS,即式(I)所示的金屬烷氧化物)、11重量份的3-甲基丙烯醯氧丙基三甲氧基矽烷(以下簡稱KBM503,即式(II)所示的金屬烷氧化物)、64重量份 的四正丁氧基鈦(以下簡稱TBT,即式(III)所示的金屬烷氧化物)[上述所有金屬烷氧化物之重量總計為100克]及600克的丙二醇單乙醚(以下簡稱PGEE),並於室溫下一邊攪拌一邊於30分鐘內添加草酸水溶液(0.40克草酸/75克水)。接著,將燒瓶浸漬於30℃的油浴中並攪拌30分鐘,然後於30分鐘內將油浴升溫至120℃,待溶液的內溫達到105℃時,持續加熱攪拌進行聚縮合6小時,再利用蒸餾方式將溶劑移除,即可得實驗例1的光硬化性聚合物。In a three-necked flask having a volume of 1,000 ml, 25 parts by weight of phenyltrimethoxydecane (hereinafter referred to as PTMS, that is, a metal alkoxide represented by the formula (I)), and 11 parts by weight of 3-methylpropene were added.醯 propyl trimethoxy decane (hereinafter referred to as KBM 503, that is, a metal alkoxide represented by formula (II)), 64 parts by weight Tetra-n-butoxytitanium (hereinafter referred to as TBT, that is, metal alkoxide represented by formula (III)) [all of the above metal alkoxides have a total weight of 100 g] and 600 g of propylene glycol monoethyl ether (hereinafter referred to as PGEE) And, an aqueous oxalic acid solution (0.40 g of oxalic acid / 75 g of water) was added over 30 minutes while stirring at room temperature. Next, the flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes, and then the oil bath was heated to 120 ° C in 30 minutes. When the internal temperature of the solution reached 105 ° C, heating and stirring were continued for polycondensation for 6 hours. The photocurable polymer of Experimental Example 1 was obtained by removing the solvent by distillation.
將100重量份的實驗例1的光硬化性聚合物及1,900重量份的PGEE,以搖動式攪拌器攪拌均勻後,即可得到實驗例1的光硬化性塗佈組成物(固形份:5重量%)。100 parts by weight of the photocurable polymer of Experimental Example 1 and 1,900 parts by weight of PGEE were uniformly stirred by a shaking stirrer to obtain a photocurable coating composition of Experimental Example 1 (solid content: 5 weight) %).
以與實驗例1類似的方式製備實驗例2至實驗例6的光硬化性塗佈組成物。差異在於,製備實驗例2至實驗例6的光硬化性聚合物時,式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物或式(III)所示的金屬烷氧化物的種類或用量與實驗例1不同,其細節詳列於表1中。The photocurable coating compositions of Experimental Examples 2 to 6 were prepared in the same manner as Experimental Example 1. The difference is that when the photocurable polymer of Experimental Example 2 to Experimental Example 6 is prepared, the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II) or the formula (III) The kind or amount of the metal alkoxide is different from that of Experimental Example 1, and the details thereof are shown in Table 1.
以與實驗例1類似的方式製備實驗例7的光硬化性塗 佈組成物。差異在於,製備實驗例7的光硬化性聚合物時,除了式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物或式(III)所示的金屬烷氧化物的種類或用量與實驗例1不同(細節詳列於表1中)外,還包括添加3重量份的四乙氧基矽烷(以下簡稱TEOS)。The photocurable coating of Experimental Example 7 was prepared in the same manner as Experimental Example 1. Cloth composition. The difference is that when the photocurable polymer of Experimental Example 7 is prepared, in addition to the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II) or the metal alkoxide represented by the formula (III) The kind or amount of the substance was different from that of Experimental Example 1 (details are detailed in Table 1), and 3 parts by weight of tetraethoxysilane (hereinafter referred to as TEOS) was further added.
以與實驗例1類似的方式製備實驗例8的光硬化性塗佈組成物。差異在於,製備實驗例8的光硬化性聚合物時,未使用式(I)所示的金屬烷氧化物,另外式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的用量與實驗例1不同,其細節詳列於表1中。The photocurable coating composition of Experimental Example 8 was prepared in the same manner as Experimental Example 1. The difference is that when the photocurable polymer of Experimental Example 8 is prepared, the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II) and the metal represented by the formula (III) are not used. The amount of alkoxide used was different from that of Experimental Example 1, and the details thereof are shown in Table 1.
以與實驗例1類似的方式製備比較例1至比較例7的光硬化性塗佈組成物。差異在於,製備比較例1至比較例7的光硬化性聚合物時,式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物或式(III)所示的金屬烷氧化物的種類或用量與實驗例1不同,其細節詳列於表2中。The photocurable coating compositions of Comparative Examples 1 to 7 were prepared in the same manner as Experimental Example 1. The difference is that when the photocurable polymer of Comparative Example 1 to Comparative Example 7 is prepared, the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II) or the formula (III) The type or amount of the metal alkoxide is different from that of Experimental Example 1, and the details thereof are shown in Table 2.
以與實驗例1類似的方式製備比較例8的光硬化性塗佈組成物。差異在於,製備比較例8的光硬化性聚合物時,未 使用式(I)所示的金屬烷氧化物,而是添加TEOS。另外,比較例8所使用的式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的種類及添加量以及TEOS的添加量詳列於表2中。The photocurable coating composition of Comparative Example 8 was prepared in the same manner as Experimental Example 1. The difference is that when the photocurable polymer of Comparative Example 8 was prepared, The metal alkoxide represented by the formula (I) is used, but TEOS is added. The type and amount of the metal alkoxide represented by the formula (II) used in the comparative example 8 and the metal alkoxide represented by the formula (III) and the amount of TEOS added are shown in Table 2.
接著,將實驗例1至實驗例8及比較例1至比較例8的光硬化性塗佈組成物分別製備成光硬化塗佈膜,詳細步驟如下。首先,以孔徑0.5μm的膜濾器分別加壓過濾實驗例1至實驗例8及比較例1至比較例8的光硬化性塗佈組成物,並使用旋塗法將其塗佈於基板上以形成預烤塗膜。接著,將形成有預烤塗膜的基板置於溫度設定為90℃的加熱板上,加熱5分鐘使其乾燥。之後,使用紫外線照射裝置(Eye Graphics公司製造,型號:UB 011-3A),以高壓水銀燈(輸入電源1000W)以16mW/cm2 (波長365nm)的光強度照射紫外線75秒,其中紫外線照射量為1200mJ/cm2 。於紫外線照射後,將基板移至溫度設定為250℃的熱風循環式烘箱內,進行後烤處理30分鐘,以於基板上形成實驗例1至實驗例8及比較例1至比較例8的光硬化塗佈膜(膜厚為100nm)。Next, the photocurable coating compositions of Experimental Examples 1 to 8 and Comparative Examples 1 to 8 were each prepared into a photocurable coating film, and the detailed procedure was as follows. First, the photocurable coating compositions of Experimental Examples 1 to 8 and Comparative Examples 1 to 8 were separately filtered under pressure with a membrane filter having a pore diameter of 0.5 μm, and coated on a substrate by spin coating. A pre-baked coating film is formed. Next, the substrate on which the prebaked coating film was formed was placed on a hot plate set to a temperature of 90 ° C, and dried by heating for 5 minutes. Thereafter, ultraviolet rays were irradiated for 75 seconds at a light intensity of 16 mW/cm 2 (wavelength 365 nm) with a high-pressure mercury lamp (input power supply 1000 W) using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., model: UB 011-3A), wherein the ultraviolet irradiation amount was 1200mJ/cm 2 . After the ultraviolet irradiation, the substrate was transferred to a hot air circulating oven set to a temperature of 250 ° C, and post-baked for 30 minutes to form light of Experimental Example 1 to Experimental Example 8 and Comparative Example 1 to Comparative Example 8 on the substrate. Hardened coating film (film thickness: 100 nm).
之後,對實驗例1至實驗例8及比較例1至比較例8的光硬化塗佈膜以下述測試方法進行評估,而其評估結果示於表1及表2。Thereafter, the photo-curing coating films of Experimental Examples 1 to 8 and Comparative Examples 1 to 8 were evaluated by the following test methods, and the evaluation results thereof are shown in Tables 1 and 2.
光硬化性:在製得實驗例1至實驗例8及比較例1至比較例8的光硬化塗佈膜後,以肉眼觀察各光硬化塗佈膜來評估光硬化性塗佈組成物的光硬化性,其評估標準如下:○:塗佈膜表面平滑;×:塗佈膜表面凹凸或是碎裂。Photocurability: After the photocurable coating films of Experimental Examples 1 to 8 and Comparative Examples 1 to 8 were obtained, each of the photocurable coating films was observed with the naked eye to evaluate the light of the photocurable coating composition. The hardening property was evaluated as follows: ○: the surface of the coating film was smooth; ×: the surface of the coating film was uneven or broken.
折射率測試:使用薄膜量測儀(Mission Peak Optics Inc.製造,型號:MP100-ST),對實驗例1至實驗例8及比較例1至比較例8的光硬化塗佈膜測定波長550nm下的折射率。當應用於一般觸控面板時,折射率的標準至少要大於1.6,越佳介於1.6至1.7之間。Refractive index test: The photohardenable coating films of Experimental Examples 1 to 8 and Comparative Examples 1 to 8 were measured at a wavelength of 550 nm using a film measuring instrument (manufactured by Mission Peak Optics Inc., model: MP100-ST). Refractive index. When applied to a general touch panel, the standard of the refractive index is at least greater than 1.6, and more preferably between 1.6 and 1.7.
穿透率測試:使用UV/Vis光譜儀(Hitachi製造,型號:U3300),對實驗例1至實驗例7及比較例1至比較例8的光硬化塗佈膜測定波長範圍380nm至450nm下的穿透率,其評估標準如下:○:穿透率≧95%;×:穿透率<95%。Penetration test: The photohardenable coating films of Experimental Examples 1 to 7 and Comparative Examples 1 to 8 were measured for the wavelength range of 380 nm to 450 nm using a UV/Vis spectrometer (manufactured by Hitachi, model: U3300). The permeability is evaluated as follows: ○: penetration rate ≧ 95%; ×: penetration rate < 95%.
黃化測試:將實驗例1至實驗例7及比較例1至比較例8的光硬化塗佈膜放置於黑布上,以由上部日光燈照亮的狀態,透過肉眼觀察所形成的光硬化塗佈膜,其評估標準如下:○:透明略為黃化; ×:嚴重黃化。Yellowing test: The photohardening coating films of Experimental Examples 1 to 7 and Comparative Examples 1 to 8 were placed on a black cloth, and the light hardening coating formed by visual observation was observed in a state illuminated by the upper fluorescent lamp. The film is evaluated as follows: ○: the transparency is slightly yellow; ×: Severe yellowing.
值得說明的是,在表2中,若評估光硬化性塗佈組成物的光硬化性不佳(×),則後續對光硬化塗佈膜進行的折射率、穿透率及黃化測試就不進行。實驗例8在後續對光硬化塗佈膜進行的穿透率及黃化測試不進行。It is worth noting that in Table 2, if the photocurability of the photocurable coating composition is evaluated to be poor (x), the refractive index, transmittance, and yellowing test of the subsequent photocurable coating film are performed. Not done. Experimental Example 8 did not perform the subsequent penetration and yellowing test on the photo-curing coating film.
以下說明下述表1及表2中的簡稱: The following abbreviations in Tables 1 and 2 are described below:
由上述表1可知,實驗例1至實驗例7的光硬化性塗佈組成物皆具有良好的光硬化性,且所製得的光硬化塗佈膜在折射率、穿透率、和黃化測試方面均有良好表現。實驗例8的光硬化性塗佈組成物具有良好的光硬化性,且所製得的光硬化塗佈膜在折射率測試方面有良好表現。相反地,由上述表2可知,比較例2、比較例4及比較例8的光硬化性塗佈組成物不具有良好的光硬化性,而比較例1、比較例3及比較例5至比較例7的光硬化性塗佈組成物雖然皆具有良好光硬化性,但所製得的光硬化塗佈膜皆無法同時在折射率、穿透率、和黃化測試方面有良好表現。As is apparent from the above Table 1, the photocurable coating compositions of Experimental Examples 1 to 7 all have good photocurability, and the obtained photohardenable coating film has refractive index, transmittance, and yellowing. Tests have performed well. The photocurable coating composition of Experimental Example 8 had good photocurability, and the obtained photocurable coating film exhibited good performance in refractive index test. On the other hand, as seen from the above Table 2, the photocurable coating compositions of Comparative Example 2, Comparative Example 4, and Comparative Example 8 did not have good photocurability, and Comparative Example 1, Comparative Example 3, and Comparative Example 5 were compared. Although the photocurable coating compositions of Example 7 all had good photocurability, the obtained photohardenable coating films could not perform well in refractive index, transmittance, and yellowing test at the same time.
綜上所述,本發明所提出的光硬化性塗佈組成物,其包括由至少式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物反應而得的光硬化性聚合物,其中以式(I)所示的金屬烷氧化物、式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物的總量為100重量份計,式(I)所示的金屬烷氧化物的含量為25重量份至50重量份,式(II)所示的金屬烷氧化物的含量為5重量份至20重量份,式(III)所示的金屬烷氧化物的含量為45重量份至70重量份。藉由包括上述光硬化性聚合物,本發明的光硬化性塗佈組成物具有良好光硬化性,且可製得在折射率、穿透率、和黃化測試方面有良好表現的光硬化塗佈膜。本發明所提出的另一光硬化性塗佈組成物,其包括基本上由式(II)所示的金屬烷氧化物及式(III)所示的金屬烷氧化物組成反應而得的光硬化性聚合物,其中以式(II)所示的金屬烷氧化物及式(III)所示的 金屬烷氧化物的總量為100重量份計,式(III)所示的金屬烷氧化物的含量為55重量份至70重量份。藉由包括上述光硬化性聚合物,本發明的光硬化性塗佈組成物具有良好光硬化性,且可製得在折射率測試方面有良好表現的光硬化塗佈膜。如此一來,使用本發明的光硬化塗佈膜的觸控面板可具備良好的視別性及顯示品質。In summary, the photocurable coating composition of the present invention comprises at least a metal alkoxide represented by the formula (I), a metal alkoxide represented by the formula (II), and a formula (III) a photocurable polymer obtained by reacting a metal alkoxide shown, wherein the metal alkoxide represented by the formula (I), the metal alkoxide represented by the formula (II), and the formula (III) The content of the metal alkoxide represented by the formula (I) is from 25 parts by weight to 50 parts by weight based on 100 parts by weight of the total amount of the metal alkoxide, and the content of the metal alkoxide represented by the formula (II) is 5. The metal alkoxide represented by the formula (III) is contained in an amount of from 45 parts by weight to 70 parts by weight per part by weight to 20 parts by weight. By including the above photocurable polymer, the photocurable coating composition of the present invention has good photocurability, and can be used to obtain a photohardenable coating which exhibits good performance in refractive index, transmittance, and yellowing test. Cloth film. Another photocurable coating composition according to the present invention, which comprises a photohardening reaction consisting essentially of a metal alkoxide represented by the formula (II) and a metal alkoxide represented by the formula (III) a polymer, wherein the metal alkoxide represented by the formula (II) and the formula (III) The metal alkoxide represented by the formula (III) is contained in an amount of from 55 parts by weight to 70 parts by weight based on 100 parts by total of the metal alkoxide. By including the photocurable polymer described above, the photocurable coating composition of the present invention has good photocurability, and a photocurable coating film which is excellent in refractive index test can be obtained. As a result, the touch panel using the photo-curing coating film of the present invention can have good visibility and display quality.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.
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