CN101243149B - Method for producing coating liquid for film formation - Google Patents

Method for producing coating liquid for film formation Download PDF

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CN101243149B
CN101243149B CN 200680029437 CN200680029437A CN101243149B CN 101243149 B CN101243149 B CN 101243149B CN 200680029437 CN200680029437 CN 200680029437 CN 200680029437 A CN200680029437 A CN 200680029437A CN 101243149 B CN101243149 B CN 101243149B
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film
solution
solvent
step
coating
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CN 200680029437
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CN101243149A (en )
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元山贤一
沼尻悟
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日产化学工业株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

Abstract

Disclosed is a method for producing a coating liquid which enables to form a coating film that is sufficiently cured under low-temperature curing conditions and enables to form an alignment film thereon which is suppressed in repelling or pinholes. Specifically disclosed is a method for producing a coating liquid for film formation characterized by comprising a step for obtaining a solution whichcontains a condensation product produced by subjecting a metal alkoxide (A) to a hydrolysis-condensation reaction in a solvent (B) [step 1], and a step for obtaining a solution by substituting the solution obtained in step 1 with a solvent (C) [step 2]. In this connection, the metal alkoxide (A) is at least one metal alkoxide selected from compounds represented by the following formula (1): Ti(OR<SUP>1</SUP>)<SUB>4</SUB> (1) (wherein R<SUP>1</SUP> represents an alkyl group having 1-5 carbon atoms); the solvent (B) is at least one organic solvent selected from the group consisting of alcohols having 1-10 carbon atoms, esters having 2-5 carbon atoms, tetrahydrofuran, and ethers having 2-5 carbon atoms; and the solvent (C) is at least one organic solvent selected from glycols having 2-10 carbon atoms.

Description

被膜形成用涂布液的制造方法技术领域 Forming a coating TECHNICAL FIELD The coating solution

[0001] 本发明涉及被膜形成用涂布液的制造方法。 [0001] The present invention relates to a method for producing a film forming coating solution. 详细而言涉及形成含有钛原子的被膜的被膜形成用涂布液的制造方法。 More specifically relates to forming a film coating containing a titanium atom by a method for producing the coating solution is formed.

背景技术 Background technique

[0002] 伴随着液晶显示元件的大型化,出于透明电极的绝缘、保护的目的,进行形成氧化物被膜的操作。 [0002] With the size of the liquid crystal display element, a transparent electrode for insulation protection purposes, the operation of forming the oxide film. 氧化物被膜的形成方法,已知有以蒸镀法、溅射法等为代表的气相法和使用氧化物被膜形成用涂布液的涂布法。 The method of forming an oxide film, there is known a deposition method, a sputtering method or the like and represented by fumed method using an oxide film is formed by coating a coating liquid. 其中,从生产性、大型基板上的被膜形成容易性的观点出发,多采用涂布法。 Wherein, of productivity, a film is formed on a large substrate easily viewpoint, the use of a coating method. 作为涂布液,已知有四烷氧基硅烷的水解产物以及与其他烷氧基金属、金属螯合物的复合物。 As the coating solution, there is known a hydrolyzate of tetraalkoxysilane, and other metal alkoxide, metal chelate complexes.

[0003] 用烷氧基金属制备涂布液时,除有机硅烷氧化物外,一般使用的烷氧基金属的水解速度慢。 [0003] When using a coating solution for preparing a metal-alkoxy, in addition to the organic silane oxide, the rate of hydrolysis of metal alkoxides used is generally slow. 因此,为了调节烷氧基金属的水解速度,尝试利用乙酰丙酮等螯合剂的作用。 Accordingly, in order to adjust the rate of hydrolysis of metal alkoxides, attempts action of acetylacetone chelating agent. 但是,通常螯合后的化合物的热解温度提高,烧结以450°C以上为宜(例如参照专利文献1)。 However, after the pyrolysis temperature is typically chelate compound increase, sintering preferably above 450 ° C (e.g., refer to Patent Document 1).

[0004] 作为其他方法,尝试了在二氧化硅_ 二氧化钛系涂布液中,通过在有机硅烷氧化物和烷氧基钛的水解产物中添加无机酸,在不使用螯合等稳定化手段的情况下制造透明的涂布剂。 [0004] As another method, attempted _ titania silica-based coating solution, by adding mineral acid hydrolyzate of the organosilane and alkoxy titanium oxide, the chelating stabilizing means, which are not used the case of producing a transparent coating agent. 即使在这种情况下,也至少需要300°C以上的烧结(例如参照专利文献2)。 Even in this case, at least more than 300 ° C sintering (see Patent Document 2).

[0005] 近年来,伴随着液晶显示元件的轻薄化,基于液晶显示元件中使用的透明电极膜的电阻值变化、基板玻璃的薄型化、滤光器的耐热性等问题,希望降低绝缘膜(氧化物被膜)的形成温度。 [0005] In recent years, along with the insulating thin film of liquid crystal display elements, based on the resistance value of the transparent electrode film element using a change, the thin glass substrate, the heat resistance of the filter the liquid crystal display and other issues, it is desirable to reduce (oxide film) formation temperature. 此外,基于液晶显示元件的制造成本削减、节能取向等情况,特别是对于在250°C以下固化的绝缘膜(氧化物被膜)的需求越来越高。 Further, based on the liquid crystal display device manufacturing cost reduction, the energy conservation orientation, etc., especially at the increasingly high demand for the 250 ° C cured insulating film (oxide film) of.

[0006] 与此同时,关于液晶显示元件的高精细化,由绝缘膜引起的液晶取向膜的凹陷、针孔等对液晶显示元件的显示特性影响大,因此希望改善绝缘膜。 [0006] Meanwhile, regarding high definition liquid crystal display element, liquid crystal alignment film of an insulating film due to the recess, the liquid crystal display such as a pinhole element display characteristics of the large impact, it is desirable to improve the insulating film. 此外,还希望随着上述改善使液晶显示元件在制造过程中的合格率提高。 In addition, as the above improvement is also desirable that the yield of the liquid crystal display element manufacturing process is improved.

[0007] 专利文献1 :日本专利特开昭63-258959号公报 [0007] Patent Document 1: Japanese Patent Laid-Open Publication No. Sho 63-258959

[0008] 专利文献2 :日本专利特开昭55-25487号公报 [0008] Patent Document 2: Japanese Patent Laid-Open Publication No. Sho 55-25487

[0009] 发明的揭示 [0009] Disclosure of the Invention

[0010] 本发明的目的在于提供能在150〜250°C这样的低温固化条件下形成充分固化的被膜并能在该被膜上形成抑制了凹陷和针孔的取向膜的被膜形成用涂布液的制造方法。 [0010] The object of the present invention to provide a fully cured coating film can be formed at a low temperature curing conditions such 150~250 ° C and can be formed in the coating film is suppressed and recessed alignment film coating liquid for forming pinholes the manufacturing methods.

[0011] 本发明者鉴于上述情况潜心研究,从而完成了本发明。 [0011] The present inventors have intensive studies in view of the above, and thus completed the present invention.

[0012] 即,本发明的技术内容如下所述。 [0012] That is, the technical details of the present invention is as follows.

[0013] 1.被膜形成用涂布液的制造方法,其特征在于,具有以下工序: [0013] 1. A method for producing a film-forming coating liquid, comprising the steps of:

[0014][工序1],得到含有使烷氧基金属(A)在溶剂(B)中进行水解·缩合反应而生成的缩合物的溶液; [0014] [Step 1], to obtain an alkoxy-containing metal (A) in a solvent (B) the hydrolysis-condensation reaction of the resulting condensate solution;

[0015][工序2],得到将所述[工序1]中得到的溶液用溶剂(C)置换后的溶液。 [0015] [Step 2], the resulting solution after the [step 1] was replaced with the solvent to give (C).

[0016] 其中,烷氧基金属(A)是选自式(1)表示的化合物(式中,R1表示碳原子数为1〜 5的烷基)中的至少1种烷氧基金属;[0017] Ti(OR1)4 (1) [0016] wherein the metal alkoxide (A) is selected from a compound represented by the formula (1) (wherein, R1 represents an alkyl group having a carbon number of 1 ~ 5) at least one kind of metal alkoxide; [ 0017] Ti (OR1) 4 (1)

[0018] 溶剂⑶是选自碳原子数为1〜10的醇、碳原子数为2〜5的酯、四氢呋喃以及碳原子数为2〜5醚中的至少1种有机溶剂;溶剂(C)是选自碳原子数为2〜10的二醇中的至少1种有机溶剂。 [0018] The solvent ⑶ carbon atoms selected from the group of 1~10 alcohol, 2 ~ 5 carbon atoms, esters, tetrahydrofuran, and 2 ~ 5 carbon atoms, an ether of at least one organic solvent; solvent (C) carbon atoms is at least one selected from organic solvents of 2~10 diol.

[0019] 2.根据1所述的制造方法,其中,烷氧基金属㈧还含有选自式(2)表示的化合物中的至少1种烷氧基硅烷。 [0019] The production method of claim 1, wherein the metal alkoxide (viii) further comprises at least one alkoxysilane compound selected from the group represented by the formula (2).

[0020] (R2)nSi(OR3)4^n (2) [0020] (R2) nSi (OR3) 4 ^ n (2)

[0021] 式中,R2表示烷基、链烯基或芳基,R3表示碳原子数为1〜5的烷基,η表示0〜2 的整数。 [0021] In the formula, R2 represents an alkyl group, an alkenyl group or an aryl group, R3 represents an alkyl group of 1 ~ 5 carbon atoms, [eta] represents an integer of 0 to 2.

[0022] 3.根据上述2所述的制造方法,其中,烷氧基硅烷是选自式(2)的η为0的化合物中的至少1种硅化合物。 [0022] The manufacturing method according to 2 above, wherein the alkoxysilane is selected from η formula (2) is at least one kind of silicon compound in the 0.

[0023] 4.根据上述1〜3中任一项所述的被膜形成用涂布液的制造方法,其中,烷氧基金属(A)含有相对于1摩尔烷氧基钛为0. 05〜4摩尔的烷氧基硅烷。 [0023] 4. The film of any one of the above-described method of producing 1~3 forming coating liquid, wherein the metal alkoxide (A) contains 1 mol of titanium alkoxide 0. 05~ 4 moles of the alkoxysilane.

[0024] 5.根据上述1〜4中任一项所述的制造方法,其中,在[工序1]中使用选自金属盐类的1种或多种催化剂。 [0024] The above-described manufacturing method according to any of 1 ~ 4, wherein the catalyst used is selected from one or more metal salts in the [step 1].

[0025] 6.根据上述1〜5中任一项所述的制造方法,其中,具有向[工序2]得到的溶液添加与该溶液互溶的溶剂(D)的[工序3]。 [0025] The production method according to any one of the above 1 ~ 5, wherein, with the [step 2] obtained was added a solution miscible with the solvent (D) in [Step 3].

[0026] 7.被膜形成用涂布液,用上述1〜6中任一项所述的制造方法得到。 [0026] 7. The film-forming coating solution, the manufacturing method according to any one of the above 1~6 obtained.

[0027] 8.被膜,用上述7所述的被膜形成用涂布液得到。 [0027] 8. The film, to give a coating liquid for forming a coating film according to 7 above.

[0028] 9.绝缘膜,用上述7所述的被膜形成用涂布液得到。 [0028] 9. The insulating film, with the film 7 formed as described above to give a coating liquid.

[0029] 10.液晶显示元件用基板,具有用上述7所述的被膜形成用涂布液形成的被膜。 [0029] 10. A liquid crystal display element substrate having a film formed by coating the coating liquid 7 above.

[0030] 11.液晶显示元件,具有用上述7所述的被膜形成用涂布液形成的被膜。 [0030] The liquid crystal display element having a film formed with the coating liquid for forming a coating film according to 7 above.

[0031] 用本发明的制造方法得到的被膜形成用涂布液,能在150〜250°C这样的低温固化条件下充分固化,并能在该被膜上形成抑制了凹陷和针孔的液晶取向膜。 [0031] forming coating liquid, can be sufficiently cured at a low temperature curing conditions such 150~250 ° C by the method for producing the film obtained according to the present invention, and can inhibit the formation of liquid crystal alignment pin holes and the recesses being film membrane. 因此,在显示特性优异的液晶显示元件的制造中有用。 Thus, manufacturing an element useful in the display characteristics of the liquid crystal display excellent.

[0032] 附图的简单说明 [0032] BRIEF DESCRIPTION OF DRAWINGS

[0033][图1]被膜形成用涂布液Z2的干燥粉末(实施例)以及涂布液Tl的干燥粉末(比较例)的重量减少率测定结果。 Z2 dried powder coating liquid (Example) [0033] [FIG 1] and the weight of the film forming coating solution Tl dry powder (Comparative Example) The results of the measurements reduced.

[0034][图2]被膜形成用涂布液Z2的干燥粉末(实施例)以及涂布液Tl的干燥粉末(比较例)的差热测定结果。 [0034] [2] The measurement results film forming coating solution Z2 dried powder (Example), and the coating solution was dried powder of Tl (Comparative Example) of the differential thermal.

[0035] 实施发明的最佳方式 [0035] BEST MODE FOR CARRYING OUT THE INVENTION

[0036] 本发明是被膜形成用涂布液的制造方法的最大特征在于,具有从溶剂(B)即选自碳原子数为1〜10的醇、碳原子数为2〜5的酯、四氢呋喃以及碳原子数为2〜5的醚中的至少1种有机溶剂向溶剂(C)即二醇置换的溶剂置换工序。 [0036] The present invention is characterized by the maximum film forming method for producing a coating liquid comprising the solvent (B) i.e. 1~10 carbon atoms selected from an alcohol, carbon atoms, esters of 2 ~ 5, tetrahydrofuran 2 ~ 5 carbon atoms and the ether substitution of at least one organic solvent to the solvent as the step (C) i.e., substituted glycols. 用本发明的制造方法得到的被膜形成用涂布液,能提供在150〜250°C这样的低温下充分固化的被膜。 The method for producing a film according to the present invention is obtained by forming coating liquid, can provide such a low temperature at 150~250 ° C sufficiently cured film. 而且,将该被膜作为液晶显示元件的电极保护膜(绝缘膜)使用时,具有如下优异的效果:能在该被膜上印刷液晶取向膜,进而能形成抑制了凹陷和针孔的取向膜。 Further, the film display element electrode protecting film (insulating film), with the following excellent effects as the liquid crystal: film can be printed in the liquid crystal alignment film, and further an alignment film is suppressed can be formed recess and pinholes.

[0037] 以往,使用烷氧基钛的水解·缩合反应,在醇等溶剂中,为了调节烷氧基钛的水解速度而在乙酰丙酮或二醇等稳定剂的存在下进行。 [0037] Conventionally, the use of titanium alkoxide hydrolysis and condensation reaction in a solvent such as an alcohol, in order to adjust the rate of hydrolysis of the titanium alkoxide and the like in the presence of acetylacetone diol or stabilizers. 这使烷氧基钛在稳定的状态下进行水解•缩合反应,生成缩合物。 This makes • hydrolyzing titanium alkoxide in a stable state condensation reaction to produce condensate. 与此相对,本发明在含有烷氧基钛的烷氧基金属进行水解•缩合反应而生成缩合物后,用二醇进行溶剂置换。 After contrast, in the present invention contains a metal alkoxide and titanium alkoxide hydrolysis • This condensation reaction to generate a condensate, the solvent was replaced with diol.

[0038] 以往是二醇等稳定剂配位的烷氧基钛或含有烷氧基钛的烷氧基金属进行水解•缩合反应而生成缩合物。 [0038] stabilizers such conventional diol is coordinated titanium alkoxide or a metal alkoxide containing titanium alkoxide hydrolysis condensation reaction to generate • condensate. 后者(本发明)则是在烷氧基钛或含有烷氧基钛的烷氧基金属进行水解·缩合反应而生成缩合物后进行二醇配位。 The latter diol complex (present invention) is the hydrolysis and condensation reaction in the titanium alkoxide or a metal alkoxide containing titanium alkoxide to generate condensate.

[0039] 考虑通过本发明获得的显著效果,推测以往进行的反应中生成的缩合物与作为稳定剂的二醇之间的配位状态和通过本发明生成的缩合物与二醇之间的配位状态是非常不同的状态。 [0039] Consider a remarkable effect obtained by the present invention, between the presumed ligand coordinated state between conventional reaction carried out with the condensate generated glycol as a stabilizer of the present invention and the resulting condensate with a diol bit state is a very different state.

[0040] 特别是缩合体的钛原子与二醇之间的配位状态,在本发明中二醇处于更易脱离的状态。 [0040] in particular between the coordinated state and the titanium atoms condensate diol, the diol in the present invention in more disengaged state.

[0041] 而且,该配位状态在涂布液以及由其得到的涂膜中继续维持,因此推测其使本发明的效果得以实现。 [0041] Further, the coordinated state and continue to maintain the coating liquid in the coating film obtained therefrom, it is presumed that the effect of the present invention which is achieved.

[0042] 换言之,对于前者,可以认为后者(本发明)中,二醇的脱离相对容易,因而在低温下涂膜易固化。 [0042] In other words, for the former, the latter may be considered (the present invention), the diol disengaged relatively easily, thereby easily curing the coating film at a low temperature.

[0043] 此外,将涂膜作为液晶显示元件的电极保护膜(绝缘膜)使用时,涂膜中的钛原子上配位的二醇少,这与抑制液晶取向膜的凹陷和针孔相关。 [0043] Further, the coating film display element electrode protecting film (insulating film) is used, the coating film of titanium atom-coordinated less diol, which is associated with inhibition of the recess and the liquid crystal alignment film a liquid crystal pinholes. 即,对于本发明,将涂膜作为液晶显示元件的电极保护膜(绝缘膜)使用时,具有使液晶取向膜的印刷性良好这一十分优异的效果。 That is, the present invention, the coating film as a liquid crystal display element electrode protecting film (insulating film) is used, the printing having good liquid crystal alignment film is excellent in the effect.

[0044] 下面,具体说明本发明。 [0044] Hereinafter, the present invention is specifically described.

[0045] 关于[工序1]: [0045] on [Step 1]:

[0046] 在该工序1中,将烷氧基金属(A)在溶剂(B)中进行水解·缩合反应。 [0046] the metal alkoxide (A) hydrolysis and condensation reaction in a solvent (B), in the step 1.

[0047] 作为该工序1中使用的烷氧基金属(A),采用选自式(1)表示的化合物中的至少1 种烷氧基钛。 [0047] As the metal alkoxide (A) used in this step 1, using at least one titanium alkoxide compound selected from the group represented by the formula (1).

[0048] Ti(OR1)4 (1) [0048] Ti (OR1) 4 (1)

[0049] 式中,R1表示碳原子数为1〜5、优选为2〜4的烷基。 [0049] formula, R1 represents a number of 1 ~ 5 carbon atoms, preferably 2 ~ 4 alkyl.

[0050] 作为式(1)表示的四烷氧基钛的具体例子,可列举四甲氧基钛、四乙氧基钛、四异丙氧基钛、四正丙氧基钛、四正丁氧基钛、四异丁氧基钛、四叔丁氧基钛、四戊氧基钛等。 [0050] Specific examples of the tetraalkoxy titanium represented by the formula (1) include tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra n-propoxy titanium, tetra-n-butyl butoxy titanium, tetraisobutoxy titanium, tetra-t-butoxy titanium, tetra pentoxy titanium. 优选为四乙氧基钛、四异丙氧基钛或四正丁氧基钛。 Preferably titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra n-butoxide or titanium.

[0051] 工序1中使用的(A)成分,只要以式(1)表示的烷氧基钛中的至少1种作为必须成分即可,不受特殊限制。 In [0051] Step 1 used in component (A), as long as the formula (1) as an essential component at least one titanium alkoxide can be represented, is not particularly limited. 因此,例如可以并用式(1)表示的烷氧基钛以外的烷氧基金属(以下称为其他烷氧基金属)。 Thus, for example, may be used in the formula (1) metal alkoxide other than the titanium alkoxide represented by (hereinafter referred to as other metal alkoxide). 作为该其他烷氧基金属,可列举Si、Al、Sn、In、Bi、Zn、Pb、Ti、 Ta、Mn、Zr等的烷氧基金属。 Examples of the other metal alkoxide include Si, Al, Sn, In, Bi, Zn, Pb, Ti, Ta, Mn, Zr or the like metal alkoxide. 这些其他烷氧基金属可以根据需要从具有1个以上烷氧基的化合物中适当选择地使用,也可以多种并用。 These other metal alkoxide may be suitably selected according to need from a compound having one or more alkoxy groups, a plurality may be used in combination.

[0052] 其中,有机硅烷氧化物(以下称为烷氧基硅烷)由于种类丰富且易于从市场购入, 因而便于使用。 [0052] wherein the organic silane oxide (hereinafter referred to as alkoxysilane) The range is broad and easily purchase from the market, and therefore easy to use. 特别是将通过本发明的制造方法得到的被膜用涂布液用于液晶显示元件时,由被膜用涂布液得到的被膜的折射率易于调节,因而优选。 The particular method of the present invention, by coating the obtained liquid crystal display element for a coating liquid, the refractive index of the coating film obtained from the coating liquid for easy adjustment, is preferable.

[0053] 此时使用的烷氧基硅烷,可以是单体,也可以使用硅酸甲酯以及硅酸乙酯的缩合体,可以使用从中选择的1种或多种。 [0053] The alkoxysilanes used in this case, may be a monomer, may be used methyl silicate and ethyl silicate condensate, may be used one or more kinds selected therefrom.

[0054] 作为硅酸甲酯以及硅酸乙酯的缩合体的具体例子,可列举硅酸乙酯40(商品名,多摩化学工业公司制)、硅酸乙酯48 (商品名,日本克罗克特(COLCOAT)公司制)、MKC硅酸酉旨(MKC Silicate,商品名,三菱化学公司制)、东丽·道康宁(T0RAY · DOW CORNING)公司制有机硅树脂、GE东芝有机硅(GETOSHIBA SILICONES)公司制有机硅树脂、信越化学工业公司制有机硅树脂、道康宁亚洲(DOW CORNING -ASIA)公司制含羟基的聚二甲基硅氧烷、日本尤丽卡(UNICA)公司制有机硅低聚物等。 [0054] Specific examples of the condensate of methyl silicate and ethyl silicate include ethyl silicate 40 (trade name, produced by Tama Chemical Industry Co., Ltd.), ethyl silicate 48 (trade name, Japan Crow Specter (COLCOAT) Corporation), MKC silicate unitary purpose (MKC silicate, trade name, manufactured by Mitsubishi chemical Corporation), Dow Corning Toray (T0RAY · DOW CORNING) manufactured silicone resin, GE Toshiba silicones (GETOSHIBA sILICONES ) a silicone resin manufactured by Shin-Etsu chemical Co., Ltd. the silicone resin, Dow Corning Asia (DOW CORNING -ASIA) Corporation hydroxyl group-containing polydimethylsiloxane, Japan You Lika (UNICA) silicone Corporation oligo and the like.

[0055] 在本发明中,特别优选使用式(2)表示的烷氧基硅烷,可以使用从中选择的1种或多种。 [0055] In the present invention, it is particularly preferable to use the formula (2) an alkoxysilane represented, may be used one or more kinds selected therefrom.

[0056] (R2)nSi(OR3)4^n (2) [0056] (R2) nSi (OR3) 4 ^ n (2)

[0057] 式中,R2表示烷基、链烯基、芳基,R3表示碳原子数为1〜5的烷基,η表示0〜2 的整数。 [0057] the formula, R2 represents an alkyl group, an alkenyl group, an aryl group, R3 represents an alkyl group of 1 ~ 5 carbon atoms, [eta] represents an integer of 0 to 2.

[0058] 下面,列举上述式(2)表示的烷氧基硅烷的具体例子,但不限于此。 [0058] Next, specific examples include alkoxysilane represented by the above formula (2), but is not limited thereto.

[0059] 可列举四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、四丁氧基硅烷等四烷氧基硅烷;甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、丁基三甲氧基硅烷、丁基三乙氧基硅烷、戊基三甲氧基硅烷、戊基三乙氧基硅烷、庚基三甲氧基硅烷、庚基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷、十二烷基三甲氧基硅烷、十二烷基三乙氧基硅烷、十六烷基三甲氧基硅烷、 十六烷基三乙氧基硅烷、十八烷基三甲氧基硅烷、十八烷基三乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、Y -氨基丙基三甲氧基硅烷、Y -氨基丙基三乙氧基硅烷、Y -环氧丙氧基丙基三甲氧基硅烷、Y -环氧丙氧基丙基三乙氧基硅烷、Y-巯基丙基三甲氧基 [0059] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like tetraalkoxysilanes; methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, propyltrimethoxysilane, propyl triethoxysilane, butyl trimethoxysilane, butyl triethoxysilane, pentyl trimethoxy silane, pentyl triethoxysilane, heptyl trimethoxysilane, heptyl triethoxysilane, octyl trimethoxysilane, octyl triethoxysilane, dodecyl trimethoxy silane, ten dialkyl triethoxysilane, hexadecyl trimethoxysilane, hexadecyl triethoxysilane, octadecyl trimethoxysilane, octadecyl triethoxysilane, phenyl trimethoxysilane silane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Y - aminopropyl trimethoxy silane, Y - aminopropyl triethoxysilane, Y - glycidoxypropyl trimethoxysilane, Y - glycidoxypropyl triethoxy silane, Y- mercaptopropyl trimethoxy 硅烷、Y-巯基丙基三乙氧基硅烷、Y-甲基丙烯酰氧基丙基三甲氧基硅烷、Y -甲基丙烯酰氧基丙基三乙氧基硅烷、Y-脲基丙基三甲氧基硅烷、Y -脲基丙基三乙氧基硅烷、三氟丙基三甲氧基硅烷、三氟丙基三乙氧基硅烷、十三氟辛基三甲氧基硅烷、十三氟辛基三乙氧基硅烷、十七氟癸基三甲氧基硅烷、十七氟癸基三乙氧基硅烷等三烷氧基硅烷;二甲基二甲氧基硅烷、二甲基二乙氧基硅烷等二烷氧基硅烷。 Silane, Y- mercapto propyl triethoxy silane, Y- methacryloxypropyl trimethoxy silane, Y - methacryloxy propyl triethoxy silane, Y- ureidopropyl trimethoxysilane, Y - ureido propyl triethoxy silane, trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane, tridecafluorooctyl trimethoxysilane, tridecafluoro-octyl triethoxysilane, heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triethoxysilane trialkoxysilane; dimethyl dimethoxy silane, dimethyl diethoxy silane dialkoxy silane.

[0060] 上述烷氧基硅烷中,η为0的四烷氧基硅烷最易获得,且价格便宜,因而便于使用。 [0060] The alkoxy silane, [eta] 0 is a tetraalkoxysilane of the most readily available, and cheap, and therefore easy to use.

[0061] 作为(A)成分,当使用式(2)表示的烷氧基硅烷时,相对于烷氧基钛1摩尔,烷氧基硅烷优选为0. 05〜4摩尔、特别优选为0. 25〜4摩尔,这易于获得如下效果:能在150〜 250°C的低温下充分固化,形成液晶取向材料的印刷性良好的涂膜。 [0061] As the component (A), when an alkoxysilane represented by the formula (2), with respect to 1 mol of titanium alkoxide, the alkoxysilane is preferably 0. 05~4 mol, particularly preferably 0. 25~4 mole, an effect which is easily obtained: sufficiently cured at a low temperature of 150~ 250 ° C, forming a printed coating film having excellent liquid crystal alignment material.

[0062] 此效果取决于工序1中生成的缩合体中的钛原子和作为(C)成分的二醇之间的配位状态。 [0062] between the coordinated state of this effect depends glycol condensate produced in step 1 as the titanium atom and (C) component. 因此,当烷氧基硅烷多于4摩尔时,上述配位以及结合状态下的二醇的量相对减少,难以获得本发明的效果。 Thus, when more than 4 mol of alkoxysilane, wherein the ligand and the amount of glycol in the coupled state relative reduction is difficult to obtain the effect of the present invention.

[0063] 另外,通过使用上述量的烷氧基硅烷,易将固化被膜的折射率在1. 50〜2. 1的范围内任意调节。 [0063] Further, by using the amount of the alkoxysilane, the refractive index of the cured film is easy to be adjusted in the range of 1. 50~2. 1.

[0064] 工序1中使用的溶剂(B)是选自碳原子数为1〜10、优选为1〜8、特别优选为1〜4的醇、碳原子数为2〜5的酯、四氢呋喃以及碳原子数为2〜5的醚中的至少1种有机溶剂。 Solvent (B) used in [0064] Step 1 is selected from the group of 1~10 carbon atoms, preferably 1~8, and particularly preferably 1 ~ 4 alcohol, 2 ~ 5 carbon atoms, esters, and tetrahydrofuran 2 ~ 5 carbon atoms, an ether of at least one organic solvent. 因此,溶剂⑶中的多种可以并用。 Thus, various solvents may be used in ⑶.

[0065] 而且,该溶剂(B)只要是溶解(A)成分的溶剂即可,不受特殊限制。 [0065] Also, the solvent (B) as long as it can dissolve component (A), and is not particularly limited. 其具体例子如下所示。 Specific examples thereof shown below.

[0066] 例如,可列举甲醇、乙醇、1-丙醇(正丙醇)、2_丙醇(异丙醇)、1_ 丁醇、2-丁醇、2-甲基-1-丙醇、己醇、辛醇、二丙酮醇、1-甲氧基-2-乙醇、1-乙氧基-2-乙醇、1-甲氧基-2-丙醇等醇;乙酸乙酯、乳酸乙酯、乙酸丁酯等酯;四氢呋喃、乙醚、1,4_ 二卩恶烷等醚 [0066] Examples thereof include methanol, ethanol, 1-propanol (n-propanol), 2_-propanol (isopropanol), 1_ butanol, 2-butanol, 2-methyl-1-propanol, hexanol, octanol, diacetone alcohol, 1-methoxy-2-ethanol, 1-ethoxy-2-ethanol, 1-methoxy-2-propanol and the like alcohols; ethyl acetate, ethyl lactate , butyl acetate and the like esters; tetrahydrofuran, diethyl ether, dioxane 1,4_ two ether Jie

Inch

[0067] 这些溶剂(B)中,最好选择难以与后述的溶剂(C)共沸且常压下的蒸气压高于溶剂(C)的溶剂。 [0067] The solvent (B), preferably selected solvent (C) described later is difficult and the vapor pressure of the azeotrope at normal pressure higher than solvent a solvent (C) is. 通过选择这样的溶剂(B),可以高效地进行从溶剂(B)向溶剂(C)的置换。 , Can be displaced from the solvent (B) to the solvent (C) efficiently by selecting such a solvent (B).

[0068] 另外,从经济方面考虑,易于使用甲醇、乙醇、丙醇、丁醇等。 [0068] Further, from the viewpoint of economy, ease of use methanol, ethanol, propanol, butanol and the like.

[0069] 工序1中,将(A)成分在溶剂⑶中进行水解·缩合反应,为了促进㈧成分的缩合,优选使用催化剂。 In [0069] Step 1, the component (A) in the hydrolysis and condensation reaction in a solvent ⑶, (viii) component in order to promote the condensation catalyst is preferably used. 催化剂的使用量,相对于烷氧基金属中的金属原子1摩尔,优选为0. 005〜0. 5摩尔。 The amount of the catalyst, relative to the metal atom in the metal alkoxide 1 mol, preferably 0.5 005~0. 5 mol.

[0070] 作为催化剂,使用酸、碱、金属无机酸盐、有机金属化合物等。 [0070] As the catalyst, an acid, an alkali metal inorganic acid salts, organic metal compounds and the like. 通常,优选使用酸或金属无机酸盐。 Generally it is preferred to use an acid or an inorganic metal salt. 该催化剂的具体例子如下所示,但不限于此。 Specific examples of the catalyst are shown below, but not limited thereto.

[0071] 酸中,作为无机酸,可列举盐酸、硝酸、硫酸、磷酸等。 [0071] acids, inorganic acids, include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like. 作为有机酸,可列举甲酸、乙酸、丙酸等单羧酸类;草酸、柠檬酸、苹果酸、琥珀酸等多元羧酸类。 The organic acids include formic, acetic, propionic monocarboxylic acids; oxalic acid, citric acid, malic acid, succinic acid and other polycarboxylic acids. 作为碱,可列举氨、苛性钠、氢氧化钾等无机碱;单乙醇胺;二乙醇胺;三乙醇胺;吡啶等。 Examples of the base include ammonia, sodium hydroxide, potassium hydroxide and the like inorganic bases; monoethanolamine; diethanolamine; triethanolamine; pyridine.

[0072] 作为催化剂使用的金属无机酸盐,是Ilia、IVa, Va族的金属或过渡金属的盐酸、 硝酸、硫酸等的无机酸盐,它们的碱式盐或它们的水合物。 [0072] As the metal catalyst used inorganic acid salts, inorganic acid salts Ilia, IVa, Va group metals or transition metals as hydrochloric acid, nitric acid, sulfuric acid and the like, basic salts thereof or hydrates thereof.

[0073] 作为Ilia、IVa、Va族的金属,可列举Al、In、Sn、Sb、Pb、Bi等。 [0073] As Ilia, IVa, Group Va metals include Al, In, Sn, Sb, Pb, Bi and the like. 作为过渡金属,可列举Ti、Mn、Fe、Ni、Zn、Y、Zr、Mo、Cu、W、Ce 等。 Examples of the transition metal include Ti, Mn, Fe, Ni, Zn, Y, Zr, Mo, Cu, W, Ce and the like.

[0074] 作为这样的金属无机酸盐的具体例子,可列举氯化铝、硝酸铝、硫酸铝、碱式氯化铝、氯化铟、硝酸铟、氯化锡、氯化锑、氯化铅、硝酸铅、硫酸铅、氯化铋、硝酸铋、氯化铁、硝酸铁、硫酸铁、氯化镍、硝酸镍、氯化锌、硝酸锌、硫酸锌、氯化钇、硝酸钇、氯化锆、硝酸锆、硫酸锆、碱式氯化锆、碱式硝酸锆、氯化钼、氯化铜、硝酸铜、硫酸铜、氯化钨、硝酸钨、氯化铈、硝酸铈等或它们的水合物等。 [0074] Specific examples of inorganic acid salts of such metals include aluminum chloride, aluminum nitrate, aluminum sulfate, basic aluminum chloride, indium chloride, indium nitrate, tin chloride, antimony chloride, lead chloride , lead nitrate, lead sulfate, bismuth chloride, bismuth nitrate, ferric chloride, ferric nitrate, ferric sulfate, nickel chloride, nickel nitrate, zinc chloride, zinc nitrate, zinc sulfate, yttrium chloride, yttrium nitrate, chloride zirconium, zirconium nitrate, zirconium sulfate, basic zirconium chloride, basic zirconium nitrate, molybdenum chloride, copper chloride, copper nitrate, copper sulfate, tungsten chloride, tungsten nitrate, cerium chloride, cerium nitrate or a hydrate.

[0075] 另外,作为有机金属化合物的具体例子,可列举乙酸铝、乙酸锌、二月桂酸二丁基锡、马来酸二丁基锡、二乙酸二丁基锡、辛酸锡、环己烷甲酸锡、双(乙酰丙酮酸)二丁基锡、 三异丙氧基铝、二异丙氧基·乙基乙酰乙酸铝、二异丙氧基·乙酰丙酮酸铝、异丙氧基· 二(乙基乙酰乙酸)铝、异丙氧基•二(乙酰丙酮酸)铝、三(乙基乙酰乙酸)铝、三(乙酰丙酮酸)铝、单乙酰丙酮酸•二(乙基乙酰乙酸)铝、四正丁氧基锆、三正丁氧基·乙基乙酰乙酸锆、二正丁氧基•二(乙基乙酰乙酸)锆、正丁氧基•三(乙基乙酰乙酸)锆、四(正丙基乙酰乙酸)锆、四(乙基乙酰乙酸)锆、四(乙基乙酰乙酸)锆等或它们的化合物的部分水解产物。 [0075] Further, specific examples of the organic metal compound include aluminum acetate, zinc acetate, dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin diacetate, tin octylate, cyclohexanecarboxylic acid, tin bis (acetylacetonate pyruvate) dibutyltin, aluminum isopropoxide, di-i-propoxy ethylacetoacetate aluminum, di-isopropoxy · acetylacetonato aluminum, isopropoxy · bis (ethylacetoacetate) aluminum, isopropoxy • bis (acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, mono- acetylacetonate • bis (ethylacetoacetate) aluminum, zirconium tetra n-butoxide , tri-n-butoxy ethyl acetoacetate zirconium, di-n-butoxy • bis (ethylacetoacetate) zirconium, n-butoxy • tris (ethylacetoacetate) zirconium, tetrakis (n-propyl acetoacetate) partial hydrolysis products of zirconium, tetrakis (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, or a compound thereof.

[0076] 上述金属无机酸盐及有机金属化合物只要在溶剂(B)中溶解即可,不受特殊限制,可以根据需要适当选择地使用。 Inorganic acid salts of the metal and the organometallic compound [0076] Just be dissolved, is not particularly limited in the solvent (B) can be suitably selected according to need. 此时,可以使用1种或多种并用。 In this case, one or more may be used in combination.

[0077] 用于电子材料领域时,优选金属硝酸盐、其碱式盐或其水合物或有机金属化合物。 [0077] When used in the field of electronic materials, preferably metal nitrates, basic salts or hydrate thereof, or an organic metal compound. 更优选Al、In、Zn、Zr、Ce、Sn的硝酸盐、其碱式盐或其水合物或有机金属化合物。 More preferably Al, In, Zn, Zr, Ce, Sn nitrate, basic salts or hydrate thereof, or an organic metal compound.

[0078] 另外,在工序1中,只要不损害本发明的效果,可以将上述金属无机盐、有机金属化合物与其他催化剂并用。 [0078] Further, in the step 1, they do not impair the effects of the present invention, the metal may be an inorganic salt, an organometallic compound and with other catalyst.

[0079] 工序1中的水解·缩合反应,可以是部分水解和/或完全水解中的任一种。 Hydrolysis-condensation reaction of the [0079] Step 1 may be partially hydrolyzed and / or in any of a fully hydrolyzed. 完全水解时,理论上,加入(A)成分中的总烷氧基的0.5倍摩尔的水即可,通常加入多于0.5倍的过剩量的水。 When fully hydrolyzed, theoretically, water was added to 0.5 mole of component (A) the total alkoxy groups, usually more than 0.5 times the addition of an excess amount of water. 部分水解时,加入0. 2〜0. 5倍摩尔的水即可。 When partially hydrolyzed, was added 0.5 2~0. 5-fold moles of water can.

[0080] 本发明中,上述反应中使用的水的量,可以根据需要适当选择,一般是(A)成分中的总烷氧基的0. 2〜2. 5倍摩尔。 [0080] In the present invention, the amount of water used in the above reaction, may be suitably selected according to, generally 0.5 2~2. 5-fold molar component (A) the total alkoxy groups. 当金属盐是含水盐时,其水分也算入上述水解中使用的水的量。 When the aqueous metal salt is a salt that can be considered the amount of water into the water used for the hydrolysis described above. [0081] 工序1将(A)成分在溶剂(B)中进行水解·缩合反应,(A)成分和溶剂(B)的添加顺序不受特殊限制。 [0081] Step 1 The component (A) hydrolysis and condensation reaction in a solvent (B) is, component (A) and a solvent (B), the order of addition is not particularly limited. 通常,采用在事先混合(A)成分中的烷氧基钛和溶剂(B)而得到的溶液中添加水、催化剂等成分的方法。 Typically, the method employed in the prior mixing component (A) and a titanium alkoxide in the solvent (B) component is added water, the resulting catalyst solution. 与其他烷氧基金属并用时,可以与烷氧基钛同时与溶剂(B)混合,也可以之后添加。 When other metal alkoxide and dried, may be mixed simultaneously with the titanium alkoxide with a solvent (B), can be added later. 此时,其他烷氧基金属可以事先用溶剂(B)稀释。 In this case, other metal alkoxides can be previously diluted with a solvent (B).

[0082] 另外,为了抑制烷氧基钛的水解,可以事先冷却后进行水解·缩合反应。 [0082] Further, in order to suppress the hydrolysis of the titanium alkoxide can be pre-cooled condensation reaction after hydrolysis. 此外,也可以在水解·缩合反应中冷却,还可以在水解·缩合反应后冷却。 Further, cooling may be in the hydrolysis-condensation reaction may also be cooled after the hydrolysis-condensation reaction.

[0083] 水和催化剂可以混合后添加,也可以分别添加。 [0083] After adding water and catalyst may be mixed, may be added separately. 通常,水和催化剂制成经溶剂(B) 稀释后的溶液来添加。 Typically, water and a catalyst solution was prepared by diluting solvent (B) be added.

[0084] 而且,为了促进㈧成分的水解•缩合反应,也可以对㈧成分和溶剂⑶的混合溶液进行加热。 [0084] Further, in order to promote the hydrolysis of component (viii) • condensation reaction may be heated to a mixed solution of the solvent and (viii) components of ⑶. 加热温度以及加热时间,可以根据需要适当选择。 The heating temperature and the heating time may be appropriately selected according to need. 例如,可列举50°C下加热·搅拌24小时,或在回流下加热·搅拌8小时等方法。 Examples thereof include 50 ° C for heated and stirred for 24 hours, or heating at reflux for 8 hours and stirring the like.

[0085] 另外,还可以在㈧成分和溶剂⑶的混合溶液的加热过程中添加水和催化剂。 [0085] Further, water may be added to the catalyst during heating and the mixed solution of the solvent and (viii) component of ⑶.

[0086] 关于经上述工序1后得到的溶液,该溶液中的总金属原子换算成氧化物的浓度(金属氧化物固体成分换算浓度)优选在20质量%以下,特别好是15质量%以下。 [0086] concentration of about 1 was obtained after the solution step, the total metal atoms in the solution in terms of an oxide (metal oxide concentration in terms of solid content) is preferably 20% by mass or less, particularly preferably 15 mass% or less. 通过在该浓度范围内选择任意的浓度,可以抑制凝胶的生成,得到勻质的溶液。 By selecting an arbitrary concentration in this concentration range, gel formation can be suppressed, homogeneous solution was obtained. 如上所述,经过工序1,可以得到含有使(A)成分在溶剂(B)中进行水解•缩合而生成的缩合物的溶液(以下称为置换前溶液)。 As described above, after step 1, can be obtained so that contain component (A) hydrolysis condensation of the resulting solution • condensate (hereinafter referred to as the replaced solution) in a solvent (B),.

[0087] 关于[工序2]: [0087] on [Step 2]:

[0088] 工序2是以将上述工序1中得到的置换前溶液的溶剂⑶置换成溶剂(C)的溶剂置换为主的工序。 [0088] Step 2 The solvent is ⑶ above step 1 was replaced with the solution before the solvent is replaced with the solvent (C) is replaced with the main step.

[0089] 这里,溶剂(C)是选自碳原子数为2〜10、优选为2〜6的二醇中的至少1种有机溶剂,也可以并用选自溶剂(C)的多种溶剂。 [0089] Here, the solvent (C) is selected from the group of 2~10 carbon atoms, preferably 2 ~ 6 diol, at least one kind of organic solvent may be selected from a variety of solvents and solvent (C) of. 下面列举溶剂(C)的具体例子,但不限于此。 Specific examples of the solvent (C) include the following, but is not limited thereto.

[0090]可列举乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、 1,4-丁二醇、1,5-戊二醇、2-甲基_2,4-戊二醇(己二醇)、3_甲基_1,5-戊二醇、1,6-己二醇、2-乙基-1,3-己二醇等。 [0090] include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4- diol, 1,5-pentanediol, 2-methyl _2,4- pentanediol (hexylene glycol), methyl _1,5- 3_ pentanediol, 1,6-hexanediol, ethyl-1,3-hexanediol.

[0091] 其中,己二醇对基板的润湿性良好,因而优选。 [0091] wherein, hexanediol good wettability to a substrate, is preferable.

[0092] 工序2中,关于将置换前溶液用溶剂(C)置换的方法,不受特殊限定。 [0092] In Step 2, a solution with a solvent front on a method (C) will be replaced with replacement, is not particularly limited.

[0093] 作为简便方法,可列举从在置换前溶液中混合了溶剂(C)的溶液馏去以溶剂(B) 为主的溶剂的方法。 [0093] As a simple method, include the mixed solvent (C) was distilled off the solvent (B) based solvent displacement method before the solution. 还可以列举边从置换前溶液馏去以溶剂(B)为主的溶剂边添加溶剂(C)的方法等。 The method may further include while adding the solvent (C) was distilled off from the solution prior to displacement solvent (B) based solvent.

[0094] 关于溶剂置换时的条件,为了提高溶剂的置换效率,通常在减压下进行,也可以在常压下进行。 [0094] About conditions for solvent replacement, in order to improve the efficiency of solvent replacement is usually carried out under reduced pressure may be carried out at normal pressure. 即,可以优选在0. lmmHg(13. 3Pa)〜760mmHg(101. 3kPa)、特别优选在5mmHg(666. 6Pa)〜200mmHg(26. 7kPa)的条件下进行溶剂置换。 That is, ~760mmHg (101. 3kPa), particularly preferably a solvent substitution under ~200mmHg (26. 7kPa) is preferably 0. lmmHg (13. 3Pa) in 5mmHg (666. 6Pa). 此时,为了进一步提高溶剂的置换效率,也可以加热。 In this case, in order to further improve the displacement efficiency of the solvent may be heated. 考虑到成本,加热温度优选为100°C以下的温度,只要是低于溶剂(C)的沸点的温度即可。 Taking into account the cost, the heating temperature is preferably a temperature below 100 ° C as long as it is below boiling point of the solvent (C) to a temperature. [0095] 在本发明中,不必将置换前溶液中的有机溶剂全部用溶剂(C)置换,优选置换前溶液中的总有机溶剂的80质量%以上置换成溶剂(C),特别优选为85质量%以上。 [0095] In the present invention, need not be replaced with the solution prior to the organic solvent completely replaced with a solvent (C), preferably substitutions 80 mass before a solution of total organic solvent% or more is replaced with the solvent (C), particularly preferably 85 mass% or more. 这样, 对于后述的被膜形成用涂布液,易于获得良好的涂布性,且柔性印刷时的涂布形成变得容易。 Thus, for a film described later coating liquid for forming easy to obtain good coating properties, and the coating is formed when the flexible printed easily. 而且,虽不明确,但在工序2的溶剂置换时,水与置换前溶液的有机溶剂共沸而被除去一部分,经工序2后得到的溶液(以下称为置换溶液)中的水分量减少,置换溶液以及使用该置换溶液得到的被膜形成用涂布液的储藏稳定性显著提高。 Moreover, is not clear, but the solvent substitution step 2, water and an organic solvent azeotropically the replaced part of the solution is removed, the solution obtained after step 2 (hereinafter referred to as replacement solution) to reduce the water content, the use of replacement solution and the coating solution was replaced with significantly improved by forming the storage stability of the coating liquid.

[0096] 工序2中,通过调节溶剂(C)的量,也可以调节置换溶液的金属氧化物固体成分换算浓度。 In [0096] Step 2, by adjusting the amount of the solvent (C), the replacement solution can be adjusted to the metal oxide concentration in terms of solid content. 此时,金属氧化物固体成分换算浓度优选为20质量%以下,特别优选为15质量% 以下。 In this case, the metal oxide solid content concentration is preferably 20% by mass or less, particularly preferably 15 mass% or less. 另外,可以根据需要选择所需的浓度。 Furthermore, you can be selected as desired concentration. [0097] 如上所述,通过进行上述工序1和工序2,可以得到将含有使(A)成分在溶剂(B) 中进行水解·缩合而生成的缩合物的溶液(置换前溶液)用溶剂(C)置换而得到的溶液, 即置换溶液。 [0097] As described above, by performing the above step 1 and step 2, containing the so obtained component (A) was performed condensate hydrolysis-condensation generated (before substitution solution) in a solvent with a solvent (B), ( C) replacement solution obtained, i.e. replacement solution.

[0098] 关于[工序3]: [0098] on [Step 3]:

[0099] 工序3是制备被膜形成用涂布液的工序,但将上述得到的置换溶液直接作为被膜形成用涂布液时,也可以省略该工序。 [0099] Step 3 is a step of preparing a coating liquid for forming a coating film, but the replacement solution obtained as described above directly as a coating liquid for forming a coating film, this step may be omitted.

[0100] 通常,为了调节被膜形成用涂布液的氧化物固体成分换算浓度、改善涂布性而进一步添加溶剂(D),制备被膜形成用涂布液。 [0100] Generally, in order to adjust an oxide film is formed in terms of solid content concentration of the coating solution to improve coatability and further by adding a solvent (D), a film forming coating solution was prepared.

[0101] 另外,只要不损害本发明的效果,还可以根据需要,添加无机微粒、表面活性剂、均化剂等其他成分。 [0101] In addition, unless impair the effects of the present invention may also be necessary, inorganic fine particles, surfactants, leveling agents other components.

[0102] 在本发明中,被膜形成用涂布液的金属氧化物换算浓度优选为0. 5〜20质量%, 特别优选为1〜15质量%。 [0102] In the present invention, the film is preferably formed in terms of the concentration of metal oxide coating solution is 0.5 5~20% by mass, and particularly preferably 1~15% by mass. 使用无机微粒时,优选使置换溶液中的金属原子和无机微粒中的金属原子的总量经氧化物换算后的浓度为0. 5〜20质量%。 When using inorganic fine particles, it is preferable that the substitution of metal atoms and metal atoms in solution in the total amount of the inorganic fine particles was calculated as the oxide concentration 0. 5~20 mass%.

[0103] 关于添加上述溶剂(D)及其他成分的方法,只要能获得勻质的溶液即可,不受特殊限定。 [0103] For adding the solvent (D) and other components of the method, as long as a homogeneous solution can be obtained, is not particularly limited.

[0104] 作为溶剂(D),使用与置换溶液互溶的溶剂,此外不受特殊限制,也可以多种并用。 [0104] As the solvent (D), using a solvent miscible with a replacement solution, addition is not particularly limited, and may be used more.

[0105] 作为其具体例子,可列举甲醇、乙醇、1-丙醇(正丙醇)、2_丙醇(异丙醇)、1_ 丁醇、2- 丁醇、2-甲基-1-丙醇、1,1- 二甲基乙醇、己醇、辛醇、二丙酮醇等醇类;乙酸乙酯、乳酸乙酯、乙酸丁酯、Y-丁内酯等酯类;四氢呋喃、乙醚、1,4_ 二卩恶烷等醚类;丙酮、2-丁酮、 3-甲基-2- 丁酮、4-甲基-2-戊酮等酮类;乙二醇、1,2-丙二醇、1,3-丙二醇、1,2- 丁二醇、 1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、1,5-戊二醇、2-甲基-2,4-戊二醇(己二醇)、3-甲基-1,5-戊二醇、1,6-己二醇、2-乙基-1,3-己二醇等二醇类;丙酮、2- 丁酮、3-甲基-2- 丁酮、4-甲基-2-戊酮等酮类;1-甲氧基-2-乙醇、1-乙氧基-2-乙醇、1-丙氧基-2-乙醇、 1- 丁氧基-2-乙醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1- 丁氧基-2-丙醇、二乙二醇单甲基醚、二乙二醇单乙基醚、二乙二醇单丁基醚、二 [0105] Specific examples thereof include methanol, ethanol, 1-propanol (n-propanol), 2_-propanol (isopropanol), 1_ butanol, 2-butanol, 2-methyl- alcohols propanol, 1,1-dimethyl ethanol, hexanol, octanol, and diacetone alcohol; ethyl acetate, ethyl lactate, butyl acetate, Y- butyrolactone; tetrahydrofuran, diethyl ether, 1,4_ two Jie and dioxane; acetone, 2-butanone, 3-methyl-2-butanone, 4-methyl-ketone; ethylene glycol, 1,2-propylene glycol , 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2- -2,4-pentanediol (hexylene glycol), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, etc. Second alcohols; acetone, 2-butanone, 3-methyl-2-butanone, 4-methyl-ketone; 1-methoxy-2-ethanol, 1-ethoxy -2 - ethanol, 1-propoxy-2-ethanol, 1-butoxy-2-ethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy 2-propanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, di 乙二醇二甲基醚、二乙二醇二乙基醚、 二乙二醇二丁基醚、二丙二醇单甲基醚、二丙二醇单乙基醚、二丙二醇单丁基醚、二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇二丁基醚、乙基卡必醇、丁基卡必醇、二乙基卡必醇等二醇醚类;N-甲基吡咯烷酮;二甲基甲酰胺、二甲基乙酰胺等酰胺类等。 Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol di glycol ether methyl ether, dipropylene glycol diethyl ether, diethylene glycol dibutyl ether, ethyl carbitol, butyl carbitol, diethyl carbitol and the like; N-methylpyrrolidone; dimethyl formamide, dimethyl acetamide and the like amides.

[0106] 作为无机微粒,优选二氧化硅微粒、氧化铝、二氧化钛、沸石等金属氧化物微粒; ATO (锑锡氧化物:antimony-tin oxide)、ITO (铟锡氧化物:indium_tinoxide)、IZO (铟锌氧化物dndium-zinc oxide)等复合氧化物微粒。 [0106] As the fine particulate inorganic metal oxide, preferably silica fine particles, alumina, titania, and zeolite; ATO (Antimony Tin Oxide: antimony-tin oxide), ITO (indium tin oxide: indium_tinoxide), IZO ( indium zinc oxide dndium-zinc oxide) composite oxide fine particles and the like. 特别优选胶体溶液。 Particularly preferably a colloidal solution. 该胶体溶液可以是将无机微粒在分散介质中分散形成的胶体溶液,也可以是市售的胶体溶液。 The colloidal solution may be a colloidal solution of the inorganic fine particles dispersed in the dispersion medium are formed, it may be a commercially available colloidal solution.

[0107] 本发明中,通过含有无机微粒,可以赋予形成的固化被膜的表面形状及其他功能。 [0107] In the present invention, by containing inorganic fine particles can be imparted to the surface shape and other features of the cured film is formed. 作为无机微粒,其平均粒径优选为0. 001〜0. 2 μ m,更优选为0. 001〜0. 1 μ m。 Examples of the inorganic fine particles having an average particle diameter is preferably 0. 001~0. 2 μ m, more preferably 0. 001~0. 1 μ m. 当无机微粒的平均粒径超过0. 2 μ m时,用制备的涂布液形成的固化被膜的透明性有时降低。 When the average particle diameter of the inorganic fine particles exceeds 0. 2 μ m, the transparency of the cured film formed with the coating liquid prepared may be lowered.

[0108] 关于无机微粒的分散介质,为了保持被膜形成用涂布液良好的保存稳定性,优选为有机溶剂。 [0108] As the inorganic fine particle dispersion medium, forming a film in order to maintain a good storage stability of the coating solution, preferably an organic solvent. 作为胶体溶液,从被膜形成用涂布液的稳定性的观点出发,PH或pKa优选调节到2〜10,特别是3〜7。 As a colloidal solution, the film is formed starting from a viewpoint of stability of coating solution, PH or pKa preferably adjusted to 2~10, particularly 3~7.

[0109] 作为胶体溶液的分散介质使用的有机溶剂,可列举甲醇、乙醇、异丙醇(2-丙醇)、 1-丁醇等醇类;乙二醇、丙二醇、己二醇、乙二醇单丙基醚等二醇类;丙酮、甲基乙基酮(2- 丁酮)、甲基异丁基酮(3-甲基-2- 丁酮)、4_甲基-2-戊酮等酮类;甲苯、二甲苯等芳香族烃类;二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮等酰胺类;乙酸乙酯、乙酸丁酯、 Y-丁内酯等酯类;四氢呋喃、1,4_二卩恶烷等醚类,以及作为溶剂(B)、溶剂(C)、溶剂⑶分别在上述例示过的溶剂。 [0109] Examples of the organic solvent solution of a colloidal dispersion medium used include methanol, ethanol, isopropanol (2-propanol), 1-butanol; glycol, propylene glycol, hexylene glycol, ethylene alcohol glycol monopropyl ether; acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone (3-methyl-2-butanone), methyl-2-4_ ketone; toluene, xylene and the like aromatic hydrocarbons; dimethylformamide, dimethylacetamide, N- methyl pyrrolidone; ethyl acetate, butyl acetate, Y- butyrolactone esters; tetrahydrofuran, 1,4_ two Jie and dioxane, as well as a solvent (B), a solvent (C), respectively, in the solvent exemplified above ⑶ off the solvent. 其中,优选醇类或二醇类。 Among these, alcohols or glycols. 这些有机溶剂可以单独或2种以上混合后作为分散介质使用。 These organic solvents may be used alone or two or more mixed as a dispersion medium.

[0110] 另外,均化剂和表面活性剂等可以使用公知的物质,特别优选市售品,因其易于获得。 [0110] Further, leveling agents and surfactants can be used known compounds, commercially available product is particularly preferable because it is readily available.

[0111] 如上所述,通过本发明得到的被膜形成用涂布液用包含[工序1]和[工序2]的制造方法来制备,根据需要也可以用包含[工序3]的方法来制备。 [0111] As described above, the film obtained by the present invention is prepared by a manufacturing method comprising a coating solution [step 1] and [step 2] is formed, according to need may be prepared by a method comprising [Step 3].

[0112][被膜的形成] [0112] [film formation]

[0113] 通过本发明的制造方法得到的被膜形成用涂布液,通过在基材上涂布,热固化,可以得到所需的固化被膜。 The coating solution is coated on a substrate by thermal curing, a cured film can give the desired [0113] formed by a coating method of the present invention is obtained. 涂布方法可以采用公知或周知的方法。 Coating method or well known method may be employed. 例如,可以采用浸涂法、流动涂布法、喷雾法、棒涂法、凹版涂布法、辊涂法、刮刀涂布法、气刀涂布法、柔性印刷法、喷墨法等。 For example, a dip coating method, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, air knife coating method, a flexographic printing method, an inkjet method or the like. 其中,柔性印刷法可以形成良好的涂膜。 Wherein the flexographic printing method can form a good coating film.

[0114] 此时,所用基材可列举塑料;玻璃;ΑΤΟ、FT0(掺氟的氧化锡dluorine-dopedtin oxide), ITO, IZO等带透明电极的玻璃;陶瓷等基材。 [0114] At this time, the base material include plastic; glass; ΑΤΟ, FT0 (fluorine doped tin oxide dluorine-dopedtin oxide), ITO, IZO transparent electrode like glass; ceramics and other substrates. 作为塑料,可列举聚碳酸酯、聚(甲基)丙烯酸酯、聚醚砜、多芳基化合物、聚氨酯、聚砜、聚醚、聚醚酮、聚烯烃、聚对苯二甲酸乙二酯、聚丙烯腈、三乙酰基纤维素、二乙酰基纤维素、乙酸丁酯纤维素等。 Examples of the plastic include polycarbonate, poly (meth) acrylates, polyether sulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketones, polyolefins, ethylene terephthalate, polyacrylonitrile, triacetyl cellulose, diacetyl cellulose, cellulose acetate, butyl acetate and the like. 其形状可列举板状或薄膜状等。 It includes a plate shape or a film shape.

[0115] 被膜形成用涂布液在涂布前通常用过滤器等过滤。 [0115] film-forming coating liquid filter is usually filtered before coating the like.

[0116] 在基材上形成的涂膜,在室温〜120°C的温度下干燥后,优选在150〜250°C温度下热固化。 [0116] The coating film formed on a substrate, at a temperature from room temperature ~120 ° C after drying, preferably at 150~250 ° C temperature of the thermal curing. 此时,干燥所需时间为30秒以上10分钟以下。 In this case, the time required for drying is 10 minutes or less 30 seconds or more.

[0117] 热固化所需时间可以根据所需固化被膜特性来适当选择,10分钟以上即可。 [0117] Time required for thermal curing can be appropriately selected depending on the desired properties of the cured film, more than 10 minutes. 当选择低固化温度时,通过延长固化时间易于获得具有充分硬度的固化被膜。 When choosing low curing temperature, the curing time extended easily obtained cured film has sufficient hardness.

[0118] 另外,本发明的被膜形成用涂布液,即使在超过250°C温度的固化温度下也可以得到具有充分硬度的固化被膜。 [0118] Further, the present invention is a film-forming coating liquid, even at temperatures exceeding 250 ° C curing temperature can be obtained a cured coating having a sufficient hardness.

[0119] 另外,在热固化之前,用汞灯、金属卤灯、氙灯、准分子灯等照射能量线(紫外线等)也有效。 [0119] Further, prior to heat curing, energy ray irradiation using a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp (ultraviolet rays) is also effective. 通过在干燥后的涂膜上照射能量线,可以进一步降低固化温度,提高被膜的硬度,提高折射率。 Irradiating energy ray through the film after drying, the curing temperature can be further reduced, to improve the hardness of the film, increase the refractive index. 能量线的照射量可以根据需要适当选择,但通常以数百〜数千mj/cm2为且。 The energy ray irradiation amount may be suitably selected according to need, but is usually several hundreds to several thousands mj / cm2 and is.

[0120] 通过本发明得到的被膜形成用涂布液,在柔性印刷领域的涂膜形成能力优异,能在低温下形成可充分固化的被膜。 [0120] This invention was formed by coating the coating liquid is excellent in film-forming ability in the field of flexographic printing, capable of forming a film can be sufficiently cured at a low temperature.

[0121] 而且,由于在该被膜上的液晶取向材料的印刷性良好,从而可以形成抑制了凹陷和针孔的液晶取向膜。 [0121] Further, since being good in printability of the alignment film of the liquid crystal material, thereby forming a liquid crystal alignment film to suppress dishing and pinholes.

[0122] 因此,通过本发明得到的被膜形成用涂布液,由于能形成具有上述特性的被膜,因而对提高液晶显示元件的显示特性非常有用。 [0122] Accordingly, the present invention is obtained by coating the coating liquid, since the coating can be formed having the above characteristics, and thus the display characteristic of the element is very useful for improving the liquid crystal display is formed.

[0123][实施例] [0123] [Example]

[0124] 下面,列举实施例和比较例,具体说明本发明,但本发明不限于下述实施例。 [0124] The following Examples and Comparative Examples, the present invention is specifically described, but the present invention is not limited to the following examples.

[0125] 本实施例中的缩略语的说明如下所示。 FIG DESCRIPTION [0125] The abbreviations in the embodiment according to the present embodiment is as follows.

[0126] TEOS :四乙氧基硅烷 [0126] TEOS: tetraethoxysilane

[0127] MTES :甲基三乙氧基硅烷 [0127] MTES: methyltriethoxysilane

[0128] ΤΕΤ:四乙氧基钛 [0128] ΤΕΤ: titanium tetraethoxide

[0129] TIPT :四异丙氧基钛 [0129] TIPT: titanium tetraisopropoxide

[0130] HG:己二醇(别名:2-甲基_2,4-戊二醇) [0130] HG: hexanediol (alias: 2-Methyl-pentanediol _2,4-)

[0131] THF:四氢呋喃 [0131] THF: Tetrahydrofuran

[0132] PG:丙二醇(别名:1,2_丙二醇) [0132] PG: Propylene glycol (alias: 1,2_ propylene glycol)

[0133] EG:乙二醇 [0133] EG: ethylene glycol

[0134] PGME :丙二醇单甲基醚(别名:1-甲氧基_2_丙醇) [0134] PGME: propylene glycol monomethyl ether (also known as: _2_ 1-methoxy-propanol)

[0135] BCS :丁基溶纤剂(别名:1- 丁氧基-2-乙醇) [0135] BCS: butyl cellosolve (alias: 1-butoxy-2-ethanol)

[0136] PB :丙二醇单丁基醚(别名:1- 丁氧基-2-丙醇) [0136] PB: propylene glycol monobutyl ether (alias: 1-butoxy-2-propanol)

[0137] AN:硝酸铝九水合物 [0137] AN: aluminum nitrate nonahydrate

[0138] CN:硝酸铈六水合物 [0138] CN: cerium nitrate hexahydrate

[0139] IN:硝酸铟三水合物 [0139] IN: indium nitrate trihydrate

[0140] 下述实施例中的测定方法如下所示。 [0140] Determination of the embodiment as shown in the following.

[0141][残留溶剂⑶的测定方法] [0141] [Measurement of the residual solvent ⑶]

[0142] 将二乙二醇二丁基醚作为稀释溶剂,将二乙二醇二乙基醚作为内标物质,制备稀释溶剂/内标物质/被膜形成用涂布液的质量比为97. 5/0. 5/2. 0的样品,通过使用了气相色谱(以下称为GC)的内标法,测定被膜形成用涂布液中残留的溶剂⑶的量。 [0142] diethylene glycol dibutyl ether as a dilution solvent, diethylene glycol diethyl ether as an internal standard substance, prepared by diluting solvent / internal standard substance / the mass ratio of film-forming coating liquid was 97. samples 5/0. 5/2. 0, by using gas chromatography (hereinafter referred to as GC) of the internal standard method of measuring the amount of film remaining in the coating liquid for forming ⑶ solvent. GC的测定条件如下所示。 GC measurement conditions are as follows.

[0143] GC测定条件: [0143] GC measurement conditions:

[0144]装置:Shimadzu GC-14B。 [0144] Apparatus: Shimadzu GC-14B.

[0145]柱子:毛细管柱、CBP1-W25-I00(25mmx0.53mm0xiym)。 [0145] Column: capillary column, CBP1-W25-I00 (25mmx0.53mm0xiym).

[0146] 柱温:柱温用升温程序控制。 [0146] Column temperature: column temperature with the temperature program control. 起始温度40°C下保持4分钟后,以15°C /分升温,终止温度300°C下保持3分钟。 After maintaining the starting temperature 40 ° C 4 min at 15 ° C / min temperature rise, the termination temperature of 300 ° C for 3 minutes.

[0147]进样量:lyL。 [0147] Injection volume: lyL.

[0148]进样温度:270°C。 [0148] Injection temperature: 270 ° C.

[0149] 检测器温度:320°C。 [0149] Detector temperature: 320 ° C.

[0150]载气:氮(流量 30mL/min)。 [0150] Carrier gas: nitrogen (flow rate 30mL / min). [0151] 检测方法:FID法。 [0151] Detection method: FID method.

[0152][制备例1] [0152] [Preparation Example 1]

[0153] 在300mL烧瓶中装入纯水2. 70g、作为溶剂(B)的乙醇62. 53g以及作为催化剂的AN 2. 96g,搅拌得到均勻的溶液。 [0153] 2. 70g of pure water was charged in a 300mL flask, ethanol as a solvent (B), 62. 53g of the catalyst as well as the AN 2. 96g, stirring to obtain a homogeneous solution. 在该溶液中加入作为其他烷氧基金属的TEOS 24.98g,室温下搅拌30分钟。 Examples of the other metal alkoxide is added TEOS 24.98g of this solution, stirred at room temperature for 30 minutes. 然后,添加TET 6. 84g,室温下搅拌30分钟。 Then, TET 6. 84g, was stirred at room temperature for 30 minutes. 将该溶液作为置换前溶液(Pl)。 This solution was used as the replaced solution (Pl).

[0154][制备例2〜11] [0154] [Preparation Example 2~11]

[0155] 按表1所示的组成,用与制备例1同样的方法制备置换前溶液(P2〜Pll)。 [0155] according to the composition shown in Table 1, was prepared by the same method as in Example 1 was prepared before the replacement solution (P2~Pll).

[0156] 但是,在制备例4中未使用其他烷氧基金属。 [0156] However, in the preparation of Example 4 other metal alkoxide is not used.

[0157] 另外,表1中的硝酸表示60质量%硝酸水溶液。 [0157] Further, in Table 1 represents 60 mass% nitric acid aqueous solution of nitric acid.

[0158] [表1] [0158] [Table 1]

[0159] [0159]

Figure CN101243149BD00121
Figure CN101243149BD00131

[0160][实施例1] [0160] [Example 1]

[0161] 在300mL烧瓶中,将制备例1中得到的置换前溶液(Pl) 24. OOg和作为溶剂(C)的HG 25.87g混合。 [0161] in 300mL flask, prepared in Example 1 was replaced with the solution before (Pl) 24. OOg as HG 25.87g and a mixed solvent (C) is. 然后,利用新型真空旋转蒸发器(东京理化器械公司制,NE-1)在60°C下边缓慢减压到20mmHg(2. 67kPa)边馏去溶剂,得到28. 91g置换溶液(Ql)。 Then, using a new vacuum rotary evaporator (manufactured by Tokyo Rikakikai Co., NE-1) at 60 ° C under gradually reduced pressure to 20mmHg (2. 67kPa) while distilling off the solvent, to give 28. 91g replacement solution (Ql). 然后,在置换溶液(Ql) 28. 91g中混合作为溶剂(D)的PGME 11. 09g,制备被膜形成用涂布液(Zl)。 Then, the replacement solution (Ql,) 28. 91g as mixed solvent (D) of PGME 11. 09g, prepared film-forming coating liquid (Zl). 对该涂布液(Zl),用GC测定溶剂⑶的残留量,结果为5.7质量%。 The coating liquid (Zl), the residual amount of the solvent ⑶ measured by GC, the result was 5.7% by mass.

[0162] 另外,对得到的被膜形成用涂布液(Zl),用后述的方法评价铅笔硬度、折射率、印刷性以及液晶取向膜印刷性。 [0162] Further, evaluation of coating solution (Zl), the method described later pencil hardness, refractive index, and printing properties of the liquid crystal alignment film is formed on the printing film obtained. 结果如表3所示。 The results are shown in Table 3.

[0163][实施例2〜15] [0163] [Example 2~15]

[0164] 按表2所示的组成,将置换前溶液(P2〜Pll)用溶剂(C)通过与实施例1同样的方法进行置换,得到置换溶液(Q2〜Q15)。 [0164] according to the composition shown in Table 2, replacing the former solution (P2~Pll) with a solvent (C) was replaced with the same manner as in Example 1, to give replacement solution (Q2~Q15). 而且,按表2所示的组成,在置换溶液(Q2〜 Q15)中加入溶剂(D),制备被膜形成用涂布液(Z2〜Z15)。 Further, according to the composition shown in Table 2, addition of solvent (D) in a replacement solution (Q2~ Q15) to prepare a film-forming coating liquid (Z2~Z15). 用GC测定该涂布液(Z2〜Z15) 中的残留溶剂(B)的量。 The amount of the coating solution (Z2~Z15) residual solvent (B) was determined by GC.

[0165] 另外,对得到的被膜形成用涂布液(Z2〜Z15),用后述的方法评价铅笔硬度、折射率、印刷性以及液晶取向膜印刷性。 [0165] Further, evaluation of coating solution (Z2~Z15), the method described later pencil hardness, refractive index, and printing properties of the liquid crystal alignment film is formed on the printing film obtained. 结果如表3所示。 The results are shown in Table 3.

[0166] [表2] [0166] [Table 2]

[0167] [0167]

Figure CN101243149BD00132
Figure CN101243149BD00141

[0168][实施例 16] [0168] [Example 16]

[0169] 在将teos 20. 8g混合到乙醇中得到的溶液中,将在乙醇23. 2g中溶解、混合水5. 4g和作为碱性催化剂的28质量%氨水溶液0. 6g得到的溶液,在室温下边搅拌边混合。 [0169] In the teos 20. 8g ethanol mixed solution obtained in 23. 2g dissolved in ethanol, and a mixed solution of water 5. 4g% aqueous ammonia solution was 28 mass 0. 6g as a basic catalyst, mixing at room temperature with stirring. 30分钟后,溶液开始呈胶体色,证实为粒状生成物。 After 30 minutes, the solution begins to form colloidal color, proved to be a granular product. 然后,在室温下继续搅拌24小时,得到Si02换算浓度为6质量%的分散于乙醇的二氧化硅胶体溶液。 Then, stirring was continued at room temperature for 24 hours, to give a concentration of Si02 in terms of 6% by mass of colloidal silica dispersed in ethanol solution. 将所得溶液的胶体粒子的粒径用dls-7000 (大塚电子公司制)测定,结果:动态光散射法得到的平均粒径为20nm。 The particle size of the colloidal particles of the resulting solution (Otsuka Electronics Co., Ltd.) was measured by dls-7000, the results: average particle diameter obtained by the dynamic light scattering method 20nm.

[0170] 接着,在300mL烧瓶中,将得到的二氧化硅胶体溶液40. Og和HG 22. 8混合。 [0170] Next, in a 300mL flask, and the resulting silica sol and HG 22. 8 40. Og mixing. 然后,利用新型真空旋转蒸发器(东京理化器械公司制,ne-1)在60°c下边缓慢减压到20mmhg (2. 67kpa)边馏去溶剂,得到25. 3g分散于hg的二氧化硅胶体溶液。 Then, using a new vacuum rotary evaporator (manufactured by Tokyo Rikakikai Co., ne-1) at 60 ° c under reduced pressure to gradually 20mmhg (2. 67kpa) while distilling off the solvent, to give 25. 3g of colloidal silica dispersed in hg body solution. 之后,在得到的分散于HG的二氧化硅胶体溶液中加入PGME14. 7g,制备粒子分散溶液K。 Thereafter, PGME14. 7g in the silica sol dispersed in HG's obtained in the preparation of particulate material dispersion K.

[0171] 将表2所示的被膜形成用涂布液(Z2) 10. OOg和粒子分散溶液K 10. OOg混合,制备被膜形成用涂布液(z16)。 [0171] The coating film is formed shown in Table 2 and 10. OOg 10. OOg mixing particulate material dispersion coating solution K (Z2), prepared film-forming coating liquid (z16).

[0172] 另外,对得到的被膜形成用涂布液(Z16),用后述的方法评价铅笔硬度、折射率、印刷性以及液晶取向膜印刷性。 [0172] Further, a coating liquid (Z16), the evaluation method described later pencil hardness, refractive index, and printing properties of the liquid crystal alignment film is formed on the printing film obtained. 结果如表3所示。 The results are shown in Table 3.

[0173][比较例1] [0173] [Comparative Example 1]

[0174] 在300mL烧瓶中,将在纯水1. 49g中溶解AN 1. 63g得到的溶液和PGME23. 66g禾口HG 26.94g混合。 [0174] in 300mL flask, dissolve AN 1. 63g and the resulting solution PGME23. 66g Hekou HG 26.94g of pure water were mixed in 1. 49g. 在其中添加TEOS 8. 60g,室温下搅拌30分钟。 Added thereto TEOS 8. 60g, it was stirred at room temperature for 30 minutes. 然后,加入事先混合TET 9. 42g和HG 28. 26g得到的溶液,室温下搅拌30分钟得到涂布液(Tl)。 Then, the mixed solution was added in advance TET 9. 42g HG 28. 26g and the resulting mixture was stirred at room temperature for 30 minutes to obtain a coating liquid (Tl). [0175] 另外,对得到的涂布液(Tl),用后述的方法评价铅笔硬度、折射率、印刷性以及液晶取向膜印刷性。 [0175] Further, the coating liquid (Tl) obtained, the evaluation method described later pencil hardness, refractive index, and a liquid crystal alignment film printing properties printability. 结果如表3所示。 The results are shown in Table 3.

[0176][比较例2] [0176] [Comparative Example 2]

[0177] 在300mL烧瓶中,将在纯水1. 31g中溶解AN 1. 43g得到的溶液和PGME24. 20g禾口HG 6. 74g混合。 [0177] in 300mL flask, and dissolved solution PGME24. 20g Hekou HG 6. 74g AN 1. 43g mixed in pure water to give 1. 31g. 在其中添加事先混合TET 16. 58g和HG 49. 74g得到的溶液,室温下搅拌30分钟得到涂布液(T2)。 Solution was added thereto and TET 16. 58g HG 49. 74g obtained mixed in advance, was stirred at room temperature for 30 minutes to obtain a coating liquid (T2).

[0178] 另外,对得到的涂布液(T2),用后述的方法评价铅笔硬度、折射率、印刷性以及液晶取向膜印刷性。 [0178] Further, the coating liquid (T2) is obtained, the evaluation method described later pencil hardness, refractive index, and a liquid crystal alignment film printing properties printability. 结果如表3所示。 The results are shown in Table 3.

[0179][比较例3] [0179] [Comparative Example 3]

[0180] 在300mL烧瓶中,将在纯水1. 49g中溶解ANl. 63g得到的溶液和PGME23. 66g 和EG 7.89g和HG 19.07g混合。 [0180] in 300mL flask, dissolved in water ANl 1. 49g. 63g and the resulting solution PGME23. 66g and HG 19.07g EG 7.89g and mixed. 在其中添加TEOS 8. 60g,室温下搅拌30分钟。 Added thereto TEOS 8. 60g, it was stirred at room temperature for 30 minutes. 然后,加入事先混合TET 9. 42g和HG 28. 25g得到的溶液,室温下搅拌30分钟得到涂布液(T3)。 Then, the mixed solution was added in advance TET 9. 42g HG 28. 25g and the resulting mixture was stirred at room temperature for 30 minutes to obtain a coating liquid (T3).

[0181] 另外,对得到的涂布液(T3),用后述的方法评价铅笔硬度、折射率、印刷性以及液晶取向膜印刷性。 [0181] Further, the coating liquid (T3) obtained, the evaluation method described later pencil hardness, refractive index, and a liquid crystal alignment film printing properties printability. 结果如表3所示。 The results are shown in Table 3.

[0182][铅笔硬度] [0182] [Pencil hardness]

[0183] 将实施例的被膜形成用涂布液以及比较例的涂布液用色谱盘(仓敷纺织公司制, 孔径0.45 μ m)过滤。 [0183] The embodiment of the film forming coating solution and the coating solution of Comparative Example (manufactured textile cladding cartridge, pore size 0.45 μ m) was filtered through a chromatography disc. 然后,滴加到带ITO的玻璃基板(ΙΤ0的膜厚为0. 7mm)上,用旋转涂布机(密卡萨(MIKASA)公司制,1H-DX2)以转速300rpm预转动5秒后,以转速4000rpm转动20秒,形成涂膜。 Then, ITO was added dropwise to a glass substrate (thickness ΙΤ0 of 0. 7mm) on a spin coater (Casa density (MIKASA) Corporation, 1H-DX2) at the pre-rotation speed of 300rpm for 5 seconds, in the rotation speed of 4000rpm for 20 seconds to form a coating. 接着,在温度80°C的热板上干燥3分钟后,在热板上以固化温度180°C 加热15分钟,得到固化被膜。 Subsequently, drying on a hot plate temperature to 80 ° C for 3 minutes, heated for 15 minutes to cure 180 ° C temperatures on a hot plate to obtain a cured film. 根据试验法(JIS K5400)测定所得的固化被膜的铅笔硬度。 (JIS K5400) measured pencil hardness of the cured film obtained according to the test method.

[0184] 在实施例3、实施例14以及比较例3中,固化温度为200°C,在实施例4和比较例2中,固化温度为250°C。 [0184] In Example 3, Example 14 and Comparative Example 3, the curing temperature is 200 ° C, in Example 4 and Comparative Example 2, the curing temperature is 250 ° C.

[0185][折射率] [0185] [Refractive Index]

[0186] 除了将基板用有机硅基板(100)代替带ITO的玻璃基板外,用与上述[铅笔硬度] 评价相同的方法形成固化被膜。 [0186] In addition to the substrate instead of a glass substrate with ITO with an organic silicon substrate (100), using the above-mentioned [Pencil Hardness] evaluated in the same manner forming a cured film. 用椭偏仪(沟尻光学工业公司制,DVA-36L型)测定波长633nm处的折射率。 Having a wavelength 633nm was measured with an ellipsometer (manufactured by Mizojiri Optical Co., DVA-36L type).

[0187][印刷性] [0187] [Printability]

[0188] 将实施例的被膜形成用涂布液以及比较例的涂布液用色谱盘(仓敷纺织公司制, 孔径0. 45 μ m)过滤。 [0188] The embodiment of the film forming coating solution and the coating solution of Comparative Example (manufactured textile cladding cartridge, aperture 0. 45 μ m) was filtered through a chromatography disc. 然后,用DR型印刷机(日本写真印刷公司制,网纹辊(360#),凸版(网点400L30% 70°C )),在带ITO的玻璃基板(ΙΤ0的膜厚为0. 7mm)上形成涂膜。 Then, the DR-type printer (Nissha Printing Co., Ltd. of Japan, the anilox roll (# 360), the relief (dot 400L30% 70 ° C)), a glass substrate with ITO (film thickness ΙΤ0 of 0. 7mm) on form a coating film. 将该涂膜在温度80°C的热板上干燥3分钟后,在热板上以固化温度180°C加热15分钟,得到固化被膜。 After the coated film was dried on a hot plate temperature to 80 ° C for 3 minutes, heated for 15 minutes to cure 180 ° C temperatures on a hot plate to obtain a cured film. 肉眼观察得到的固化被膜,当固化被膜上为没有针孔•不均的良好状态时记为〇,产生了针孔·不均的情况记为Δ,产生凹陷而未在基板上充分成膜的状态记为X。 The resulting cured film was visually observed, when cured film is not as good condition pinholes • unevenness referred to as a square, a pinhole-generating unevenness referred to as a case where [Delta] is generated in the recess without forming a film on a substrate sufficiently state referred to as X.

[0189] 在实施例3、实施例14以及比较例3中,固化温度为200°C,在实施例4和比较例2中,固化温度为250°C。 [0189] In Example 3, Example 14 and Comparative Example 3, the curing temperature is 200 ° C, in Example 4 and Comparative Example 2, the curing temperature is 250 ° C.

[0190][液晶取向膜印刷性] [0190] [liquid crystal alignment film printability]

[0191] 在用与上述[印刷性]相同的方法形成的固化被膜上,用DR型印刷机(日本写真印刷公司制,网纹辊(360#),凸版(网点400L30% 70°C )),涂布液晶取向材料(日产化学工业公司制,SUNEVER(注册商标)SE-5291032B(商品名))。 [0191] In forming the above-mentioned curable [printability] film are the same method, the DR type printer (Nissha Printing Co., Ltd. of Japan, the anilox roll (# 360), the relief (dot 400L30% 70 ° C)) coating the liquid crystal alignment material (Nissan chemical industries, Ltd., SUNEVER (registered trademark) SE-5291032B (trade name)). 然后,在温度80°C的热板上,干燥3分钟形成液晶取向膜。 Then, the temperature of a hot plate to 80 ° C, dried for 3 minutes to form a liquid crystal alignment film. 肉眼观察所形成的液晶取向膜,当液晶取向膜上为没有凹陷、 针孔和不均的良好状态时记为〇,产生了针孔或不均的情况记为Δ,产生凹陷而未在基板上充分成膜的状态记为X。 The liquid crystal alignment film formed was visually observed, when the liquid crystal alignment film is not depressed, pinholes and unevenness in good condition referred to as a square, produce pinholes or unevenness referred to as [Delta], is generated in the substrate without recess forming the full state referred to as X.

[0192] [表3] [0192] [Table 3]

[0193] [0193]

Figure CN101243149BD00161
Figure CN101243149BD00171

[0194][实施例 17] [0194] [Example 17]

[0195] 对实施例1中得到的被膜形成用涂布液(Zl),通过下述方法,评价铅笔硬度(有UV照射)、折射率(有UV照射)以及液晶取向膜印刷性(有UV照射)。 [0195] The film formed in Example 1 coating solution obtained in (Zl), by the following method, the pencil hardness evaluated (with a UV irradiation), the refractive index (with a UV irradiation) and a liquid crystal alignment film printing property (with a UV irradiation). 结果如表4所示。 The results are shown in Table 4.

[0196][实施例 18] [0196] [Example 18]

[0197] 对实施例2中得到的被膜形成用涂布液(Ζ2),通过下述方法,评价铅笔硬度(有UV照射)、折射率(有UV照射)以及液晶取向膜印刷性(有UV照射)。 [0197] Example 2 was a film-forming coating liquid (Ζ2), by the following method, the pencil hardness evaluated (with a UV irradiation), the refractive index (with a UV irradiation) and a liquid crystal alignment film printing property (with a UV irradiation). 结果如表4所示。 The results are shown in Table 4.

[0198][铅笔硬度(有UV照射)] [0198] [Pencil hardness (with a UV irradiation)]

[0199] 将被膜形成用涂布液用色谱盘(仓敷纺织公司制,孔径0. 45 μ m)过滤后,滴加到带ITO的玻璃基板上,用旋转涂布机(密卡萨(MIKASA)公司制,1H-DX2),以转速300rpm预转动5秒后,以转速4000rpm转动20秒,形成涂膜。 [0199] The film forming coating solution (manufactured textile cladding cartridge, aperture 0. 45 μ m) was filtered through a chromatography disc, dropwise added with a glass substrate with ITO by a spin coater (Casa dense ( MIKASA) Corporation, 1H-DX2), after pre-rotation rotational speed of 300rpm for 5 seconds to 20 seconds rotation speed of 4000rpm to form a coating film. 接着,在温度80°C的热板上干燥3分钟。 Subsequently, drying on a hot plate temperature to 80 ° C for 3 minutes. 之后,用紫外线照射装置(爱古拉菲克斯(EYEGRAPHICS)公司制,UB 011-3A形)、高压汞灯(输入电源1000W)以50mW/cm2 (波长350nm换算)照射2分钟(累积6000mJ/cm2), 在热板上以固化温度150°C加热15分钟,得到固化被膜。 Thereafter, the ultraviolet irradiation apparatus (爱古拉菲克斯 (Eyegraphics) Corporation, UB 011-3A-shaped), a high-pressure mercury lamp (1000W input power) irradiated 50mW / cm2 (in terms of wavelength 350nm) for 2 minutes (accumulated 6000mJ / cm2), heated for 15 minutes at a curing temperature of 150 ° C on a hot plate to obtain a cured film. 根据试验法(JISK5400)测定所得的固化被膜的铅笔硬度。 (JIS K5400) pencil hardness of the cured film was measured according to the test method obtained.

[0200][折射率(有UV照射)] [0200] [refractive index (with a UV irradiation)]

[0201] 除了将基板用有机硅基板(100)代替带ITO的玻璃基板外,用与上述[铅笔硬度(有UV照射)]评价相同的方法形成固化被膜。 [0201] In addition to the substrate instead of a glass substrate with ITO with an organic silicon substrate (100), using the above-mentioned [pencil hardness (with a UV irradiation)] The same evaluation method for forming a cured film. 用椭偏仪(沟尻光学工业公司制,DVA-36L 型)测定波长633nm处的折射率。 Having a wavelength 633nm was measured with an ellipsometer (manufactured by Mizojiri Optical Co., DVA-36L type).

[0202][液晶取向膜印刷性] [0202] [liquid crystal alignment film printability]

[0203] 在用与上述[铅笔硬度(有UV照射)]评价相同的方法形成的固化被膜上,用DR 型印刷机(日本写真印刷公司制,网纹辊(360#),凸版(网点400L30% 70°C )),涂布液晶取向材料(日产化学工业公司制,SUNEVER(注册商标)SE-5291032B(商品名))。 [0203] In the film is cured by the above-mentioned [pencil hardness (with a UV irradiation)] formed by the same evaluation method, the DR type printer (Nissha Printing Co., Ltd. of Japan, the anilox roll (# 360), the relief (dot 400L30 % 70 ° C)), applying a liquid crystal alignment material (Nissan chemical industries, Ltd., SUNEVER (registered trademark) SE-5291032B (trade name)). 之后,在温度80°C的热板上,干燥3分钟形成液晶取向膜。 Thereafter, the temperature of a hot plate to 80 ° C, dried for 3 minutes to form a liquid crystal alignment film. 肉眼观察所形成的液晶取向膜,当液晶取向膜上为没有凹陷、针孔以及不均的良好状态时记为〇,产生了针孔或不均的情况记为Δ, 产生凹陷而未在基板上充分成膜的状态记为X。 Liquid crystal alignment film formed was visually observed, when the liquid crystal alignment film is not depressed, pinholes and unevenness in good condition referred to as a square, produce pinholes or unevenness referred to as a case where [Delta] is generated in the substrate without recess forming the full state referred to as X.

[0204] [表4] [0204] [Table 4]

[0205] [0205]

Figure CN101243149BD00172

[0206][参考例1] [0206] [Reference Example 1]

[0207] 对实施例1中得到的被膜形成用涂布液(Zl),除了将固化温度由150°C变为300°C夕卜,用与实施例17同样的方法,评价铅笔硬度(有UV照射)、折射率(有UV照射)以及液晶取向膜印刷性(有UV照射)。 [0207] The film obtained in Example 1 of the embodiment forming coating liquid (Zl), except that the curing temperature of 150 ° C 300 ° C Xi Bu changed, using the same method of 17, a pencil hardness evaluation Example (with UV irradiation), the refractive index (with a UV irradiation) and a liquid crystal alignment film printing property (with a UV irradiation). 结果如表5所示。 The results are shown in Table 5.

[0208][参考例2] [0208] [Reference Example 2]

[0209] 对实施例2中得到的被膜形成用涂布液(Z2),除了将固化温度由150°C变为300°C 夕卜,用与实施例18同样的方法,评价铅笔硬度(有UV照射)、折射率(有UV照射)以及液晶取向膜印刷性(有UV照射)。 [0209] Example 2 obtained coating film forming coating solution (Z2 of), except that the curing temperature of 150 ° C 300 ° C Xi Bu changed, using the same method, the pencil hardness evaluated as in Example 18 (with UV irradiation), the refractive index (with a UV irradiation) and a liquid crystal alignment film printing property (with a UV irradiation). 结果如表5所示。 The results are shown in Table 5.

[0210] [表5] [0210] [Table 5]

[0211] [0211]

Figure CN101243149BD00181

[0212][实施例 19] [0212] [Example 19]

[0213] 称量Ig实施例2的被膜形成用涂布液(Ζ2)于称量瓶中,用烘箱在温度120°C下干燥1小时后,在温度180°C下烧结2小时。 Example 2 film is formed on the weighing bottle coating solution (Ζ2) [0213] Ig embodiment weighed, dried for 1 hour and burnt for two hours at 180 ° C temperatures in an oven at a temperature of 120 ° C. 测定烧结残分的质量,用下式算出残留有机成分量。 Determination of residue is sintered mass, calculating the amount of remaining organic component represented by the following formula. 此时,将被膜形成用涂布液中含有的全部金属原子作为氧化物算出的值作为金属氧化物固体成分量。 At this time, all of the film-forming coating liquid containing a metal atom as the value calculated as an oxide solid content of the metal oxide. 结果如表6所示。 The results are shown in Table 6.

[0214] (i)残留有机成分量(质量%) = {(烧结残分的质量-金属氧化物固体成分)/ (烧结残分的质量)}xioo [0214] (i) an amount of residual organic components (mass%) = {(mass of a residue of the sintering - a solid content of the metal oxide) / (mass of sintered residues min)} xioo

[0215] (ii)固体成分浓度(质量% ) = {(烧结残分的质量)/(被膜形成用涂布液的质fi)} XlOO [0215] (ii) a solid content concentration (mass%) = {(mass of sintered residues min) / (film forming coating liquid mass fi)} XlOO

[0216] (iii)金属氧化物换算浓度(质量%) = {(金属氧化物固体成分量)/(被膜用形成涂布液的质量)} [0216] (iii) converted to metal oxide concentration (mass%) = {(amount of the solid metal oxide) / (mass of the coating film formed with the liquid)}

[0217][比较例4] [0217] [Comparative Example 4]

[0218] 对比较例1的涂布液(Tl),除了将实施例19的被膜形成用涂布液(Z2)用涂布液(Tl)替代外,与实施例19同样,算出残留有机成分量。 [0218] The coating liquid (Tl) of Comparative Example 1, Example 19 except that the film forming coating embodiments of the liquid (Z2) is replaced with the coating liquid (Tl), the same as in Example 19, was calculated residual organic components the amount. 结果如表6所示。 The results are shown in Table 6.

[0219] [表6] [0219] [Table 6]

[0220] [0220]

Figure CN101243149BD00182

[0221][实施例 20] [0221] [Example 20]

[0222] 对实施例2的被膜形成用涂布液(Ζ2),将Ζ2滴加到玻璃基板上,用旋转涂布机(密卡萨(MIKASA)公司制,1H-DX2),以转速300rpm预转动5秒后,以转速4000rpm转动20 秒,成膜。 [0222] The forming coating liquid (Ζ2), was added dropwise to the Ζ2 on a glass substrate with a spin coater (Casa density (MIKASA) Corporation, 1H-DX2), a rotational speed of 300rpm film of Example 2 5 seconds after the pre-rotation, a rotational speed of rotation of 4000rpm for 20 seconds, the film formation. 接着,将成膜后的玻璃基板在热板上于温度80°C下干燥3分钟。 Subsequently, the glass substrate after the film formation was dried at a temperature of 80 ° C 3 minutes on a hot plate. 削取该涂膜,得到Z2的干燥粉末。 The coating film was scraped off, to obtain a dry powder Z2. 将得到的粉末用热重量差热分析测定装置(马克科学公司(Mac Science) 制,MODEL WS 002),从室温以每分钟5°C的速度升温至500°C,测定粉末的TG(重量减少率) 以及DTA(差热)。 Powder thermogravimetric differential thermal obtained measuring apparatus (Mark Scientific Co. (Mac Science) Ltd., MODEL WS 002), heated from room temperature at a rate of 5 ° C per minute to 500 ° C, measured powder TG (weight loss rate) and DTA (differential thermal). 测定结果如图1和图2所示。 The measurement results shown in FIGS. 1 and 2.

[0223] 该结果证实了140°C附近伴随着吸热的重量减少,200°C附近吸热后伴随着放热的重量减少。 [0223] This result confirms the vicinity of 140 ° C accompanied by a reduction of the weight of the endothermic, the vicinity of 200 ° C associated with an endothermic heat of weight reduction.

[0224][比较例5] [0224] [Comparative Example 5]

[0225] 除了将实施例20中的被膜形成用涂布液(Z2)用比较例1的涂布液(Tl)替代外, 与实施例20同样,测定Tl的干燥粉末的重量减少率和差热。 [0225] The procedure of Example 20 film-forming coating liquid (Z2) is replaced with the coating liquid (Tl) of Comparative Example 1, the same as in Example 20, the weight reduction rate of the dry powder and the difference between Tl heat. 测定结果如图1和图2所示。 The measurement results shown in FIGS. 1 and 2.

[0226] 该结果证实了160°C附近伴随着吸热的重量减少,230°C附近伴随着吸热的重量减少以及270°C附近伴随着放热的重量减少。 [0226] This result confirms the vicinity of 160 ° C accompanied by a reduction in the weight of the endothermic, with near 230 ° C, and the weight reduction accompanied by heat absorption near 270 ° C by weight of exotherm reduction.

[0227][总结] [0227] [summary]

[0228] 由实施例1〜实施例16的结果(参照表3)可知:通过本发明得到的被膜形成用涂布液,在低温的固化温度下,通常将其被膜作为液晶显示元件的电极保护膜(绝缘膜)使用时,显示出充分的硬度即5H以上的铅笔硬度。 [0228] 1 ~ Results Example 16 Example (see Table 3) shows that: according to the present invention is obtained by film-forming coating liquid, the curing temperature at a low temperature, it is generally used as an electrode protective film liquid crystal display element when the film (insulating film) is used, i.e., it exhibits sufficient hardness above pencil hardness of 5H.

[0229] 而且,还证实在该被膜上形成抑制了凹陷和针孔的液晶取向膜。 [0229] Moreover, the film was also confirmed that the liquid crystal alignment film formed recess suppressed and pinholes.

[0230] 另外,热固化之前,通过在干燥的涂膜上照射紫外线,可以进一步降低固化温度, 在150°C下可提高被膜的硬度和折射率,此外,在该被膜上形成的液晶取向膜显示出无凹陷和针孔的优异的成膜性。 [0230] Further, before thermal curing, by drying the coating film irradiated with ultraviolet rays, the curing temperature can be further reduced, at 150 ° C for the coating can increase the hardness and refractive index, in addition, the liquid crystal alignment film is formed on the film It exhibits excellent film formability and pinhole-free recess.

[0231] 此外,形成了可以在1. 5〜2. 1的范围内任意调节折射率的被膜。 [0231] Furthermore, a film can be adjusted to a refractive index in the range of 1. 5~2. 1.

[0232] 此外,实施例1〜实施例16的置换溶液(Ql〜Q16)以及被膜形成用涂布液(Zl〜 Z16)即使在25°C、湿度50% RH下保存1个月后,也未发现析出物的生成,证明保存稳定性非常优异。 [0232] Further, Example Embodiment 1 ~ replacement solution (Ql~Q16) Example 16 and 1 month after the film forming coating solution (Zl~ Z16) even when stored at 25 ° C, humidity 50% RH, but also No precipitation was generated, proved extremely excellent storage stability.

[0233] 实施例19和比较例4的结果(参照表6)证实,通过本发明得到的被膜形成用涂布液,在低温下固化得到的被膜中残留的有机成分(碳成分)少。 Example 19 and Comparative Example [0233] Embodiment 4 of the results (see Table 6) was confirmed, with a coating solution, coating film obtained by curing at a low temperature remaining in the organic component (component C) less film obtained by the present invention is formed. 由此可推测在低温的固化条件下有机成分(主要为二醇)发生脱离·分解。 Whereby the organic component can be estimated at a low temperature curing conditions (mainly diol) detachment and decomposition.

[0234] 由实施例20和比较例5的热重量差热分析的结果(图1和图2)可推测,用通过本发明得到的被膜形成用涂布液而形成的涂膜的残留有机成分处于更易脱离·分解的状态。 [0234] The results of thermogravimetric analysis and differential thermal Comparative Example 20 Example 5 (FIG. 1 and FIG. 2) can be estimated, the residual coating film formed by coating liquid composition for forming an organic film obtained by the present invention in more out-decomposed state. 认为该状态与促进涂膜的固化,在低温下更易固化相关。 This state is considered to promote the cured coating film, cured more relevant at low temperatures.

[0235] 产业上利用的可能性 [0235] possibility INDUSTRIAL

[0236] 通过本发明得到的被膜形成用涂布液,在柔性印刷领域的涂膜形成能力优异,能在低温下形成可充分固化的被膜。 [0236] This invention was formed by coating the coating liquid is excellent in film-forming ability in the field of flexographic printing, capable of forming a film can be sufficiently cured at a low temperature. 此外,在该被膜上可以形成抑制了凹陷和针孔的液晶取向膜。 Further, the film may be formed by a liquid crystal alignment film to suppress dishing and pinholes.

[0237] 因此,在各种电子构件、显示装置,特别是液晶显示装置中有用。 [0237] Accordingly, various electronic components, display devices, particularly useful in the liquid crystal display device.

[0238] 在此引用2005年8月19日提出申请的日本专利申请2005-239057号的说明书、 权利要求书、附图以及摘要的全部内容作为本发明的说明书的揭示。 [0238] In this specification, reference to Japanese Patent Application No. 2005-239057 filed August 19, 2005, the drawings and summary is incorporated herein is disclosed in the claims.

Claims (9)

  1. 被膜形成用涂布液的制造方法,其特征在于,具有以下工序:得到含有使烷氧基金属(A)在溶剂(B)中进行水解·缩合反应而生成的缩合物的溶液的工序1,得到将所述工序1中得到的溶液用溶剂(C)置换后的溶液的工序2;其中,烷氧基金属(A)是选自式(1)表示的化合物中的至少1种烷氧基金属,Ti(OR1)4 (1)式中,R1表示碳原子数为1~5的烷基;溶剂(B)是选自碳原子数为1~10的醇、碳原子数为2~5的酯、四氢呋喃以及碳原子数为2~5醚中的至少1种有机溶剂;溶剂(C)是选自碳原子数为2~10的二醇中的至少1种有机溶剂。 The method for producing a film forming coating liquid, comprising the steps of: obtaining a solution comprising a condensate of an alkoxy metal (A) hydrolysis and condensation reaction to form (B) in a solvent in the step 1, the resulting solution after the step of the step 1 was replaced with a solvent solution of (C) 2; wherein the metal alkoxide (a) is at least one selected from alkoxy compound represented by the formula (1) metal, Ti (OR1) 4 (1) formula, R1 represents an alkyl group having a carbon number of 1 to 5; solvent (B) selected from carbon atoms and an alcohol having 1 to 10 carbon atoms, from 2 to 5 esters, tetrahydrofuran, and the number of carbon atoms, ether having 2 to 5 at least one organic solvent; solvent (C) is selected from a diol having a carbon number of 2 to 10, at least one organic solvent.
  2. 2.如权利要求1所述的被膜形成用涂布液的制造方法,其特征在于,烷氧基金属(A)还并用选自式(2)表示的化合物中的至少1种烷氧基硅烷,(R2)nSi(OR3)4^n (2)式中,R2表示烷基、链烯基或芳基,R3表示碳原子数1〜5的烷基,η表示0〜2的整数。 2. A film according to claim 1 A method for producing coating solution is formed, characterized in that the metal alkoxide (A) and the further compound selected from the formula (2) at least one alkoxysilane , (R2) nSi (OR3) 4 ^ n (2) of formula, R2 represents an alkyl group, an alkenyl group or an aryl group, R3 represents an alkyl group of 1 ~ 5 carbon atoms, [eta] represents an integer of 0 to 2.
  3. 3.如权利要求2所述的被膜形成用涂布液的制造方法,其特征在于,烷氧基硅烷是选自式(2)的η为0的化合物中的至少1种硅化合物。 The film as claimed in claim 2, the method for producing a solution for forming a coating, wherein the alkoxysilane is selected from η formula (2) is at least one kind of silicon compound in the 0.
  4. 4.如权利要求1所述的被膜形成用涂布液的制造方法,其特征在于,烷氧基金属(A)并用相对于1摩尔烷氧基钛为0. 05〜4摩尔的烷氧基硅烷。 4. A film according to claim 1 for producing a method for forming a coating liquid, wherein the metal alkoxide (A) and treated with 1 mol of titanium alkoxide molar 0. 05~4 alkoxy silane.
  5. 5.如权利要求2所述的被膜形成用涂布液的制造方法,其特征在于,烷氧基金属(A)并用相对于1摩尔烷氧基钛为0. 05〜4摩尔的烷氧基硅烷。 5. The film according to claim 2 for producing a method for forming a coating liquid, wherein the metal alkoxide (A) and treated with 1 mol of titanium alkoxide molar 0. 05~4 alkoxy silane.
  6. 6.如权利要求1所述的被膜形成用涂布液的制造方法,其特征在于,在工序1使用选自金属盐类的1种或多种催化剂。 The film as claimed in claim 1, method of producing the coating liquid for forming, wherein, in step 1 one or more catalysts selected from metal salts.
  7. 7.如权利要求2或者5所述的被膜形成用涂布液的制造方法,其特征在于,在工序1使用选自金属盐类的1种或多种催化剂。 7. The film 2 or the method of claim 5 for producing coating solution is formed, wherein, in the step 11 one or more catalysts selected from metal salts.
  8. 8.如权利要求1所述的被膜形成用涂布液的制造方法,其特征在于,具有向工序2得到的溶液中添加与该溶液互溶的溶剂(D)的工序3。 8. A film according to claim 1 A method for producing coating solution is formed, characterized in that, with added miscible with the solution solvent (D) obtained in the step 2 to step 3 solution.
  9. 9.如权利要求2或者5所述的被膜形成用涂布液的制造方法,其特征在于,具有向工序2得到的溶液中添加与该溶液互溶的溶剂(D)的工序3。 9. The film 2 or the method of claim 5 for producing coating liquid for forming, wherein, with added miscible with the solution solvent (D) obtained in the step 2 to step 3 solution.
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CN104583350B (en) * 2012-06-14 2018-04-10 日产化学工业株式会社 Metal oxide coating a coating liquid and a metal oxide film
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