TWI411854B - A silica-based liquid crystal alignment agent, a liquid crystal alignment film, and the like - Google Patents

A silica-based liquid crystal alignment agent, a liquid crystal alignment film, and the like Download PDF

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TWI411854B
TWI411854B TW096107871A TW96107871A TWI411854B TW I411854 B TWI411854 B TW I411854B TW 096107871 A TW096107871 A TW 096107871A TW 96107871 A TW96107871 A TW 96107871A TW I411854 B TWI411854 B TW I411854B
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decane
polyoxyalkylene
liquid crystal
crystal alignment
formula
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TW200745698A (en
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Yumie Nakajima
Kenichi Motoyama
Kazuki Eguchi
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Nissan Chemical Ind Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a silicon-containing liquid crystal aligning agent which enables to produce a liquid crystal alignment film having good liquid crystal alignment and high voltage holding ratio during device operation at a low frequency under high temperature conditions. Also disclosed is a method for producing such a silicon-containing liquid crystal aligning agent. Specifically disclosed is a liquid crystal aligning agent characterized by containing the following polysiloxane (A) and polysiloxane (B). Polysiloxane (A): a polysiloxane obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the following formula (1). R<SUP>1</SUP>Si(OR<SUP>2</SUP>)<SUB>3</SUB> (1) (In the formula, R<SUP>1</SUP> represents an organic group having 8-30 carbon atoms, and R<SUP>2</SUP> represents a hydrocarbon group having 1-5 carbon atoms.) Polysiloxane (B): a polysiloxane obtained by polycondensing an alkoxysilane containing a tetraalkoxysilane represented by the following formula (2). Si(OR<SUP>3</SUP>)<SUB>4</SUB> (2) (In the formula, R<SUP>3</SUP> represents a hydrocarbon group having 1-5 carbon atoms.)

Description

矽系液晶配向劑、液晶配向膜及此等之製造方法Lanthanide liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof

本發明係關於含有將烷氧基矽烷縮聚合所得之聚矽氧烷之混合物為主之液晶配向劑及該製造方法、由上述液晶配向劑所得之液晶配向膜、及具有該液晶配向膜之液晶顯示元件。The present invention relates to a liquid crystal alignment agent containing a mixture of a polyoxyalkylene obtained by polycondensation of an alkoxysilane, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal having the liquid crystal alignment film. Display component.

液晶顯示元件係已知於透明電極上對向配置設有以聚醯胺酸或聚亞醯胺為主要成份之液晶配向膜之2枚基板，使填充液晶物質於該間隙內之構造。作為最為熟知之方式係開發扭曲向列(TN,Twisted Nematic)型液晶顯示元件，可實現比其高對比之超扭曲向列(STN,Super Twisted Nematic)型、或視角依賴性少之橫向電場效應(IPS,In-Plane Switching)型或垂直配向(VA：Vertical Alignment)型。In the liquid crystal display device, it is known that two substrates of a liquid crystal alignment film containing polyacrylic acid or polyamidamine as a main component are disposed oppositely on a transparent electrode, and a liquid crystal material is filled in the gap. The most well-known method is to develop a TN (Twisted Nematic) type liquid crystal display element, which can achieve a super-twisted nematic (STN) type with less contrast, or a transverse electric field effect with less viewing angle dependence. (IPS, In-Plane Switching) type or vertical alignment (VA: Vertical Alignment) type.

其中，以薄膜電晶體(TFT：Thin Flim Transistor)驅動之垂直配向型液晶顯示元件係具有應答速度快、超廣視角、高對比之特徵，提出要求更高品質化之多象限垂直配向(MVA,Multi-Domain Vertical Alignment)或高畫質(ASV,Advanced Super View)、垂直取向構型(PVA,Patterned Vertical Alignment)之新穎垂直配向型之液晶顯示元件。Among them, a vertical alignment type liquid crystal display element driven by a thin film transistor (TFT: Thin Flim Transistor) has the characteristics of fast response speed, wide viewing angle, and high contrast, and proposes a multi-quadrant vertical alignment (MVA, which requires higher quality). Multi-Domain Vertical Alignment) or a vertical vertical alignment type liquid crystal display element of an Advanced Super View (ASV) or a Vertically Alignment (PVA).

於此等之液晶顯示元件所設置之液晶配向膜係已知使 液晶配向，並且對於液晶顯示元件之電特性等之各種特性所造成的影響大。因此，即使對於如此新穎之垂直配向型顯示元件，開發適合其之液晶配向膜。Liquid crystal alignment films provided by such liquid crystal display elements are known to The liquid crystal is aligned and has a large influence on various characteristics such as electrical characteristics of the liquid crystal display element. Therefore, even for such a novel vertical alignment type display element, a liquid crystal alignment film suitable for the same is developed.

例如作為得到良好的垂直配向性之液晶配向膜，揭示導入長鏈烷基鏈於聚醯胺酸或聚亞醯胺之方法(例如參考專利文獻1。)、或導入環狀取代基之方法。(例如參考專利文獻2。)For example, as a liquid crystal alignment film which obtains a good vertical alignment property, a method of introducing a long-chain alkyl chain to poly-proline or poly-liminamide (for example, refer to Patent Document 1) or a method of introducing a cyclic substituent is disclosed. (For example, refer to Patent Document 2.)

另外，揭示賦予良好的垂直配向性，及高電壓保持率或低殘留DC之電特性於元件為目的，導入特定的環狀取代基於聚醯胺酸或聚亞醯胺之方法。(例如參考專利文獻3。)Further, a method of imparting a good vertical alignment property and a high voltage holding ratio or a low residual DC electrical property to an element for introducing a specific cyclic substitution based on polyglycolic acid or polyamidamine is disclosed. (For example, refer to Patent Document 3.)

最近，使用照射強度強之金屬鹵素燈作為商業用途及家庭電影院用之液晶投影機用光源，需要不僅對熱，且對光具有耐性之高液晶配向膜材料。作為該解決方法之一係揭示適用與至今之聚醯胺酸或聚亞醯胺系液晶配向膜相異物質於液晶配向膜。Recently, a metal halide lamp having a high irradiation intensity has been used as a light source for a liquid crystal projector for commercial use and home cinema, and a liquid crystal alignment film material which is not only resistant to heat but also resistant to light is required. As one of the solutions, a liquid crystal alignment film which is different from the polyamic acid or polyamidomethine liquid crystal alignment film to date has been disclosed.

例如揭示含有四烷氧基矽烷、三烷氧基矽烷及水之反應產物及甘醇醚(Glycol Ether)系溶劑之液晶配向劑組成物，開發可形成防止顯示不良，長時間驅動後亦殘存特性良好，不降低使液晶配向之能力，且對光及熱之電壓保持率降低少之液晶配向膜之液晶配向劑。(例如參考專利文獻4。)For example, a liquid crystal alignment agent composition containing a reaction product of a tetraalkoxy decane, a trialkoxy decane, and water, and a Glycol Ether solvent can be developed to prevent display defects and to remain after long-term driving. A liquid crystal alignment agent which is good in liquid crystal alignment film which does not reduce the ability to align liquid crystals and which has a low voltage retention ratio of light and heat. (For example, refer to Patent Document 4.)

如此地液晶顯示元件高機能化，另一方面，元件信賴性提昇係成為至今最大的課題。In this way, the liquid crystal display element is highly functional, and on the other hand, the component reliability improvement system has become the biggest problem to date.

傳統上，TFT型液晶顯示元件之信賴性，尤其電信賴性係藉由對應於液晶顯示元件之30赫茲動作之電壓保持率或該溫度特性而確認，如此特性係難以檢測出微小差異。因此，作為進一步確認高信賴性之方法，揭示擴大外加脈衝電壓於液晶顯示元件之間隔，以低頻率驅動元件，測定電壓保持率之方法。(例如參考專利文獻5。)Conventionally, the reliability of a TFT-type liquid crystal display device, particularly electrical reliability, is confirmed by a voltage holding ratio corresponding to a 30-Hz operation of a liquid crystal display element or the temperature characteristic, and it is difficult to detect a small difference in such characteristics. Therefore, as a method of further confirming high reliability, a method of expanding the interval between the applied pulse voltages at the liquid crystal display elements, driving the elements at a low frequency, and measuring the voltage holding ratio is disclosed. (For example, refer to Patent Document 5.)

液晶顯示元件之信賴性係不僅對於螢幕或電視機等之顯示特性之信賴性，因為直接影響提昇製造步驟之良率(yield rate)，所以係非常重要的。The reliability of the liquid crystal display element is not only reliable for display characteristics such as a screen or a television, but is directly important because it directly affects the yield rate of the manufacturing step.

另外，近年來，液晶顯示元件大型化狀況中，製造步驟之良率對液晶顯示元件的生產性比傳統影響更大，逐漸認為液晶顯示元件之電信賴性非常重要。亦即，於提昇大型液晶顯示元件生產性，提昇液晶顯示元件之信賴性是不可或缺。尤其，大多使用於電視機用或投影機用途之垂直配向型液晶顯示元件，對於電特性之信賴性之重要度大，因此，對可得到液晶配向性良好，且於高溫下藉低頻率之元件驅動中電壓保持率高之元件特性之液晶配向膜之要求非常高。Further, in recent years, in the case where the liquid crystal display element is enlarged, the yield of the manufacturing step has a greater influence on the productivity of the liquid crystal display element than the conventional one, and it is considered that the electrical reliability of the liquid crystal display element is very important. That is, it is indispensable to improve the productivity of large-sized liquid crystal display elements and improve the reliability of liquid crystal display elements. In particular, most of the vertical alignment type liquid crystal display elements used for televisions or projectors have a high importance for reliability of electrical characteristics. Therefore, components having good liquid crystal alignment and low frequency at high temperatures are available. The requirement for a liquid crystal alignment film that has a high voltage holding ratio in the driving element is very high.

專利文獻1：特開平06－3678號公報專利文獻2：特開平09－278724號公報專利文獻3：特開2001－311080號公報專利文獻4：特開2005－250244號公報專利文獻5：特開2001－264805號公報Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin 2001-264805

發明之揭示Invention disclosure

本發明係以提供可得到液晶配向性良好，且於高溫下藉低頻率之元件驅動中，電壓保持率高之液晶配向膜之矽系液晶配向劑及該製造方法、由矽系液晶配向劑所得之液晶配向膜、及具有上述液晶配向膜之液晶顯示元件為目的。The present invention provides a ruthenium-based liquid crystal alignment agent which is excellent in liquid crystal alignment and which is driven by a low-frequency element at a high temperature, and has a high voltage holding ratio, and a method for producing the same, which is obtained from a lanthanide liquid crystal alignment agent. The liquid crystal alignment film and the liquid crystal display element having the above liquid crystal alignment film are intended.

本發明者等係基於上述狀況努力研究的結果，而完成本發明。The inventors of the present invention have completed the present invention based on the results of an effort to study based on the above circumstances.

亦即，本發明係具有下述要旨者。That is, the present invention has the following gist.

1.含有下述之聚矽氧烷(A)、聚矽氧烷(B)、及溶解此等聚矽氧烷之有機溶劑為特徵之液晶配向劑。A liquid crystal alignment agent comprising a polyoxyalkylene (A), a polyoxyalkylene (B), and an organic solvent in which the polyoxyalkylene is dissolved.

聚矽氧烷(A)：將含有式(1)所表示之烷氧基矽烷之烷氧基矽烷，縮聚合所得之聚矽氧烷，[化1]R1 Si(OR2 )3 (1)(R1 係碳原子數為8至30個之有機基，R2 係表示碳原子數為1至5個之烴基。)Polyoxane (A): a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the formula (1), [Chemical Formula 1] R 1 Si(OR 2 ) 3 (1) (R 1 is an organic group having 8 to 30 carbon atoms, and R 2 is a hydrocarbon group having 1 to 5 carbon atoms.)

聚矽氧烷(B)：將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷，縮聚合所得之聚矽氧烷，但是，不併用式(1)所表示之烷氧基矽烷。Polyoxane (B): a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing a tetraalkoxydecane represented by the formula (2), but not using the alkoxy group represented by the formula (1) Base decane.

[化2]Si(OR3 )4 (2)(R3 係表示碳原子數為1至5個之烴基。)[Chem. 2] Si(OR 3 ) 4 (2) (R 3 represents a hydrocarbon group having 1 to 5 carbon atoms).

2.含有下述之聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液為特徵之液晶配向劑。2. A liquid crystal alignment agent characterized by a solution of the polyoxane (A) described below and a solution of polyoxyalkylene (B).

聚矽氧烷(A)之溶液：將含有式(1)所表示之烷氧基矽烷之烷氧基矽烷，於有機溶劑中縮聚合所得之聚矽氧烷之溶液，[化3]R1 Si(OR2 )3 (1)(R1 係碳原子數為8至30個之有機基，R2 係表示碳原子數為1至5個之烴基。)a solution of polyoxyalkylene (A): a solution of a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the formula (1) in an organic solvent, [Chemical 3]R 1 Si(OR 2 ) 3 (1) (R 1 is an organic group having 8 to 30 carbon atoms, and R 2 is a hydrocarbon group having 1 to 5 carbon atoms.)

聚矽氧烷(B)之溶液：將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷，於有機溶劑中縮聚合所得之聚矽氧烷之溶液，但是，不併用式(1)所表示之烷氧基矽烷。a solution of a polyoxane (B): a solution of a polyoxyalkylene obtained by polycondensation of an alkoxysilane having a tetraalkoxydecane represented by the formula (2) in an organic solvent, but not in combination (1) Alkoxydecane represented.

[化4]SI(OR3 )4 (2)(R3 係表示碳原子數為1至5個之烴基。)SI(OR 3 ) 4 (2) (R 3 represents a hydrocarbon group having 1 to 5 carbon atoms.)

3.上述1或2記載之液晶配向劑，其中聚矽氧烷(A)係併用至少1種式(3)所表示之烷氧基矽烷，縮聚合所得之聚矽氧烷。3. The liquid crystal alignment agent according to the above 1 or 2, wherein the polyoxyalkylene oxide (A) is a polyoxyalkylene obtained by polycondensation using at least one alkoxysilane represented by the formula (3).

[化5](R5 )n Si(OR4 )4－n (3)(R4 係分別碳原子數為1至5個之烴基，R5 係表示氫原子或碳原子數為1至5個之有機基，n係表示0至3之整數。)(R 5 ) n Si(OR 4 ) 4-n (3) (R 4 is a hydrocarbon group having 1 to 5 carbon atoms, respectively, and R 5 represents a hydrogen atom or a carbon number of 1 to 5 The organic basis, n is an integer from 0 to 3.)

4.上述1至3中任一項記載之液晶配向劑，其中聚矽氧烷(B)係更併用至少1種式(4)所表示之烷氧基矽烷，縮聚合所得之聚矽氧烷。4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein the polyoxyalkylene oxide (B) is further obtained by using at least one alkoxydecane represented by the formula (4), and polycondensed by polycondensation. .

[化6](R7 )m Si(OR6 )4－m (4)(R6 係碳原子數為1至5個之烴基，R7 係表示氫原子或碳原子數為1至6個之有機基，m係表示1或2之整數。)(R 7 ) m Si(OR 6 ) 4-m (4) (R 6 is a hydrocarbon group having 1 to 5 carbon atoms, and R 7 is a hydrogen atom or a carbon number of 1 to 6 The organic group, m represents an integer of 1 or 2.)

5.上述1或2記載之液晶配向劑，其中聚矽氧烷(A)係將式(1)所表示之烷氧基矽烷、及四乙氧基矽烷縮聚合所得之聚矽氧烷，聚矽氧烷(B)係將四乙氧基矽烷縮聚合所得之聚矽氧烷。5. The liquid crystal alignment agent according to the above 1 or 2, wherein the polyoxyalkylene (A) is a polyoxyalkylene obtained by polycondensation of an alkoxydecane represented by the formula (1) and tetraethoxysilane. The decane (B) is a polyoxyalkylene obtained by polycondensation of tetraethoxy decane.

6.上述1至5中任一項記載之液晶配向劑，其中聚矽氧烷(A)係將含有2至30莫耳%比率之式(1)所表示之烷氧基矽烷之烷氧基矽烷，縮聚合所得之聚矽氧烷。6. The liquid crystal alignment agent according to any one of the above 1 to 5, wherein the polyoxyalkylene (A) is an alkoxy group having an alkoxydecane represented by the formula (1) in a ratio of 2 to 30 mol%. Decane, polycondensation obtained by polycondensation.

7.上述1至6中任一項記載之液晶配向劑，其中聚矽氧烷(A)之矽原子之量係相對於聚矽氧烷(A)及聚矽氧烷(B)之矽原子總量，為3至80莫耳%。7. The liquid crystal alignment agent according to any one of the above 1 to 6, wherein the amount of the germanium atom of the polyoxyalkylene (A) is relative to the germanium atom of the polyoxyalkylene (A) and the polyoxyalkylene (B). The total amount is 3 to 80 mol%.

8.使用如上述1至7中任一項記載之液晶配向劑所得之液晶配向膜。A liquid crystal alignment film obtained by using the liquid crystal alignment agent according to any one of the above 1 to 7.

9.使用如上述8記載之液晶配向膜之液晶顯示元件。A liquid crystal display element using the liquid crystal alignment film according to the above 8th aspect.

10.包含混合下述之聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液之步驟為特徵之液晶配向劑之製造方法。A method for producing a liquid crystal alignment agent comprising a step of mixing a solution of the polyoxane (A) described below and a solution of polyoxyalkylene (B).

聚矽氧烷(A)之溶液：將含有式(1)所表示之烷氧基矽烷之烷氧基矽烷，於有機溶劑中縮聚合所得之聚矽氧烷之溶液，[化7]R1 Si(OR2 )3 (1)(R1 係碳原子數為8至30個之有機基，R2 係表示碳原子數為1至5個之烴基。)a solution of polyoxyalkylene (A): a solution of a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the formula (1) in an organic solvent, [Chem. 7] R 1 Si(OR 2 ) 3 (1) (R 1 is an organic group having 8 to 30 carbon atoms, and R 2 is a hydrocarbon group having 1 to 5 carbon atoms.)

聚矽氧烷(B)之溶液：將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷，於有機溶劑中縮聚合所得之聚矽氧烷之溶液。但是，不併用式(1)所表示之烷氧基矽烷。A solution of polyoxyalkylene (B): a solution of a polyoxyalkylene obtained by polycondensation of an alkoxysilane having a tetraalkoxydecane represented by the formula (2) in an organic solvent. However, the alkoxydecane represented by the formula (1) is not used in combination.

[化8]Si(OR3 )4 (2)(R3 係表示碳原子數為1至5個之烴基。)[Chem. 8] Si(OR 3 ) 4 (2) (R 3 represents a hydrocarbon group having 1 to 5 carbon atoms).

11.上述10記載之液晶配向劑之製造方法，其中聚矽氧烷(A)之溶液係將含有式(1)所表示之烷氧基矽烷之烷氧基矽烷，縮聚合所得之聚矽氧烷。11. The method for producing a liquid crystal alignment agent according to the above 10, wherein the polyoxoxane (A) solution is a polyoxyxene obtained by polycondensation of an alkoxysilane having an alkoxydecane represented by the formula (1). alkyl.

12.上述10或11記載之液晶配向劑之製造方法，其中聚矽氧烷(B)之溶液係將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷，縮聚合所得之聚矽氧烷。12. The method for producing a liquid crystal alignment agent according to the above 10 or 11, wherein the polyoxoxane (B) solution is obtained by polycondensation of an alkoxy decane containing a tetraalkoxy decane represented by the formula (2). Polyoxane.

由本發明之液晶配向劑，可得到液晶配向性良好，且於高溫下藉低頻率之元件驅動中，具有電壓保持率高之液晶配向膜。因此，可提供信賴性高之液晶顯示元件。According to the liquid crystal alignment agent of the present invention, it is possible to obtain a liquid crystal alignment film having a high voltage retention ratio when the liquid crystal alignment property is good and the element is driven at a high frequency by a low frequency. Therefore, a highly reliable liquid crystal display element can be provided.

藉由本發明為何可達成如上述功效的原因並不清楚。然而，由本發明之液晶配向劑之液晶配向膜時，如圖1顯示，於表層附近存在高碳濃度層，具有聚矽氧烷(A)集中存在液晶配向膜之表面層附近之構造。認為此構造係與上述本發明之液晶配向膜的特性有關。The reason why the above effects can be achieved by the present invention is not clear. However, in the case of the liquid crystal alignment film of the liquid crystal alignment agent of the present invention, as shown in Fig. 1, a high carbon concentration layer exists in the vicinity of the surface layer, and the structure in which the polysiloxane (A) is concentrated in the vicinity of the surface layer of the liquid crystal alignment film. This structure is considered to be related to the characteristics of the liquid crystal alignment film of the present invention described above.

用以實施發明之最佳型態The best form for implementing the invention

以下係詳細地說明本發明。The invention is described in detail below.

<聚矽氧烷(A)><polyoxane (A)>

本發明使用之聚矽氧烷(A)係將含有式(1)所表示之烷氧基矽烷之烷氧基矽烷縮聚合所得。The polyoxyalkylene (A) used in the present invention is obtained by polycondensation of an alkoxysilane containing an alkoxydecane represented by the formula (1).

[化9]R1 Si(OR2 )3 (1)[Chemical 9] R 1 Si(OR 2 ) 3 (1)

式(1)之R1 係碳原子數為8至30個之有機基，如脂肪族烴、脂肪族環、芳香族環及雜環之環構造、不飽和鍵、及可含有氧原子、氮原子或硫原子等之雜原子等，亦可具有支鏈構造。並且，此有機基係亦可為鹵原子、乙烯基、胺基、環氧丙氧基、巰基、脲基、甲基丙酰氧基、異氰酸基、丙烯酰氧基等所取代。The R 1 group of the formula (1) is an organic group having 8 to 30 carbon atoms, such as an aliphatic hydrocarbon, an aliphatic ring, an aromatic ring, and a heterocyclic ring structure, an unsaturated bond, and an oxygen atom or a nitrogen atom. A hetero atom such as an atom or a sulfur atom may have a branched structure. Further, the organic group may be substituted by a halogen atom, a vinyl group, an amine group, a glycidoxy group, a decyl group, a ureido group, a methylpropionyloxy group, an isocyanate group or an acryloyloxy group.

如此有機基R1 之具體例時，可舉例如烷基、全氟烷基、鏈烯基、烯丙氧基烷基、苯乙基、全氟苯基烷基、苯基胺基烷基、苯乙烯基烷基、萘基、苯醯氧基烷基、烷氧基苯氧基烷基、環烷基胺基烷基、環氧環烷基、N-(胺基烷基)胺基烷基、N-(胺基烷基)胺基烷基苯乙基、溴化烷基、二苯基膦基、N-(甲基丙酰氧基羥基烷基)胺基烷基、N－(丙酰氧基羥基烷基)胺基烷基等。Specific examples of the organic group R 1 include an alkyl group, a perfluoroalkyl group, an alkenyl group, an allyloxyalkyl group, a phenethyl group, a perfluorophenylalkyl group, and a phenylaminoalkyl group. Styrylalkyl, naphthyl, benzomethoxyalkyl, alkoxyphenoxyalkyl, cycloalkylaminoalkyl, epoxycycloalkyl, N-(aminoalkyl)aminoalkane , N-(aminoalkyl)aminoalkylphenethyl, alkyl bromide, diphenylphosphino, N-(methylpropionyloxyhydroxyalkyl)aminoalkyl, N-( Propionyloxyhydroxyalkyl)aminoalkyl and the like.

其中，作為有機基R1 ，係以碳原子數為8至30個之烷基為宜，以碳原子數為8至20個之烷基尤佳。Among them, as the organic group R 1 , an alkyl group having 8 to 30 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is particularly preferable.

式(1)之R2 係表示烴基，因為碳原子數少，反應性高，所以以碳原子數為1至5個之飽和烴基為宜。以甲基、乙基、丙基、丁基尤佳。R 2 of the formula (1) represents a hydrocarbon group. Since the number of carbon atoms is small and the reactivity is high, it is preferred to use a saturated hydrocarbon group having 1 to 5 carbon atoms. It is especially preferred as methyl, ethyl, propyl or butyl.

本發明中可使用式(1)所表示之烷氧基矽烷中之至少1種，因應需要，亦可使用多種。In the present invention, at least one of the alkoxysilanes represented by the formula (1) can be used, and a plurality of them can be used as needed.

作為如此式(1)所表示之烷氧基矽烷之具體例，可舉例如辛基三甲氧基矽烷、辛基三乙氧基矽烷、癸基三甲氧基矽烷、癸基三乙氧基矽烷、十二烷基三甲氧基矽烷、十二烷基三乙氧基矽烷、十六烷基三甲氧基矽烷、十六烷基三乙氧基矽烷、十七烷基三甲氧基矽烷、十七烷基三乙氧基矽烷、十八烷基三甲氧基矽烷、十八烷基三乙氧基矽烷、十九烷基三甲氧基矽烷、十九烷基三乙氧基矽烷、十一烷基三乙氧基矽烷、十一烷基三甲氧基矽烷、21－二十二烷基三乙氧基矽烷、烯丙氧基十一烷基三乙氧基矽烷、十三氟辛基三甲氧基矽烷、十三氟辛基三乙氧基矽烷、異辛基三乙氧基矽烷、苯乙基三乙氧基矽烷、五氟苯基丙基三甲氧基矽烷、N－苯基胺基丙基三甲氧基矽烷、N－(三乙氧基甲矽烷基丙烷)dansilyamide、苯乙烯基乙基三乙氧基矽烷、(R)－N－1－苯基乙基－N’－三乙氧基甲矽烷基丙脲、(1－萘基)三乙氧基矽烷、(1－萘基)三甲氧基矽烷、間苯乙烯基乙基三甲氧基矽烷、對苯乙烯基乙基三甲氧基矽烷、N-[3-(三乙氧基甲矽烷基)丙基]酞醯胺酸、1-三甲氧基甲矽烷基-2-(對胺基甲基)苯基乙烷、1-三甲氧基甲矽烷基-2-(間胺基甲基)苯基乙烷、苯醯氧基丙基三甲氧基矽烷、3-(4-甲氧基苯氧基)丙基三甲氧基矽烷、N-三乙氧基甲矽烷基丙基基寧尿烷、3-(N-環己基胺基)丙基三甲氧基矽烷、1-[(2-三乙氧基甲矽烷基)乙基]環己烷-3,4-環氧化物、N-(6-胺基己基)胺基丙基三甲氧基矽烷、胺基乙基胺基甲基苯乙基三甲氧基矽烷、11-溴化十一烷基三甲氧基矽烷、2-(二苯基膦基)乙基三乙氧基矽烷、N-(3-甲基丙酰氧基-2-羥基丙基)-3-胺基丙基三乙氧基矽烷、N-(3-丙酰氧基-2-羥基丙基)-3-胺基-丙基三乙氧基矽烷等。Specific examples of the alkoxydecane represented by the formula (1) include, for example, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, and decyltriethoxydecane. Dodecyltrimethoxydecane, dodecyltriethoxydecane, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane,heptadecane Triethoxy decane, octadecyl trimethoxy decane, octadecyl triethoxy decane, nonadecyl trimethoxy decane, nonadecyl triethoxy decane, undecyl three Ethoxydecane, undecyltrimethoxydecane, 21-docosyltriethoxydecane, allyloxyundecyltriethoxydecane,tridecafluorooctyltrimethoxydecane , tridecafluorooctyltriethoxydecane, isooctyltriethoxydecane,phenethyltriethoxydecane, pentafluorophenylpropyltrimethoxydecane, N-phenylaminopropyltrimethyl Oxydecane, N-(triethoxymethane alkylpropane)dansilyamide, styrylethyltriethoxydecane, (R)-N-1-phenylethyl-N' Triethoxymethyl decyl propyl urea, (1-naphthyl) triethoxy decane, (1-naphthyl) trimethoxy decane, m-styrylethyl trimethoxy decane, p-styrylethyl Trimethoxy decane, N-[3-(triethoxymethanealkyl)propyl]proline, 1-trimethoxycarbamido-2-(p-aminomethyl)phenylethane, 1-trimethoxycarbamido-2-(m-aminomethyl)phenylethane, phenoxypropyltrimethoxydecane, 3-(4-methoxyphenoxy)propyltrimethoxy Base decane, N-triethoxymethane propyl propyl urethane, 3-(N-cyclohexylamino)propyl trimethoxy decane, 1-[(2-triethoxycarbenyl) Ethyl]cyclohexane-3,4-epoxide, N-(6-aminohexyl)aminopropyltrimethoxydecane, aminoethylaminomethylphenethyltrimethoxydecane, 11 - undecyltrimethoxydecane bromide, 2-(diphenylphosphino)ethyltriethoxydecane, N-(3-methylpropionyloxy-2-hydroxypropyl)-3- Aminopropyltriethoxydecane, N-(3-propionyloxy-2-hydroxypropyl)-3-amino-propyltriethoxydecane, and the like.

本發明所使用之聚矽氧烷(A)係縮聚合含有式(1)之烷氧基矽烷所得，於溶劑中為均質之溶液狀態即可。The polyoxyalkylene (A) used in the present invention is obtained by polycondensation polymerization containing the alkoxysilane of the formula (1), and it may be in a homogeneous solution state in a solvent.

本發明所使用之聚矽氧烷(A)之中，以使用使式(1)所表示之烷氧基矽烷及式(3)所表示之烷氧基矽烷縮聚合所得者為宜。Among the polyoxyalkylenes (A) used in the present invention, those obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (3) are preferred.

[化10](R5 )n Si(OR4 )4-n (3)式(3)之R4 係表示碳原子數為1至5個之烴基，以碳原子數為1至5個之飽和烴基為宜，以甲基、乙基、丙基、丁基為宜。(R 5 ) n Si(OR 4 ) 4-n (3) R 4 of the formula (3) represents a hydrocarbon group having 1 to 5 carbon atoms, and has 1 to 5 carbon atoms. A saturated hydrocarbon group is preferred, and a methyl group, an ethyl group, a propyl group or a butyl group is preferred.

接著，式(3)之R5 係氫原子或碳原子數為1至5個之有機基。此有機基係只要碳原子數為1至5個即可，無特別的限制。接著，此有機基亦可含有氧原子、氮原子及硫原子等之雜原子，亦可具有不飽和鍵或環構造。進而，亦可以甲基、乙基、異丙基、正丙基等之飽和烴基、如乙烯基之不飽和烴基、胺基、環氧丙氧基、巰基、脲基、異氰酸基等取代。Next, R 5 of the formula (3) is a hydrogen atom or an organic group having 1 to 5 carbon atoms. The organic group is not particularly limited as long as it has 1 to 5 carbon atoms. Next, the organic group may contain a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, or may have an unsaturated bond or a ring structure. Further, a saturated hydrocarbon group such as a methyl group, an ethyl group, an isopropyl group or a n-propyl group, or an unsaturated hydrocarbon group such as a vinyl group, an amine group, a glycidoxy group, a decyl group, a ureido group or an isocyanate group may be substituted. .

式(3)之n係表示0至3之整數。尤其n為0時，表示四烷氧基矽烷。The n of the formula (3) represents an integer of 0 to 3. In particular, when n is 0, it represents a tetraalkoxydecane.

作為如此式(3)所表示之烷氧基矽烷之具體例，可舉例如四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、甲基三丙氧基矽烷、3－胺基丙基三甲氧基矽烷、3－胺基丙基三乙氧基矽烷、N－2(胺基乙基)3－胺基丙基三乙氧基矽烷、N－2(胺基乙基)3－胺基丙基三甲氧基矽烷、3－(2－胺基乙基胺基丙基)三甲氧基矽烷、3－(2－胺基乙基胺基丙基)三乙氧基矽烷、2－胺基乙基胺基甲基三甲氧基矽烷、2－(2－胺基乙基硫乙基)三乙氧基矽烷、3－巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、3－脲基丙基三乙氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、烯丙基三乙氧基矽烷、3－異氰酸酯丙基三乙氧基矽烷、三氟丙基三甲氧基矽烷、環丙基三乙氧基矽烷、溴化丙基三乙氧基矽烷等。Specific examples of the alkoxydecane represented by the formula (3) include tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane, tetrabutoxydecane, and methyltrimethoxydecane. , methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, methyl tripropoxy decane, 3-amine Propyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2 (aminoethyl) 3-aminopropyltriethoxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane, 3-(2-aminoethylaminopropyl)trimethoxynonane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-Aminoethylaminomethyltrimethoxydecane, 2-(2-aminoethylthioethyl)triethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxy Basear, 3-ureidopropyltriethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, allyltriethoxydecane, 3-isocyanatepropyltriethoxydecane, Trifluoropropyltrimethyl Oxydecane, cyclopropyltriethoxydecane, bromopropyltriethoxydecane, and the like.

本發明中所使用之式(3)所表示之烷氧基矽烷係因應需要，可使用1種或多種。The alkoxysilane represented by the formula (3) used in the present invention may be used alone or in combination as needed.

本發明中，此等式(3)所表示之烷氧基矽烷中，使用n為0之四烷氧基矽烷，因為容易與式(1)所表示之烷氧基矽烷縮聚合，所以適合用以得到聚矽氧烷(A)。In the present invention, in the alkoxydecane represented by the formula (3), a tetraalkoxydecane having n of 0 is used, and since it is easily condensed with the alkoxysilane represented by the formula (1), it is suitable for use. To obtain polyoxyalkylene (A).

式(1)所表示之烷氧基矽烷之使用比率係為得到聚矽氧烷(A)所使用總烷氧基矽烷中，未滿2莫耳%時，因為不能得到良好液晶配向性，所以以2莫耳%以上為宜。以3莫耳%以上尤佳。另外，超過30莫耳%時，因為所形成之液晶配向膜未充分地硬化，所以以30莫耳%以下為宜，以22莫耳%以下尤佳。The use ratio of the alkoxydecane represented by the formula (1) is that when the total alkoxydecane used in the polysiloxane (A) is less than 2 mol%, since good liquid crystal alignment property cannot be obtained, More than 2% by mole is preferred. It is especially preferable to be more than 3 mol%. On the other hand, when it exceeds 30 mol%, since the formed liquid crystal alignment film is not sufficiently cured, it is preferably 30 mol% or less, more preferably 22 mol% or less.

本發明中，亦可使用1種或多種之上述聚矽氧烷(A)。In the present invention, one or more of the above polyoxyalkylene oxides (A) may also be used.

<聚矽氧烷(A)之溶液>本發明中，上述聚矽氧烷(A)之溶液係將含有式(1)所表示之烷氧基矽烷之烷氧基矽烷於有機溶劑中縮聚合，均勻溶解之溶液為宜。其中，聚矽氧烷(A)溶液係併用式(1)所表示之烷氧基矽烷及式(3)所表示之烷氧基矽烷縮聚合，均勻溶解於有機溶劑之溶液為宜。<Solution of Polyoxane (A)> In the present invention, the solution of the above polyoxane (A) is obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the formula (1) in an organic solvent. It is preferred to uniformly dissolve the solution. Among them, the polyoxane (A) solution is preferably a solution obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (3), and uniformly dissolved in an organic solvent.

本發明中所使用之縮聚合聚矽氧烷(A)之方法並無特別的限制，可舉例如將烷氧基矽烷於醇或甘醇溶劑中進行水解、縮聚合之方法。此時，水解、縮聚合反應係部份水解及完全水解中任一種皆可。完全水解時，理論上係加入烷氧基矽烷中之總烷氧基之0.5倍莫耳的水為宜，通常以加入比0.5倍莫耳過量的水尤佳。The method for polycondensation of the polyoxyalkylene (A) used in the present invention is not particularly limited, and examples thereof include a method of hydrolyzing and polycondensing alkoxydecane in an alcohol or a glycol solvent. In this case, the hydrolysis or polycondensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically preferred to add 0.5 times mole of water to the total alkoxy group of the alkoxy decane, and it is usually preferred to add water in an excess of 0.5 times the molar excess.

本發明中，上述反應所使用之水量係因應所需，可適當選擇，通常係烷氧基矽烷中之總烷氧基之0.5至2.5倍莫耳為宜。In the present invention, the amount of water used in the above reaction may be appropriately selected depending on the requirements, and is usually 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane.

另外，通常於促進水解、縮聚合之目的，可使用鹽酸、硫酸、硝酸、醋酸、甲酸、草酸、馬來酸等之酸、氨、甲基胺、乙基胺、乙醇胺、三乙基胺等之鹼、鹽酸、硫酸、硝酸等之金屬鹽等之觸媒。Further, in general, for the purpose of promoting hydrolysis and polycondensation, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid or maleic acid, ammonia, methylamine, ethylamine, ethanolamine, triethylamine or the like can be used. A catalyst such as a metal salt such as a base, hydrochloric acid, sulfuric acid or nitric acid.

除此之外，一般亦加熱溶解烷氧基矽烷之溶液，以更加促進水解、縮聚合反應。此時，加熱溫度及加熱時間係依所需而可適當選擇，可舉例如於50℃加熱、攪拌24小時，或回流下加熱、攪拌1小時等之方法。In addition to this, a solution of alkoxysilane is also heated and dissolved to further promote hydrolysis and condensation polymerization. In this case, the heating temperature and the heating time may be appropriately selected as needed, and may be, for example, a method of heating and stirring at 50 ° C for 24 hours, or heating under reflux, stirring for 1 hour or the like.

另外，作為其他方法，可舉例如將烷氧基矽烷、溶劑及草酸之混合物加熱、縮聚合之方法。具體上，預先加入草酸於醇中，成為草酸醇溶液後，以加熱該溶液之狀態，混合烷氧基矽烷之方法。此時，一般草酸之使用量係相對於1莫耳之具有烷氧基矽烷之總烷氧基，為0.2至2莫耳。於此方法中加熱係可以液溫50至180℃進行，以不引起液體蒸發、揮散等為宜，例如於密閉式容器中或回流下進行數十分鐘至十幾小時。Further, as another method, for example, a method of heating and polycondensing a mixture of alkoxysilane, a solvent, and oxalic acid can be mentioned. Specifically, a method in which oxalic acid is added to an alcohol to form an oxalic acid alcohol solution and the alkoxysilane is mixed in a state in which the solution is heated is added in advance. In this case, the amount of oxalic acid used is generally 0.2 to 2 moles per 1 mole of the total alkoxy group having an alkoxydecane. In this method, the heating system may be carried out at a liquid temperature of 50 to 180 ° C so as not to cause evaporation or volatilization of the liquid, for example, in a closed vessel or under reflux for several tens of minutes to several tens of hours.

得到聚矽氧烷(A)時，使用多種烷氧基矽烷時，可為預先混合烷氧基矽烷之混合物，亦可依次混合多種烷氧基矽烷。When a polyoxane (A) is obtained, when a plurality of alkoxy decanes are used, a mixture of alkoxy decane may be previously mixed, or a plurality of alkoxy decane may be sequentially mixed.

縮聚合烷氧基矽烷時所使用之溶劑係只要溶解烷氧基矽烷者即可，並無特別的限制。因為一般藉烷氧基矽烷之縮聚合反應而產生醇，所以可使用醇類、甘醇類或與醇類互溶性良好之有機溶劑。The solvent used in the condensation polymerization of the alkoxysilane is not particularly limited as long as it dissolves the alkoxysilane. Since alcohol is generally produced by a polycondensation reaction of alkoxysilane, an alcohol, a glycol, or an organic solvent having good miscibility with an alcohol can be used.

作為如此有機溶劑之具體例，可舉例如甲醇、乙醇、丙醇、丁醇、乙二醇、二乙二醇、丙二醇、己二醇、甲基溶纖素、乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、乙二醇單甲基醚、乙二醇二甲基醚、乙二醇正丁基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、丙二醇單甲基醚、丙二醇單丁基醚、N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、γ-丁內酯、二甲亞碸、四甲基脲、六甲基磷酸三胺(hexamethylphosphotriamide)、間甲酚等。Specific examples of such an organic solvent include methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, hexanediol, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. , ethyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N- Dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethylphosphotriamide, m-cresol, and the like.

本發明中，亦可混合多種之上述有機溶劑使用。In the present invention, a plurality of the above organic solvents may be used in combination.

由如此方法所得之聚矽氧烷(A)之溶液一般係使作為原料所加入之總烷氧基矽烷之矽原子換算成SiO2 之濃度(以下稱為SiO2 換算濃度。)為20質量%以下。於此濃度範圍，藉由選擇任意的濃度，可抑制凝膠產生，得到均質的溶液。The solution of the polyoxane (A) obtained by the above method is generally a concentration of SiO 2 in terms of a cerium atom of the total alkoxy decane to be added as a raw material (hereinafter referred to as a concentration in terms of SiO 2 ) of 20% by mass. the following. In this concentration range, by selecting an arbitrary concentration, gel formation can be suppressed, and a homogeneous solution can be obtained.

本發明中係可將上述方法所得之溶液直接作為聚矽氧烷(A)之溶液，亦可因應需要，將上述方法所得之溶液，濃縮或加入溶劑稀釋或取代成其他溶劑，作為聚矽氧 烷(A)之溶液。In the present invention, the solution obtained by the above method can be directly used as a solution of polyoxyalkylene (A), or the solution obtained by the above method can be concentrated or added to a solvent to be diluted or substituted into other solvents as a polyoxyl oxide. A solution of the alkane (A).

此時，使用的溶劑係可與縮聚合使用之溶劑相同，亦可為其他溶劑。此溶劑係只要均勻溶解聚矽氧烷(A)，並無特別的限制，可任意選擇一種或多種使用。In this case, the solvent to be used may be the same as the solvent used for the condensation polymerization, or may be another solvent. The solvent is not particularly limited as long as it dissolves the polyoxyalkylene (A) uniformly, and one or more of them can be used arbitrarily.

作為如此溶劑之具體例，可舉例如甲醇、乙醇、丙醇、丁醇、雙丙酮醇等之醇類；丙酮、甲基乙基酮、甲基異丁基酮等之酮類；乙二醇、二乙二醇、丙二醇、己二醇等之甘醇類；甲基溶纖素、乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、乙二醇單甲基醚、乙二醇二甲基醚、乙二醇正丁基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、丙二醇單甲基醚、丙二醇單丁基醚等之甘醇醚類；乙酸甲酯、乙酸乙酯、乳酸乙酯等之酯類；N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、γ-丁內酯、二甲亞碸、四甲基脲、六甲基磷酸三胺、間甲酚等。Specific examples of such a solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ethylene glycol; Glycols such as diethylene glycol, propylene glycol, hexanediol, etc.; methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylene glycol monomethyl Ether, ethylene glycol dimethyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether , glycol ethers such as propylene glycol monobutyl ether; esters of methyl acetate, ethyl acetate, ethyl lactate, etc.; N-methyl-2-pyrrolidone, N,N-dimethylformamide, N , N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethyl phosphate triamine, m-cresol and the like.

本發明中，如上述所得之聚矽氧烷(A)之溶液，可使用1種，亦可使用多種。In the present invention, the solution of the polyoxyalkylene (A) obtained as described above may be used alone or in combination of two or more.

<聚矽氧烷(B)><polyoxane (B)>

本發明所使用之聚矽氧烷(B)係將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷縮聚合所得之聚矽氧烷。但是，不併用式(1)所表示之烷氧基矽烷。The polyoxyalkylene (B) used in the present invention is a polyoxyalkylene obtained by polycondensation of an alkoxysilane containing a tetraalkoxydecane represented by the formula (2). However, the alkoxydecane represented by the formula (1) is not used in combination.

[化11]Si(OR3 )4 (2)[11] Si(OR 3 ) 4 (2)

上述式(2)之R3 係碳原子數為1至5個之烴基，因為碳原子數少，反應性高，所以碳原子數以1至5個之飽和烴基為宜。以甲基、乙基、丙基、丁基為宜。The R 3 -based hydrocarbon group having 1 to 5 carbon atoms in the above formula (2) is preferred because it has a small number of carbon atoms and high reactivity. Therefore, the number of carbon atoms is preferably 1 to 5 saturated hydrocarbon groups. Methyl, ethyl, propyl or butyl is preferred.

上述式(2)所表示之四烷氧基矽烷之具體例，可舉例如四甲烷氧基矽烷、四乙烷氧基矽烷、四丙烷氧基矽烷、四丁烷氧基矽烷等，可容易取得市售品。Specific examples of the tetraalkoxydecane represented by the above formula (2) include, for example, tetramethaneoxydecane, tetraethoxyoxydecane, tetrapropoxyoxydecane, and tetrabutoxyoxydecane, which are easily available. Commercial products.

本發明中，聚矽氧烷(B)亦可併用式(2)所表示之四烷氧基矽烷及下述式(4)所表示之烷氧基矽烷中之至少1種。In the present invention, at least one of the tetraalkoxydecane represented by the formula (2) and the alkoxydecane represented by the following formula (4) may be used in combination with the polyoxyalkylene oxide (B).

[化12](R7 )m Si(OR6 )4－m (4)(R 12 ) m Si(OR 6 ) 4-m (4)

上述式(4)所表示之烷氧基矽烷係具有2個或3個烷氧基為宜之所謂2官能基或3官能基之烷氧基矽烷。The alkoxydecane represented by the above formula (4) is a so-called bifunctional or trifunctional alkoxydecane having two or three alkoxy groups.

式(4)中之R6 係與R3 同樣地碳原子數為1至5個之烴基，因為碳原子數少，反應性高，所以碳原子數以1至5個之飽和烴基為宜。以甲基、乙基、丙基、丁基尤佳。R 6 in the formula (4) is a hydrocarbon group having 1 to 5 carbon atoms in the same manner as R 3 . Since the number of carbon atoms is small and the reactivity is high, it is preferred that the number of carbon atoms is 1 to 5 saturated hydrocarbon groups. It is especially preferred as methyl, ethyl, propyl or butyl.

上述式(4)之R7 係氫原子或碳原子數為1至6個，以1至5個之有機基為宜。作為如此有機基，可舉例如芳香族基、脂肪族基、具有脂環構造的基等。更適合之有機基之碳原子數為1至5個之有機基中，以碳原子數為1至5個之脂肪族基為宜，以碳原子數為1至5個之飽和烴基尤佳。此具體例，可舉例如甲基、乙基、丙基、丁基等。The R 7 -based hydrogen atom or the number of carbon atoms in the above formula (4) is preferably 1 to 5, and preferably 1 to 5 organic groups. Examples of such an organic group include an aromatic group, an aliphatic group, and a group having an alicyclic structure. Among the organic groups having 1 to 5 carbon atoms and more preferably an organic group, an aliphatic group having 1 to 5 carbon atoms is preferred, and a saturated hydrocarbon group having 1 to 5 carbon atoms is particularly preferred. Specific examples of this may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group.

如此之式(4)所表示之烷氧基矽烷之具體例，可舉例如甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、甲基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基丙基)三甲氧基矽烷、3-(2-胺基乙基胺基丙基)三乙氧基矽烷、2-胺基乙基胺基甲基三甲氧基矽烷、2-(2-胺基乙基硫乙基)三乙氧基矽烷、3-巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、烯丙基三乙氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、三氟丙基三甲氧基矽烷、氯丙基三乙氧基矽烷、溴化丙基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙氧基二乙基矽烷、二丁氧基二甲基矽烷、二乙氧基甲基乙烯基矽烷、二乙氧基二乙烯基矽烷、3-胺基丙基二乙氧基甲基矽烷、3-巰基丙基甲基二甲氧基矽烷、2-(2-胺基乙基硫乙基)二乙氧基甲基矽烷、二甲氧基甲基-3,3,3-三氟丙基矽烷、3-氯丙基二甲氧基甲基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二甲氧基二苯基矽烷、二乙氧基二苯基矽烷、甲氧基三苯基矽烷、乙氧基三苯基矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、環戊基三甲氧基矽烷、環戊基三乙氧基矽烷等。Specific examples of the alkoxydecane represented by the formula (4) include, for example, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, and ethyltriethoxydecane. Propyltrimethoxydecane, propyltriethoxydecane, methyltripropoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2 ( Aminoethyl)3-aminopropyltriethoxydecane, N-2(aminoethyl)3-aminopropyltrimethoxydecane, 3-(2-aminoethylaminopropyl) Trimethoxy decane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethoxydecane, 2-(2-aminoethyl) Thioethyl)triethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, 3-ureidopropyltriethoxydecane, vinyltriethoxydecane, ethylene Trimethoxy decane, allyl triethoxy decane, 3-isocyanate propyl triethoxy decane, trifluoropropyl trimethoxy decane, chloropropyl triethoxy decane, brominated propyl triethyl Oxy decane, dimethyl dimethoxy decane, dimethyl Ethoxy decane, diethoxydiethyl decane, dibutoxy dimethyl decane, diethoxymethyl vinyl decane, diethoxy divinyl decane, 3-aminopropyl di Oxymethyl decane, 3-mercaptopropylmethyldimethoxydecane, 2-(2-aminoethylthioethyl)diethoxymethylnonane, dimethoxymethyl-3,3 , 3-trifluoropropyl decane, 3-chloropropyl dimethoxymethyl decane, phenyl trimethoxy decane, phenyl triethoxy decane, dimethoxy diphenyl decane, diethoxy Diphenyl decane, methoxy triphenyl decane, ethoxy triphenyl decane, cyclohexyl trimethoxy decane, cyclohexyl triethoxy decane, cyclopentyl trimethoxy decane, cyclopentyl triethoxy Base decane and the like.

本發明中，使用至少1種式(2)所表示之四烷氧基矽烷即可，亦可因應需要，使用多種。另外，亦可併用式(4)所表示之烷氧基矽烷，此時，亦可使用多種式(4)所表示之烷氧基矽烷。In the present invention, at least one type of tetraalkoxysilane represented by the formula (2) may be used, and a plurality of types may be used as needed. Further, alkoxydecane represented by the formula (4) may be used in combination, and in this case, a plurality of alkoxydecanes represented by the formula (4) may be used.

另外，亦可併用市售品之聚矽氧烷之Colcoat公司製甲基矽酸酯51、乙基矽酸酯40等。Further, a methyl phthalate 51, an ethyl phthalate 40, or the like, manufactured by Colcoat Co., Ltd., which is a commercially available polyoxyalkylene, may be used in combination.

本發明使用之聚矽氧烷(B)係將含有式(2)所表示之四烷氧基矽烷縮聚合所得，於溶劑中為均質溶液狀態即可。The polyoxyalkylene (B) used in the present invention is obtained by polycondensation of a tetraalkoxysilane represented by the formula (2), and it may be in a homogeneous state in a solvent.

本發明中，亦可使用1種或多種上述之聚矽氧烷(B)。In the present invention, one or more of the above polyoxyalkylene oxides (B) may also be used.

<聚矽氧烷(B)之溶液>本發明中，上述之聚矽氧烷(B)之溶液係將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷於有機溶劑中縮聚合之均勻溶解溶液為宜。但是，不併用式(1)所表示之烷氧基矽烷。此時，將式(2)所表示之四烷氧基矽烷單獨，或式(2)及式(4)所表示之烷氧基矽烷縮聚合之均勻溶解溶液為宜。聚矽氧烷(B)之溶液係作為均勻溶解於有機溶劑之溶液所得。<Solution of Polyoxane (B)> In the present invention, the solution of the above polyoxane (B) is an alkoxydecane containing a tetraalkoxydecane represented by the formula (2) in an organic solvent. It is preferred to uniformly polymerize the solution by condensation polymerization. However, the alkoxydecane represented by the formula (1) is not used in combination. In this case, it is preferred to use a tetraalkyloxydecane represented by the formula (2) alone or a homogeneously dissolved solution of the alkoxysilane represented by the formula (2) and the formula (4). The solution of polyoxyalkylene (B) is obtained as a solution uniformly dissolved in an organic solvent.

得到本發明所使用之聚矽氧烷(B)之方法並無特別的限定，例如將烷氧基矽烷於醇或甘醇溶劑中進行水解、縮聚合之方法而可得之。此時，水解、縮聚合反應係部份水解及完全水解中任一種皆可。完全水解時，理論上係加入烷氧基矽烷中之總烷氧基之0.5倍莫耳的水為宜，通常加入比0.5倍莫耳過量的水。The method for obtaining the polyoxyalkylene oxide (B) used in the present invention is not particularly limited, and for example, a method in which an alkoxydecane is hydrolyzed or polycondensed in an alcohol or a glycol solvent can be obtained. In this case, the hydrolysis or polycondensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically preferred to add 0.5 times mole of water to the total alkoxy group of the alkoxysilane, usually adding water in an excess of 0.5 times mole.

本發明中，上述反應所使用之水量，因應所需，可適當選擇，通常係烷氧基矽烷中之總烷氧基之0.5至2.5倍莫耳。In the present invention, the amount of water used in the above reaction may be appropriately selected depending on the necessity, and is usually 0.5 to 2.5 times by mole based on the total alkoxy group in the alkoxydecane.

另外，通常於促進水解、縮聚合之目的，可使用鹽酸、硫酸、硝酸、醋酸、甲酸、草酸、馬來酸等之酸、氨、甲基胺、乙基胺、乙醇胺、三乙基胺等之鹼、鹽酸、硫酸、硝酸等之金屬鹽等之觸媒。Further, in general, for the purpose of promoting hydrolysis and polycondensation, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid or maleic acid, ammonia, methylamine, ethylamine, ethanolamine, triethylamine or the like can be used. A catalyst such as a metal salt such as a base, hydrochloric acid, sulfuric acid or nitric acid.

除此之外，一般亦加熱溶解烷氧基矽烷之溶液以更加促進水解、縮聚合反應。此時，加熱溫度及加熱時間係依所需而可適當選擇，可舉例如於50℃加熱、攪拌24小時，回流下加熱、攪拌1小時等之方法。In addition to this, a solution of alkoxysilane is also heated and dissolved to further promote hydrolysis and condensation polymerization. In this case, the heating temperature and the heating time may be appropriately selected as needed, and may be, for example, a method of heating at 50 ° C, stirring for 24 hours, heating under reflux, stirring for 1 hour, or the like.

另外，作為其他方法，可舉例如將烷氧基矽烷、溶劑及草酸之混合物加熱、縮聚合之方法。具體上，預先加入草酸於醇中，成為草酸醇溶液後，以加熱該溶液之狀態，混合烷氧基矽烷之方法。此時，一般草酸之使用量係相對於1莫耳之具有烷氧基矽烷之總烷氧基，為0.2至2莫耳。於此方法中加熱係可以液溫50至180℃進行，以不引起液體蒸發、揮散等為宜，例如於密閉式容器中或回流下進行數十分鐘至十幾小時。Further, as another method, for example, a method of heating and polycondensing a mixture of alkoxysilane, a solvent, and oxalic acid can be mentioned. Specifically, a method in which oxalic acid is added to an alcohol to form an oxalic acid alcohol solution and the alkoxysilane is mixed in a state in which the solution is heated is added in advance. In this case, the amount of oxalic acid used is generally 0.2 to 2 moles per 1 mole of the total alkoxy group having an alkoxydecane. In this method, the heating system may be carried out at a liquid temperature of 50 to 180 ° C so as not to cause evaporation or volatilization of the liquid, for example, in a closed vessel or under reflux for several tens of minutes to several tens of hours.

得到聚矽氧烷(B)時，使用多種烷氧基矽烷時，可混合預先混合烷氧基矽烷之混合物，亦可依次混合多種烷氧基矽烷。When a polyoxane (B) is obtained, when a plurality of alkoxy decanes are used, a mixture of alkoxy decane may be mixed in advance, or a plurality of alkoxy decane may be sequentially mixed.

縮聚合烷氧基矽烷時所使用之溶劑係只要溶解烷氧基矽烷者即可，並無特別的限制。因為一般藉由四烷氧基矽烷之縮聚合反應而產生醇，所以可使用醇類、甘醇類或與醇類互溶性良好之有機溶劑。The solvent used in the condensation polymerization of the alkoxysilane is not particularly limited as long as it dissolves the alkoxysilane. Since an alcohol is generally produced by a polycondensation reaction of a tetraalkoxydecane, an alcohol, a glycol, or an organic solvent having good miscibility with an alcohol can be used.

作為如此有機溶劑之具體例，可舉例如甲醇、乙醇、丙醇、丁醇、乙二醇、二乙二醇、丙二醇、己二醇、甲基溶纖素、乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、乙二醇單甲基醚、乙二醇二甲基醚、乙二醇正丁基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、丙二醇單甲基醚、丙二醇單丁基醚、N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、γ-丁內酯、二甲亞碸、四甲基脲、六甲基磷酸三胺、間甲酚等。Specific examples of such an organic solvent include methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, hexanediol, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. , ethyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N- Dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethyl phosphate triamine, m-cresol, and the like.

本發明中，亦可混合多種之上述有機溶劑使用。In the present invention, a plurality of the above organic solvents may be used in combination.

由如此方法所得之聚矽氧烷(B)之溶液一般係SiO2 換算濃度為20質量%以下。於此濃度範圍，藉由選擇任意的濃度，可抑制凝膠產生，得到均質的溶液。The solution of the polyoxyalkylene (B) obtained by such a method is generally 20% by mass or less in terms of SiO 2 conversion. In this concentration range, by selecting an arbitrary concentration, gel formation can be suppressed, and a homogeneous solution can be obtained.

本發明中係可將上述方法所得之溶液直接作為聚矽氧烷(B)之溶液，亦可因應需要，將上述方法所得之溶液，濃縮或加入溶劑稀釋或取代成其他溶劑，作為聚矽氧 烷(B)之溶液。In the present invention, the solution obtained by the above method can be directly used as a solution of polyoxyalkylene (B), or the solution obtained by the above method can be concentrated or added to a solvent to be diluted or substituted into other solvents as a polyoxyl oxide. A solution of the alkane (B).

此時，使用的溶劑係可與縮聚合使用之溶劑相同，亦可為其他溶劑。此溶劑係只要聚矽氧烷(B)均勻溶解，並無特別的限制，可任意選擇一種或多種使用。In this case, the solvent to be used may be the same as the solvent used for the condensation polymerization, or may be another solvent. The solvent is not particularly limited as long as the polyoxyalkylene (B) is uniformly dissolved, and one or more kinds of them can be used arbitrarily.

作為如此溶劑之具體例，可舉例如甲醇、乙醇、丙醇、丁醇、雙丙酮醇等之醇類；丙酮、甲基乙基酮、甲基異丁基酮等之酮類；乙二醇、二乙二醇、丙二醇、己二醇等之甘醇類；甲基溶纖素、乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、乙二醇單甲基醚、乙二醇二甲基醚、乙二醇正丁基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、丙二醇單甲基醚、丙二醇單丁基醚等之甘醇醚類；乙酸甲酯、乙酸乙酯、乳酸乙酯等之酯類；N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、γ-丁內酯、二甲亞碸、四甲基脲、六甲基磷酸三胺、間甲酚等。Specific examples of such a solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ethylene glycol; Glycols such as diethylene glycol, propylene glycol, hexanediol, etc.; methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylene glycol monomethyl Ether, ethylene glycol dimethyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether , glycol ethers such as propylene glycol monobutyl ether; esters of methyl acetate, ethyl acetate, ethyl lactate, etc.; N-methyl-2-pyrrolidone, N,N-dimethylformamide, N , N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethyl phosphate triamine, m-cresol and the like.

本發明中，可使用1種，亦可使用多種如上述所得之聚矽氧烷(B)之溶液。In the present invention, one type may be used, and a plurality of solutions of the polyoxane (B) obtained as described above may also be used.

<其他成份><Other ingredients>

於本發明中，只要不損害本發明之功效，除了聚矽氧烷(A)及聚矽氧烷(B)以外，亦可含有其他成份，例如無機微粒子、塗平劑、進而界面活性劑等之成份。In the present invention, in addition to the polyoxyalkylene (A) and the polyoxyalkylene (B), other components such as inorganic fine particles, a coating agent, and a surfactant may be contained as long as the effects of the present invention are not impaired. Ingredients.

作為無機微粒子，以二氧化矽微粒子、氧化鋁微粒子、氧化鈦微粒子及氟化鎂微粒子等之微粒子為宜，以膠體溶液者尤佳。此膠體溶液係可分散無機微粒子粉於分散媒，亦可為市售品之膠體溶液。本發明中，藉使含有無機微粒子，將可賦予所形成硬化被膜之表面形狀或其他功能。作為無機微粒子，該平均粒子徑係以0.001至0.2 μm為宜，以0.001至0.1 μm尤佳。無機微粒子超過0.2 μm時，使用所調製之塗佈液所形成之硬化被膜之透明性降低。As the inorganic fine particles, fine particles such as cerium oxide fine particles, alumina fine particles, titanium oxide fine particles, and magnesium fluoride fine particles are preferable, and a colloidal solution is particularly preferable. The colloidal solution is a dispersible inorganic fine particle powder in a dispersion medium, and may be a colloidal solution of a commercial product. In the present invention, the surface shape or other function of the formed cured film can be imparted by containing inorganic fine particles. As the inorganic fine particles, the average particle diameter is preferably 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the inorganic fine particles exceed 0.2 μm, the transparency of the cured film formed using the prepared coating liquid is lowered.

作為無機微粒子之分散媒，可舉例如水、有機溶劑。作為膠體溶液，就被膜形成用塗佈液之安定性之觀點，調整pH或pKa成2至10為宜。以3至7尤佳。Examples of the dispersion medium of the inorganic fine particles include water and an organic solvent. As the colloidal solution, it is preferred to adjust the pH or pKa to 2 to 10 from the viewpoint of the stability of the coating liquid for film formation. It is especially good from 3 to 7.

作為膠體溶液之分散媒所使用之有機溶劑，可舉例如甲醇、丙醇、乙二醇、丁醇、乙二醇單丙基醚等之醇類；甲基乙基酮、甲基異丁基酮等之酮類；甲苯、二甲苯等之芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、N－甲基吡咯烷酮等之醯胺類；乙酸乙酯、乙酸丁酯、γ－丁內酯等之酯類；四氫呋喃、1,4二噁烷等之醚類。此等中，以醇類及酮類為宜。此等有機溶劑係可單獨或混合2種以上作為分散媒使用。The organic solvent used as the dispersion medium of the colloidal solution may, for example, be an alcohol such as methanol, propanol, ethylene glycol, butanol or ethylene glycol monopropyl ether; methyl ethyl ketone or methyl isobutyl group; a ketone such as a ketone; an aromatic hydrocarbon such as toluene or xylene; an amide such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone; ethyl acetate or butyl acetate; An ester of γ-butyrolactone or the like; an ether such as tetrahydrofuran or 1,4-dioxane. Among these, alcohols and ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium.

另外，塗平劑及界面活性劑等係可使用已知物，因市售品容易取得，所以更適宜。Further, a known material such as a leveling agent, a surfactant, or the like can be used, and it is more preferable because it is easily obtained from a commercially available product.

<調製液晶配向劑>調製本發明之液晶配向劑之方法並無特別的限定，聚矽氧烷(A)及聚矽氧烷(B)，另外因應需要之其他成份成均勻的混合狀態即可。通常因為聚矽氧烷(A)及聚矽氧烷(B)係於溶劑中縮聚合，分別得到溶液之狀態，所以如上已經敍述之混合聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液之方法係簡便的。另外，因應需要，混合聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液後，亦可加入溶劑。<Modulation of Liquid Crystal Aligning Agent> The method for preparing the liquid crystal alignment agent of the present invention is not particularly limited, and the polyoxyalkylene (A) and the polyoxyalkylene (B) may be uniformly mixed in accordance with other components required. . Usually, since the polyoxyalkylene (A) and the polyoxyalkylene (B) are condensed and polymerized in a solvent to obtain a state of a solution, respectively, the solution of the polyoxane (A) and the polyoxyalkylene are mixed as described above. The method of the solution of (B) is simple. Further, if necessary, a solution of the polyoxane (A) and a solution of polyoxyalkylene (B) may be added, and then a solvent may be added.

此時，液晶配向劑中之SiO2 換算濃度係以0.5至15質量%為宜。於如此SiO2 換算濃度範圍時，以一次塗佈可容易得到所需膜厚度，可容易得到充分的溶液可操作期(Pot life)。In this case, the concentration in terms of SiO 2 in the liquid crystal alignment agent is preferably 0.5 to 15% by mass. In the case of such a concentration range of SiO 2 , the desired film thickness can be easily obtained by one application, and a sufficient solution life can be easily obtained.

另外，混合聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液後所加入之溶劑係可使用與聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液記載相同之溶劑。Further, a solvent obtained by mixing a solution of polyoxyalkylene (A) and a solution of polyoxyalkylene (B) may be a solution of a solution of polyoxyalkylene (A) and a solution of polyoxyalkylene (B). The same solvent is described.

另外，上述之混合其他成份之方法係可與聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液同時，亦可於混合此等之後，並無特別的限定。Further, the above-described method of mixing the other components may be carried out simultaneously with the solution of the polyoxyalkylene (A) and the solution of the polyoxyalkylene (B), or may be, after mixing, etc., and is not particularly limited.

本發明中，聚矽氧烷(A)之使用比率係相對於聚矽氧烷(A)及聚矽氧烷(B)之矽原子總量，聚矽氧烷(A)之矽原子總量係以3莫耳%至80莫耳%為宜。以5莫耳%至75莫耳%尤佳。聚矽氧烷(A)之矽原子總量未滿3莫耳%時，不能得到良好之液晶配向性，超過80莫耳%時，將難以得到於高溫下藉低頻率之元件驅動中之高電壓保持率。In the present invention, the use ratio of polyoxyalkylene (A) is based on the total amount of germanium atoms of polyoxyalkylene (A) and polyoxyalkylene (B), and the total amount of germanium atoms of polyoxyalkylene (A). It is preferably from 3 mol% to 80 mol%. It is particularly preferable to use 5 mol% to 75 mol%. When the total amount of ruthenium atoms of the polyoxyalkylene (A) is less than 3 mol%, good liquid crystal alignment property cannot be obtained, and when it exceeds 80 mol%, it is difficult to obtain a high-frequency component drive at a high temperature. Voltage retention rate.

本發明中，液晶配向劑之具體例，可舉例如下。In the present invention, specific examples of the liquid crystal alignment agent can be exemplified as follows.

[1]：含有聚矽氧烷(A)及聚矽氧烷(B)之液晶配向劑。[1]: A liquid crystal alignment agent containing polyoxyalkylene (A) and polyoxyalkylene (B).

[2]：含有聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液之液晶配向劑。[2]: A liquid crystal alignment agent containing a solution of polyoxyalkylene (A) and a solution of polyoxyalkylene (B).

[3]：如上述[1]或[2]中記載之液晶配向劑，其中聚矽氧烷(A)係將式(1)及式(3)所表示之烷氧基矽烷縮聚合所得之聚矽氧烷。[3] The liquid crystal alignment agent according to the above [1] or [2], wherein the polyoxyalkylene (A) is obtained by polycondensation of an alkoxysilane represented by the formula (1) and the formula (3). Polyoxane.

[4]：如上述[1]至[3]中任一項記載之液晶配向劑，其中聚矽氧烷(B)係將式(2)所表示之烷氧基矽烷、或式(2)及式(4)所表示之烷氧基矽烷縮聚合所得之聚矽氧烷。[4] The liquid crystal alignment agent according to any one of [1] to [3] wherein the polyoxyalkylene (B) is an alkoxydecane represented by the formula (2) or the formula (2) And a polyoxyalkylene obtained by polycondensation of an alkoxysilane represented by the formula (4).

[5]：含有如上述[1]至[4]中任一項記載之液晶配向劑及無機微粒子之液晶配向劑。[5] A liquid crystal alignment agent containing the liquid crystal alignment agent and the inorganic fine particles according to any one of the above [1] to [4].

[6]：含有如上述[1]至[5]中任一項記載之液晶配向劑、及至少1種選自塗平劑及界面活性劑之液晶配向劑。[6] The liquid crystal alignment agent according to any one of the above [1] to [5], wherein at least one liquid crystal alignment agent selected from the group consisting of a leveling agent and a surfactant is contained.

<形成液晶配向膜>本發明之液晶配向劑係塗佈於基板後，進行乾燥、煅燒，可形成液晶配向膜。<Formation of Liquid Crystal Alignment Film> The liquid crystal alignment agent of the present invention is applied to a substrate, dried, and fired to form a liquid crystal alignment film.

作為液晶配向劑之塗佈方法，可舉例如旋轉塗佈(spin coat)法、印刷法、噴墨塗佈(ink jet)法、噴霧法、輥塗法等，就生產性方法，工業上廣泛地使用轉寫印刷法，亦可適用於本發明之液晶配向劑。The coating method of the liquid crystal alignment agent may, for example, be a spin coating method, a printing method, an ink jet method, a spray method, a roll coating method, or the like, and a production method is widely used in the industry. The use of a transfer printing method can also be applied to the liquid crystal alignment agent of the present invention.

塗佈液晶配向劑後之乾燥步驟，並非一定需要，自塗佈後至煅燒之時間係依基板而非一定時，或塗佈後不立即煅燒時，以包含乾燥步驟為宜。此乾燥係蒸發溶劑至不因搬運基板等而塗膜形狀變形之程度即可，關於該乾燥手段並無特別的限制。可舉例如於溫度為50至150℃，以80至120℃為宜之加熱板上，以0.5至30分鐘，以1至5分鐘為宜乾燥之方法。The drying step after the application of the liquid crystal alignment agent is not necessarily required, and the drying step is preferably carried out from the time of coating to the calcination depending on the substrate, not necessarily, or when it is not immediately calcined after coating. In the drying, the solvent is evaporated to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like, and the drying means is not particularly limited. For example, a method of drying at a temperature of 50 to 150 ° C, preferably 80 to 120 ° C, for 0.5 to 30 minutes, and preferably 1 to 5 minutes is preferred.

以上述方法塗佈液晶配向劑所形成之塗膜係可煅燒而成液晶配向膜。此時，煅燒溫度係可以100至350℃之任意溫度進行，以150至300℃為宜，以150至220℃尤佳，以150至200℃更好。The coating film formed by coating the liquid crystal alignment agent by the above method can be calcined to form a liquid crystal alignment film. At this time, the calcination temperature may be carried out at any temperature of from 100 to 350 ° C, preferably from 150 to 300 ° C, more preferably from 150 to 220 ° C, still more preferably from 150 to 200 ° C.

液晶配向膜中之聚矽氧烷(A)及聚矽氧烷(B)係於煅燒步驟中進行縮聚合。然而，於本發明中，只要不損及本發明之功效，無須完全縮聚合。但是，於液晶盒(liquid crystal cell)之製造步驟中係必要的，以比密封劑硬化等之熱處理溫度高出10℃以上之溫度煅燒為宜。The polyoxyalkylene (A) and polyoxyalkylene (B) in the liquid crystal alignment film are subjected to polycondensation in a calcination step. However, in the present invention, it is not necessary to completely shrink the polymerization as long as the effects of the present invention are not impaired. However, it is preferable to perform calcination at a temperature higher than the heat treatment temperature of the sealant hardening or the like by 10 ° C or more in the production step of the liquid crystal cell.

液晶配向膜之厚度係可因應所需而選擇。液晶配向膜之厚度為5nm以上時，因為容易得到液晶顯示元件之信賴性，所以適宜。以10mm以上尤佳。另外，300nm以下時，因為液晶顯示元件之消耗電力不會變大，所以適宜。以150nm以下尤佳。The thickness of the liquid crystal alignment film can be selected according to the needs. When the thickness of the liquid crystal alignment film is 5 nm or more, it is suitable because the reliability of the liquid crystal display element is easily obtained. More preferably 10mm or more. Further, when it is 300 nm or less, since the power consumption of the liquid crystal display element does not become large, it is suitable. It is especially preferable to be 150 nm or less.

<液晶配向膜>以如上述方法所形成之本發明之液晶配向膜係聚矽氧烷(A)集中存在液晶配向膜之表面層附近之構造。此事係可以如X射線光電子分光(X－ray Photoelectron Spectroscopy)法之方法，分析自膜的表面至基板方向之元素分布而確認。<Liquid Crystal Alignment Film> The liquid crystal alignment film-based polyoxyalkylene (A) of the present invention formed by the above method is concentrated in the vicinity of the surface layer of the liquid crystal alignment film. This can be confirmed by analyzing the element distribution from the surface of the film to the substrate direction by a method of X-ray photoelectron spectroscopy.

由如此分析，認為具有使液晶配向於單一方向，尤其於垂直方向之效果之聚矽氧烷(A)，可達成容易集中存在於液晶配向膜之表面層附近之作用。From such an analysis, it is considered that the polyoxyalkylene (A) having an effect of aligning the liquid crystal in a single direction, particularly in the vertical direction, can be easily concentrated in the vicinity of the surface layer of the liquid crystal alignment film.

因此，本發明之液晶配向膜係具有良好的液晶配向性，接著，具有本發明之液晶配向膜之液晶顯示元件係具有於高溫下藉低頻率之元件驅動中電壓保持率高之特性。Therefore, the liquid crystal alignment film of the present invention has a good liquid crystal alignment property, and then the liquid crystal display element having the liquid crystal alignment film of the present invention has a characteristic that the voltage holding ratio is high in the case of driving at a low frequency by a low frequency element.

另外，本發明之液晶配向膜係即使於本發明之液晶配向劑中所含有聚矽氧烷(A)之構成成份之式(1)所表示之烷氧基矽烷的量少時，仍具有顯示良好的液晶配向性，並且於高溫下藉低頻率之元件驅動中電壓保持率非常高之特徵。具體上，即使聚矽氧烷(A)中之式(1)所表示之烷氧基矽烷的量為2至12莫耳%，仍具有顯示良好的液晶配向性，並且於高溫下藉低頻率之元件驅動中電壓保持率非常高之特徵。In addition, the liquid crystal alignment film of the present invention has a display even when the amount of the alkoxydecane represented by the formula (1) which is a constituent component of the polyoxyalkylene (A) contained in the liquid crystal alignment agent of the present invention is small. Good liquid crystal alignment, and high voltage retention at high temperatures by low frequency components. Specifically, even if the amount of the alkoxydecane represented by the formula (1) in the polyoxyalkylene (A) is from 2 to 12 mol%, it has a good liquid crystal alignment property and a low frequency at a high temperature. The component drive has a very high voltage retention rate.

本發明之液晶配向膜係由含有聚矽氧烷(A)及聚矽氧烷(B)之液晶配向劑所得，因此，與自單獨聚矽氧烷(A)之液晶配向劑所得之液晶配向膜相比較，尤其於高溫下藉低頻率之元件驅動中之電壓保持率顯示高的值。The liquid crystal alignment film of the present invention is obtained from a liquid crystal alignment agent containing polysiloxane (A) and polysiloxane (B), and therefore, liquid crystal alignment with liquid crystal alignment agent from polyoxyalkylene (A) alone Compared with the film, the voltage holding ratio in the component driving by the low frequency, especially at a high temperature, shows a high value.

本發明之液晶配向劑係以一液體形成如圖1所示之聚矽氧烷(A)集中存在於膜表面之構造之液晶配向膜，但所形成之液晶配向膜係具有作為單獨聚矽氧烷(A)之液晶配向劑所不能得到之作為液晶配向膜之如上述之特徵。The liquid crystal alignment agent of the present invention forms a liquid crystal alignment film in which a polyoxyalkylene (A) as shown in FIG. 1 is concentrated on the surface of the film, but the liquid crystal alignment film formed has a specific polysiloxane. The liquid crystal alignment film which is not obtained by the liquid crystal alignment agent of the alkane (A) is as described above.

<液晶顯示元件><Liquid crystal display element>

本發明之液晶顯示元件係由上述方法，於基板上形成液晶配向膜後，可以已知方法製作液晶盒而得。可舉製作液晶盒之一例，一般係將形成液晶配向膜之1對基板，包夾著間隔劑(spacer)，以密封劑固定，注入液晶而包封之方法。此時，所使用之間隔劑的大小為1至30μm，以2至10μm為宜。The liquid crystal display element of the present invention can be obtained by forming a liquid crystal cell by a known method after forming a liquid crystal alignment film on a substrate by the above method. An example of a liquid crystal cell is generally used, which is a method in which a pair of substrates of a liquid crystal alignment film are formed, a spacer is interposed, a sealant is fixed, and a liquid crystal is injected and encapsulated. At this time, the size of the spacer to be used is 1 to 30 μm, preferably 2 to 10 μm.

注入液晶的方法並無特別的限制，可舉例如將製作液晶盒減壓後，注入液晶之真空法或滴入液晶後進行包封之滴入法等。The method of injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which a liquid crystal cell is decompressed, a vacuum method in which a liquid crystal is injected, or a dropping method in which a liquid crystal is dropped and then encapsulated.

作為使用於液晶顯示元件之基板，只要為透明性高之基板即可，並無特別的限制，通常係於基板上形成驅動液晶用之透明電極之基板。The substrate to be used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, and a substrate for driving a transparent electrode for liquid crystal is usually formed on the substrate.

作為具體例，可舉例如於玻璃板、聚碳酸酯、聚(甲基)丙烯酸酯、聚醚碸、聚芳酯、聚胺基甲酸乙酯、聚碸、聚醚、聚醚酮、三甲基戊烯、聚鏈烯烴、聚對苯二甲酸乙二醇酯、(甲基)丙烯腈、三乙醯纖維素、二乙醯纖維素、醋酸丁酸纖維素等之塑膠板等上形成透明電極之基板。Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyether oximes, polyarylates, polyurethanes, polyfluorenes, polyethers, polyether ketones, and trimethyl ketones. Forming transparent on plastic plates such as pentene, polyalkene, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, cellulose acetate butyrate, etc. The substrate of the electrode.

另外，如薄膜電晶體(TFT)型元件之高功能元件中，使用於液晶驅動用之電極與基板間形成如電晶體之元件者。Further, in a high-function element such as a thin film transistor (TFT) type element, an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate.

透過型之液晶元件時，一般係使用如上述之基板，但於反射型之液晶顯示元件，僅單側基板亦可使用矽圓等之不透明基板。此時，於基板上所形成之電極，亦可使用如反射光之鋁的材料。In the case of a transmissive liquid crystal element, a substrate as described above is generally used. However, in a reflective liquid crystal display element, an opaque substrate such as a circle may be used as the single-sided substrate. At this time, a material such as aluminum which reflects light may be used as the electrode formed on the substrate.

如至今所述，使用本發明之液晶配向劑所得之液晶配向膜係可提供具有液晶配向性良好，且於高溫下藉低頻率之元件驅動中電壓保持率高之特性之液晶顯示元件。As described above, the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention can provide a liquid crystal display element having a liquid crystal alignment property and a high voltage holding ratio at a high temperature by a low frequency element.

實施例Example

以下係表示合成例、實施例及比較例，具體地說明本發明，但本發明並不侷限於此等所解釋者。Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to those explained.

如下說明本實施例中之簡稱。The abbreviation in this embodiment will be described as follows.

TEOS：四乙氧基矽烷C10：癸基三甲氧基矽烷C12：十二烷基三乙氧基矽烷C18：十八烷基三乙氧基矽烷HG：己二醇BCG：丁基溶纖劑NMP：N－甲基吡咯烷酮TEOS: Tetraethoxydecane C10: mercaptotrimethoxydecane C12: dodecyltriethoxydecane C18: octadecyltriethoxydecane HG: hexanediol BCG: butyl cellosolve NMP: N -methylpyrrolidone

<合成例1><Synthesis Example 1>

於具備回流管之500ml之4口反應燒瓶，加入51.3g之HG、15.6g之BCS及69.4之TEOS，攪拌而調製烷氧基矽烷單體之溶液。於室溫下，將預先混合25.6g之HG、7.8g之BCS、30.0g的水及作為觸媒之0.3g之草酸之草酸溶液，滴入於此溶液中，於滴入結束後攪拌30分鐘。之後，以溶液溫度70℃加熱1小時後放冷，得到溶液(Z1)。於此溶液(Z1)中，加入HG、BCS及NMP，調整使溶劑之質量比為HG：BCS：NMP＝30：50：20，且SiO2 換算濃度成為3.5質量%，得到聚矽氧烷之溶液(P1)。To a 4-ml reaction flask equipped with a reflux tube of 500 ml, 51.3 g of HG, 15.6 g of BCS and 69.4 of TEOS were added and stirred to prepare a solution of alkoxydecane monomer. 25.6 g of HG, 7.8 g of BCS, 30.0 g of water, and 0.3 g of oxalic acid of oxalic acid as a catalyst were mixed in the solution at room temperature, and stirred for 30 minutes after the end of the dropwise addition. . Thereafter, the mixture was heated at a solution temperature of 70 ° C for 1 hour, and then allowed to cool to obtain a solution (Z1). HG, BCS, and NMP were added to the solution (Z1), and the mass ratio of the solvent was adjusted to HG:BCS:NMP=30:50:20, and the concentration in terms of SiO 2 was 3.5% by mass to obtain a polyoxyalkylene. Solution (P1).

<合成例2><Synthesis Example 2>

於具備回流管之500ml之4口反應燒瓶，加入47.8g之HG、14.5g之BCS及55.6之TEOS及22.2g之作為烷氧基矽烷單體(X)之C12，攪拌而調製烷氧基矽烷單體之混合溶液。於室溫下，將預先混合23.9g之HG、7.3g之BCS、28.5g的水及作為觸媒之0.3g之草酸之草酸溶液，滴入於此溶液中，於滴入結束後攪拌30分鐘。之後，以溶液溫度70℃加熱1小時後放冷，得到溶液(Z2)。於此溶液(Z2)中，加入HG、BCS及NMP，調整使溶劑之質量比為HG：BCS：NMP＝30：50：20，且SiO2 換算濃度成為3.5質量%，得到聚矽氧烷之溶液(P2)。In a 500-ml 4-neck reaction flask equipped with a reflux tube, 47.8 g of HG, 14.5 g of BCS and 55.6 of TEOS and 22.2 g of C12 as an alkoxydecane monomer (X) were added and stirred to prepare an alkoxydecane. A mixed solution of monomers. 23.9 g of HG, 7.3 g of BCS, 28.5 g of water and 0.3 g of oxalic acid of oxalic acid as a catalyst were mixed in the solution at room temperature, and stirred for 30 minutes after the end of the dropwise addition. . Thereafter, the mixture was heated at a solution temperature of 70 ° C for 1 hour, and then allowed to cool to obtain a solution (Z2). HG, BCS, and NMP were added to the solution (Z2), and the mass ratio of the solvent was adjusted to HG:BCS:NMP=30:50:20, and the concentration in terms of SiO 2 was 3.5% by mass to obtain a polyoxyalkylene. Solution (P2).

<合成例3至10><Synthesis Examples 3 to 10>

以表1所示之組成，藉與合成例2相同的方法得到溶液(Z3至Z10)。之後，於此溶液中，加入HG、BCS及NMP，調整使溶劑之質量比為HG：BCS：NMP＝30：50：20，且SiO2 換算濃度成為3.5質量%，得到聚矽氧烷之溶液(P3至10)。With the composition shown in Table 1, a solution (Z3 to Z10) was obtained by the same method as in Synthesis Example 2. Then, HG, BCS, and NMP were added to the solution, and the mass ratio of the solvent was adjusted to HG:BCS:NMP=30:50:20, and the concentration in terms of SiO 2 was 3.5% by mass to obtain a solution of polysiloxane. (P3 to 10).

另外，表中括弧內之莫耳數係表示各烷氧基矽烷之莫耳數。Further, the number of moles in the parentheses in the table indicates the number of moles of each alkoxydecane.

<合成例11><Synthesis Example 11>

混合661.75g之乙醇、208g之TEOS，於40℃加入126g的水、4.25g之氨水(濃度為28質量%)，以40℃攪拌4天，製作含有粒子溶液。於500g之所製作之含有二氧化矽粒子溶液，加入435g之HG，濃縮成300g，調製含有二氧化矽粒子溶液(Y1)。由動態光散射法進行粒子徑測定。此粒子徑之測定方法係說明於Journal of Chemical Physics 57卷11號(1972年12月)4814頁，本發明中使用大塚電子股份有限公司製DLS－7000測定。該結果係含有二氧化矽粒子溶液(Y1)之粒子徑為20nm。661.75 g of ethanol and 208 g of TEOS were mixed, and 126 g of water and 4.25 g of ammonia water (concentration: 28% by mass) were added at 40 ° C, and the mixture was stirred at 40 ° C for 4 days to prepare a particle-containing solution. The cerium oxide particle-containing solution prepared in 500 g was added to 435 g of HG, and concentrated to 300 g to prepare a cerium oxide particle-containing solution (Y1). The particle diameter was measured by a dynamic light scattering method. The method for measuring the particle diameter is described in Journal of Chemical Physics, Vol. 57, No. 11 (December 1972), page 4814, and is measured in the present invention using DLS-7000 manufactured by Otsuka Electronics Co., Ltd. As a result, the particle diameter of the cerium oxide particle-containing solution (Y1) was 20 nm.

於此溶液(Y1)中，加入HG、BCS及NMP，調整使溶劑之質量比為HG：BCS：NMP＝30：50：20，且SiO2 換算濃度成為3.5質量%，得到含有二氧化矽粒子之溶液(Q1)。HG, BCS, and NMP were added to the solution (Y1), and the mass ratio of the solvent was adjusted to be HG:BCS:NMP=30:50:20, and the concentration in terms of SiO 2 was 3.5% by mass to obtain cerium oxide-containing particles. Solution (Q1).

<實施例1至8><Examples 1 to 8>

以表2所示之組成，於室溫下混合聚矽氧烷之溶液(P2、P5及P8)及聚矽氧烷之溶液(P1)，得到液晶配向劑(L1至L8)。With the composition shown in Table 2, a solution of polyoxyalkylene (P2, P5, and P8) and a solution of polyoxyalkylene (P1) were mixed at room temperature to obtain a liquid crystal alignment agent (L1 to L8).

進而，於室溫下混合聚矽氧烷之溶液(P2)、聚矽氧烷之溶液(P1)及含有二氧化矽粒子溶液(Q1)，得到液晶配向劑(L9)。使用此液晶配向劑(L1至L9)，製作液晶盒(元件)，測定液晶配向性及電壓保持率。結果如表3所示。Further, a solution of the polyoxyalkylene (P2), a solution of the polyoxyalkylene (P1), and a solution containing the cerium oxide particles (Q1) were mixed at room temperature to obtain a liquid crystal alignment agent (L9). Using this liquid crystal alignment agent (L1 to L9), a liquid crystal cell (element) was produced, and liquid crystal alignment property and voltage retention ratio were measured. The results are shown in Table 3.

另外，液晶盒(元件)之製作方法、液晶配向性及電壓保持率之測定方法係如下所述。Further, the method of producing the liquid crystal cell (element), the liquid crystal alignment property, and the method of measuring the voltage holding ratio are as follows.

<比較例1至8><Comparative Examples 1 to 8>

如表2所示，取代上述之液晶配向劑(L1至L8)，直接使用P1至P4、P6、P7、P9及P10(M1至M8)，與實施例同樣地製作液晶盒，測定液晶配向性及電壓保持率。As shown in Table 2, in place of the liquid crystal alignment agents (L1 to L8) described above, P1 to P4, P6, P7, P9, and P10 (M1 to M8) were directly used, and a liquid crystal cell was produced in the same manner as in the examples to measure liquid crystal alignment. And voltage retention.

結果如表3所示。The results are shown in Table 3.

[製作液晶盒][Production of liquid crystal box]

使用以孔徑0.5 μm之膜濾器加壓過濾之液晶配向劑，於附有透明電極之玻璃基板，藉由旋轉塗佈法形成膜。將此基板於80℃之加熱板上乾燥5分鐘後，以180℃之熱風循環式烤箱煅燒60分，形成膜厚度為100nm之液晶配向膜。The liquid crystal alignment agent which was pressure-filtered by a membrane filter having a pore size of 0.5 μm was used to form a film by a spin coating method on a glass substrate with a transparent electrode. The substrate was dried on a hot plate at 80 ° C for 5 minutes, and then calcined by a hot air circulating oven at 180 ° C for 60 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

準備2片之如上述所得之附有液晶配向膜之基板，於單側基板之液晶配向膜面上，散布6 μm之間隔劑後，使液晶配向膜相對互相黏合，形成空盒。注入液晶於此空盒中，得到液晶盒。Two sheets of the substrate having the liquid crystal alignment film obtained as described above were prepared, and a spacer of 6 μm was spread on the liquid crystal alignment film surface of the single-sided substrate, and then the liquid crystal alignment films were bonded to each other to form an empty cell. Liquid crystal was injected into this empty cell to obtain a liquid crystal cell.

此時，液晶係使用Merk公司製MLC－6608(商品名)及Merk公司製MLC－7021－100(商品名)之2種。In this case, the liquid crystal system used two types of MLC-6608 (trade name) manufactured by Merck Co., Ltd. and MLC-7021-100 (trade name) manufactured by Merk Co., Ltd.

[液晶配向性][Liquid alignment]

作為液晶，使用Merk公司製MLC－7021－100，以與「製作液晶箱」相同的方法所得之液晶盒，以偏光顯微鏡觀察，以目測確認液晶之配向狀態。As a liquid crystal, MLC-7021-100 manufactured by Merk Co., Ltd. was used, and a liquid crystal cell obtained by the same method as in the "production of a liquid crystal cell" was observed with a polarizing microscope, and the alignment state of the liquid crystal was visually confirmed.

無缺陷之均勻垂直配向時為○，發現配向缺陷時及未垂直配向時為×。When there is no defect, the uniform vertical alignment is ○, and when the alignment defect is found and when it is not vertically aligned, it is ×.

[電壓保持率][Voltage retention rate]

以與上述之[製作液晶盒]相同的方法，使用Merk公司製MLC－6608作為液晶，將所得之液晶盒，使用東陽(TOYO Corporation)公司製VHR－1，外加4V電壓後，於80℃恆溫槽中測定1667ms後之電壓保持率(Voltage Holding Ratio：VHR)。MLC-6608 manufactured by Merk Co., Ltd. was used as the liquid crystal in the same manner as in the above-mentioned [manufacturing of the liquid crystal cell], and the obtained liquid crystal cell was used, and VHR-1 manufactured by Toyo Corporation was used, and a voltage of 4 V was applied thereto, and then the temperature was constant at 80 ° C. The voltage holding ratio (Voltage Holding Ratio: VHR) after 1667 ms was measured in the tank.

如實施例1至9所示，聚矽氧烷(A)之溶液(P2、P5及P8)及聚矽氧烷(B)之溶液(P1)之混合物係比單獨聚矽氧烷(A)之溶液之比較例1至7及單獨聚矽氧烷(B)之溶液之比較例8，顯示高電壓保持率，觀察出非常良好的垂直配向性，液晶配向性亦優異。As shown in Examples 1 to 9, the mixture of the solution of the polyoxyalkylene (A) (P2, P5 and P8) and the solution of the polyoxyalkylene (B) (P1) is more than the polysiloxane (A) alone. Comparative Example 8 of the comparative examples 1 to 7 and the solution of the polysiloxane (B) alone showed a high voltage holding ratio, and a very good vertical alignment property was observed, and the liquid crystal alignment property was also excellent.

[X射線光電子分光法][X-ray photoelectron spectroscopy]

將液晶配向劑L5及P2，以孔徑0.5 μm之膜濾器加壓過濾後，於矽基板[(100)面]旋轉塗佈，於80℃之加熱板上乾燥5分鐘。之後，以180℃之熱風循環式烤箱煅燒60分，得到膜厚度為100nm之塗膜。對此塗膜，使用島津製作所公司製ESCA－3200，分析自膜的表面至基板方向之元素分布。該結果係如圖1及圖2所示。The liquid crystal alignment agents L5 and P2 were filtered under pressure with a membrane filter having a pore diameter of 0.5 μm, and then spin-coated on a ruthenium substrate [(100) surface], and dried on a hot plate at 80 ° C for 5 minutes. Thereafter, it was calcined by a hot air circulating oven at 180 ° C for 60 minutes to obtain a coating film having a film thickness of 100 nm. For the coating film, ESCA-3200 manufactured by Shimadzu Corporation was used to analyze the element distribution from the surface of the film to the direction of the substrate. The results are shown in Figures 1 and 2.

由此分析結果，相對於使用P2所得塗膜之膜內碳濃度均勻，確認自本發明之液晶配向劑(L5)所得之液晶配向膜，於表層附近存在高碳濃度層。As a result of the analysis, it was confirmed that the liquid crystal alignment film obtained from the liquid crystal alignment agent (L5) of the present invention had a uniform carbon concentration in the film obtained by using P2, and a high carbon concentration layer was present in the vicinity of the surface layer.

產業上利用性Industrial use

本發明之液晶配向劑係可提供可得到具有配向性良好，且於高溫下藉低頻率之元件驅動中，電壓保持率高之特性之液晶配向膜，進而可提供信賴性高之液晶顯示元件。The liquid crystal alignment agent of the present invention can provide a liquid crystal alignment film which has excellent alignment properties and is driven by a low frequency element at a high temperature and has a high voltage holding ratio, and can provide a liquid crystal display element having high reliability.

因此，本發明之液晶配向膜係可適合使用於各種液晶顯示元件，尤其垂直配向型(VA)。亦可使用於其他偏光膜、相位差膜、視角擴大膜用配向膜。Therefore, the liquid crystal alignment film of the present invention can be suitably used for various liquid crystal display elements, particularly vertical alignment type (VA). It can also be used for other polarizing films, retardation films, and alignment films for viewing angle widening films.

另外，在此引用2006年3月7日所申請之日本專利文獻2006－060807號說明書、專利申請範圍、圖式及發明摘要的全部內容，採用作為本發明說明書之揭示者。In addition, the entire contents of the specification, the patent application, the drawings and the abstract of the Japanese Patent Application No. 2006-060807, filed on Jan.

[圖1]對於本發明之液晶配向劑(L5)所得之液晶配向膜，分析自膜的表面至基板方向之元素分布的結果。Fig. 1 shows the results of analyzing the element distribution from the surface of the film to the direction of the substrate of the liquid crystal alignment film obtained by the liquid crystal alignment agent (L5) of the present invention.

[圖2]對於比較例1之聚矽氧烷溶液(P2)所得之塗膜，分析自膜的表面至基板方向之元素分布的結果。2] Results of elemental distribution from the surface of the film to the direction of the substrate of the coating film obtained in the polyaluminoxane solution (P2) of Comparative Example 1.

Claims (11)

一種液晶配向劑，其特徵為，含有下述之聚矽氧烷(A)、聚矽氧烷(B)、及溶解此等聚矽氧烷之有機溶劑，且聚矽氧烷(A)之矽原子之量係相對於聚矽氧烷(A)及聚矽氧烷(B)之矽原子總量，為3至80莫耳%；聚矽氧烷(A)：將含有2至30莫耳%比率之式(1)所表示之烷氧基矽烷之烷氧基矽烷，縮聚合所得之聚矽氧烷，[化1]R1 Si(OR2 )3 (1)(R1 係碳原子數為8至30個之有機基，R2 係表示碳原子數為1至5個之烴基)聚矽氧烷(B)：將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷，與甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、甲基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基丙基)三甲氧基矽烷、3-(2-胺基乙基胺基丙基)三乙氧基矽烷、2-胺基乙基胺基甲基三甲氧基矽烷、2-(2 -胺基乙基硫乙基)三乙氧基矽烷、3-巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、烯丙基三乙氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、三氟丙基三甲氧基矽烷、氯丙基三乙氧基矽烷、溴化丙基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙氧基二乙基矽烷、二丁氧基二甲基矽烷、二乙氧基甲基乙烯基矽烷、二乙氧基二乙烯基矽烷、3-胺基丙基二乙氧基甲基矽烷、3-巰基丙基甲基二甲氧基矽烷、2-(2-胺基乙基硫乙基)二乙氧基甲基矽烷、二甲氧基甲基-3,3,3-三氟丙基矽烷、3-氯丙基二甲氧基甲基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二甲氧基二苯基矽烷、二乙氧基二苯基矽烷、甲氧基三苯基矽烷、乙氧基三苯基矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、環戊基三甲氧基矽烷、環戊基三乙氧基矽烷之至少一種併用，縮聚合所得之聚矽氧烷，但是，不併用式(1)所表示之烷氧基矽烷，[化2]Si(OR3 )4 (2)(R3 係表示碳原子數為1至5個之烴基)。A liquid crystal alignment agent comprising the following polyoxyalkylene (A), polyoxyalkylene (B), and an organic solvent for dissolving the polyoxyalkylenes, and polyoxyalkylene (A) The amount of ruthenium atoms is 3 to 80 mol% relative to the total amount of ruthenium atoms of polyoxyalkylene (A) and polyoxyalkylene (B); polyoxyalkylene (A): will contain 2 to 30 moles The alkoxy decane of the alkoxydecane represented by the formula (1), the polyoxyalkylene obtained by condensation polymerization, [Chemical Formula 1] R 1 Si(OR 2 ) 3 (1) (R 1 -based carbon) An organic group having 8 to 30 atoms, and R 2 is a hydrocarbon group having 1 to 5 carbon atoms. Polyoxyalkylene (B): an alkane having a tetraalkoxydecane represented by the formula (2) Oxydecane, with methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, propyltrimethoxydecane, propyltriethoxydecane, Methyl tripropoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, N-2 (aminoethyl) 3-aminopropyl triethoxy Decane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane, 3-(2-aminoethylaminopropyl)trimethoxy Decane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethoxydecane, 2-(2-aminoethylthioethyl) Triethoxy decane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, 3-ureidopropyltriethoxydecane, vinyltriethoxydecane, vinyltrimethoxy Decane, allyl triethoxy decane, 3-isocyanate propyl triethoxy decane, trifluoropropyl trimethoxy decane, chloropropyl triethoxy decane, bromopropyl triethoxy decane, Dimethyldimethoxydecane, dimethyldiethoxydecane, diethoxydiethyldecane, dibutoxydimethylnonane, diethoxymethylvinylnonane, diethoxy Divinyl decane, 3-aminopropyl diethoxymethyl decane, 3-mercaptopropyl methyl dimethoxy decane, 2-(2-aminoethyl thioethyl) diethoxy group Baseline, dimethoxymethyl-3,3,3-trifluoropropylnonane, 3-chloropropyldimethoxymethylnonane, phenyltrimethoxydecane, phenyltriethoxydecane, Dimethoxydiphenyl decane, diethoxydiphenyl Decane, methoxytriphenyldecane, ethoxytriphenyldecane, cyclohexyltrimethoxydecane, cyclohexyltriethoxydecane, cyclopentyltrimethoxydecane, cyclopentyltriethoxydecane At least one of the polyoxyalkylenes obtained by polycondensation, but not the alkoxydecane represented by the formula (1), [Chemical 2]Si(OR 3 ) 4 (2) (R 3 represents a carbon number It is 1 to 5 hydrocarbon groups). 一種液晶配向劑，其特徵為，含有下述之聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液，且聚矽氧烷(A) 之矽原子之量係相對於聚矽氧烷(A)及聚矽氧烷(B)之矽原子總量，為3至80莫耳%；聚矽氧烷(A)之溶液：將含有2至30莫耳%比率之式(1)所表示之烷氧基矽烷之烷氧基矽烷，於有機溶劑中縮聚合所得之聚矽氧烷之溶液，[化3]R1 Si(OR2 )3 (1)(R1 係碳原子數為8至30個之有機基，R2 係表示碳原子數為1至5個之烴基)聚矽氧烷(B)之溶液：將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷，與甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、甲基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基丙基)三甲氧基矽烷、3-(2-胺基乙基胺基丙基)三乙氧基矽烷、2-胺基乙基胺基甲基三甲氧基矽烷、2-(2-胺基乙基硫乙基)三乙氧基矽烷、3-巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、烯丙基三乙氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、三 氟丙基三甲氧基矽烷、氯丙基三乙氧基矽烷、溴化丙基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙氧基二乙基矽烷、二丁氧基二甲基矽烷、二乙氧基甲基乙烯基矽烷、二乙氧基二乙烯基矽烷、3-胺基丙基二乙氧基甲基矽烷、3-巰基丙基甲基二甲氧基矽烷、2-(2-胺基乙基硫乙基)二乙氧基甲基矽烷、二甲氧基甲基-3,3,3-三氟丙基矽烷、3-氯丙基二甲氧基甲基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二甲氧基二苯基矽烷、二乙氧基二苯基矽烷、甲氧基三苯基矽烷、乙氧基三苯基矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、環戊基三甲氧基矽烷、環戊基三乙氧基矽烷之至少一種併用，於有機溶劑中縮聚合所得之聚矽氧烷之溶液，但是，不併用式(1)所表示之烷氧基矽烷，[化4]Si(OR3 )4 (2)(R3 係表示碳原子數為1至5個之烴基)。A liquid crystal alignment agent characterized by containing a solution of polyoxane (A) and a solution of polyoxyalkylene (B), and the amount of germanium atoms of polyoxyalkylene (A) is relative to poly The total amount of ruthenium atoms of the oxirane (A) and the polyoxy siloxane (B) is from 3 to 80 mol%; the solution of the polyoxane (A): which will have a ratio of 2 to 30 mol% ( 1) A solution of the alkoxydecane of the alkoxydecane represented by polycondensation of the polyoxyalkylene obtained by polycondensation in an organic solvent, [Chemical Formula 3] R 1 Si(OR 2 ) 3 (1) (R 1 -based carbon) A solution of 8 to 30 organic groups, R 2 represents a hydrocarbon group having 1 to 5 carbon atoms) a polyoxane (B): a tetraalkoxy decane represented by the formula (2) Alkoxydecane, with methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, propyltrimethoxydecane, propyltriethoxy Decane, methyltripropoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2(aminoethyl)3-aminopropyltriethyl Oxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane, 3-(2-aminoethylamino) Propyl)trimethoxydecane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethoxydecane, 2-(2-amino group Ethylthioethyl)triethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, 3-ureidopropyltriethoxydecane, vinyltriethoxydecane , vinyl trimethoxy decane, allyl triethoxy decane, 3-isocyanate propyl triethoxy decane, trifluoropropyl trimethoxy decane, chloropropyl triethoxy decane, brominated propyl Triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, diethoxy diethyl decane, dibutoxy dimethyl decane, diethoxy methyl vinyl Decane, diethoxydivinyldecane, 3-aminopropyldiethoxymethyldecane, 3-mercaptopropylmethyldimethoxydecane, 2-(2-aminoethylthioethyl) Diethoxymethyl decane, dimethoxymethyl-3,3,3-trifluoropropyl decane, 3-chloropropyldimethoxymethyl decane, phenyltrimethoxydecane, phenyl Triethoxy decane, dimethoxydiphenyl decane, two Ethoxydiphenyl decane, methoxy triphenyl decane, ethoxy triphenyl decane, cyclohexyl trimethoxy decane, cyclohexyl triethoxy decane, cyclopentyl trimethoxy decane, cyclopentyl a mixture of at least one of triethoxy decane, which is obtained by polycondensation of the obtained polyoxyalkylene in an organic solvent, but not using the alkoxydecane represented by the formula (1), [Chem. 4] Si (OR 3 ) 4 (2) (R 3 is a hydrocarbon group having 1 to 5 carbon atoms). 如申請專利範圍第1項之液晶配向劑，其中聚矽氧烷(A)係併用至少1種式(3)所表示之烷氧基矽烷，縮聚合所得之聚矽氧烷，[化5](R5 )n Si(OR4 )4-n (3) (R4 係分別碳原子數為1至5個之烴基，R5 係表示氫原子或碳原子數為1至5個之有機基，n係表示0至3之整數)。The liquid crystal alignment agent of claim 1, wherein the polyoxyalkylene (A) is a polyoxyalkylene obtained by polycondensation of at least one alkoxysilane represented by the formula (3), which is obtained by polycondensation. (R 5 ) n Si(OR 4 ) 4-n (3) (R 4 is a hydrocarbon group having 1 to 5 carbon atoms, respectively, and R 5 represents a hydrogen atom or an organic group having 1 to 5 carbon atoms , n is an integer from 0 to 3). 如申請專利範圍第2項之液晶配向劑，其中聚矽氧烷(A)係併用至少1種式(3)所表示之烷氧基矽烷，縮聚合所得之聚矽氧烷，[化5](R5 )n Si(OR4 )4-n (3)(R4 係分別碳原子數為1至5個之烴基，R5 係表示氫原子或碳原子數為1至5個之有機基，n係表示0至3之整數)。The liquid crystal alignment agent of claim 2, wherein the polyoxyalkylene (A) is a combination of at least one alkoxydecane represented by the formula (3), and polycondensed by polycondensation, [Chem. 5] (R 5 ) n Si(OR 4 ) 4-n (3) (R 4 is a hydrocarbon group having 1 to 5 carbon atoms, respectively, and R 5 represents a hydrogen atom or an organic group having 1 to 5 carbon atoms , n is an integer from 0 to 3). 如申請專利範圍第1項之液晶配向劑，其中聚矽氧烷(A)係將式(1)所表示之烷氧基矽烷、及四乙氧基矽烷縮聚合所得之聚矽氧烷，聚矽氧烷(B)係自四乙氧基矽烷所得之聚矽氧烷。 The liquid crystal alignment agent of claim 1, wherein the polyoxyalkylene (A) is a polyoxyalkylene obtained by polycondensation of an alkoxydecane represented by the formula (1) and tetraethoxysilane. The decane (B) is a polyoxyalkylene obtained from tetraethoxy decane. 如申請專利範圍第2項之液晶配向劑，其中聚矽氧烷(A)係將式(1)所表示之烷氧基矽烷、及四乙氧基矽烷縮聚合所得之聚矽氧烷，聚矽氧烷(B)係自四乙氧基矽烷所得之聚矽氧烷。 The liquid crystal alignment agent of claim 2, wherein the polyoxyalkylene (A) is a polyoxyalkylene obtained by polycondensation of an alkoxydecane represented by the formula (1) and tetraethoxysilane. The decane (B) is a polyoxyalkylene obtained from tetraethoxy decane. 一種液晶配向膜，其特徵為，使用如申請專利範圍第1項至第6項中任一項之液晶配向劑所得。 A liquid crystal alignment film obtained by using a liquid crystal alignment agent according to any one of claims 1 to 6. 一種液晶顯示元件，其特徵為，具有如申請專利範圍第7項之液晶配向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film according to item 7 of the patent application. 一種液晶配向劑之製造方法，其特徵為，包含混合下述之聚矽氧烷(A)之溶液及聚矽氧烷(B)之溶液之步驟，且聚矽氧烷(A)之矽原子之量係相對於聚矽氧烷(A)及聚矽氧烷(B)之矽原子總量，為3至80莫耳%；聚矽氧烷(A)之溶液：將含有2至30莫耳%比率之式(1)所表示之烷氧基矽烷之烷氧基矽烷，於有機溶劑中縮聚合所得之聚矽氧烷之溶液，[化7]R1 Si(OR2 )3 (1)(R1 係碳原子數為8至30個之有機基，R2 係表示碳原子數為1至5個之烴基)聚矽氧烷(B)之溶液：將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷，與甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、甲基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基丙基)三甲氧基矽烷、3-(2-胺基乙基胺基丙基) 三乙氧基矽烷、2-胺基乙基胺基甲基三甲氧基矽烷、2-(2-胺基乙基硫乙基)三乙氧基矽烷、3-巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、烯丙基三乙氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、三氟丙基三甲氧基矽烷、氯丙基三乙氧基矽烷、溴化丙基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙氧基二乙基矽烷、二丁氧基二甲基矽烷、二乙氧基甲基乙烯基矽烷、二乙氧基二乙烯基矽烷、3-胺基丙基二乙氧基甲基矽烷、3-巰基丙基甲基二甲氧基矽烷、2-(2-胺基乙基硫乙基)二乙氧基甲基矽烷、二甲氧基甲基-3,3,3-三氟丙基矽烷、3-氯丙基二甲氧基甲基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二甲氧基二苯基矽烷、二乙氧基二苯基矽烷、甲氧基三苯基矽烷、乙氧基三苯基矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、環戊基三甲氧基矽烷、環戊基三乙氧基矽烷之至少一種併用，於有機溶劑中縮聚合所得之聚矽氧烷之溶液，但是，不併用式(1)所表示之烷氧基矽烷，[化8]Si(OR3 )4 (2)(R3 係表示碳原子數為1至5個之烴基)。A method for producing a liquid crystal alignment agent, comprising the steps of mixing a solution of the polyoxane (A) described below and a solution of polyoxyalkylene (B), and a germanium atom of the polyoxyalkylene (A) The amount is 3 to 80 mol% relative to the total amount of deuterium atoms of polyoxyalkylene (A) and polyoxyalkylene (B); the solution of polyoxyalkylene (A): will contain 2 to 30 moles a solution of a polyoxyalkylene obtained by polycondensation of an alkoxydecane represented by the formula (1) represented by the formula (1), which is obtained by polycondensation in an organic solvent, [Chem. 7] R 1 Si(OR 2 ) 3 (1) (R 1 is an organic group having 8 to 30 carbon atoms, and R 2 is a hydrocarbon group having 1 to 5 carbon atoms) a solution of polyoxyalkylene (B): it will contain a formula represented by formula (2) Alkoxydecane of a tetraalkoxydecane, with methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, propyltrimethoxydecane, Propyltriethoxydecane, methyltripropoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2(aminoethyl)3- Aminopropyltriethoxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxysulfonium Alkyl, 3-(2-aminoethylaminopropyl)trimethoxynonane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyl Trimethoxy decane, 2-(2-aminoethyl thioethyl)triethoxy decane, 3-mercaptopropyltriethoxy decane, decylmethyltrimethoxydecane, 3-ureidopropyl Triethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, allyl triethoxy decane, 3-isocyanate propyl triethoxy decane, trifluoropropyl trimethoxy decane, Chloropropyltriethoxydecane, bromopropyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, diethoxydiethyldecane, dibutoxy Dimethyldecane, diethoxymethylvinylnonane, diethoxydivinyldecane, 3-aminopropyldiethoxymethyldecane, 3-mercaptopropylmethyldimethoxydecane , 2-(2-Aminoethylthioethyl)diethoxymethylnonane, dimethoxymethyl-3,3,3-trifluoropropylnonane, 3-chloropropyldimethoxy Methyl decane, phenyl trimethoxy decane, phenyl triethoxy decane, two Methoxy diphenyl decane, diethoxy diphenyl decane, methoxy triphenyl decane, ethoxy triphenyl decane, cyclohexyl trimethoxy decane, cyclohexyl triethoxy decane, cyclopentane a combination of at least one of a trimethoxy decane and a cyclopentyl triethoxy decane, which is obtained by polycondensation of the obtained polyoxyalkylene in an organic solvent, but the alkoxy decane represented by the formula (1) is not used in combination. Si(OR 3 ) 4 (2) (R 3 represents a hydrocarbon group having 1 to 5 carbon atoms). 如申請專利範圍第9項之液晶配向劑之製造方 法，其中聚矽氧烷(A)之溶液係將含有式(1)所表示之烷氧基矽烷之烷氧基矽烷，進行水解.縮聚合所得之聚矽氧烷。 For example, the manufacturer of the liquid crystal alignment agent of claim 9 In the method, the solution of the polyoxyalkylene (A) is an alkoxysilane having an alkoxydecane represented by the formula (1), which is subjected to hydrolysis and polycondensation. 如申請專利範圍第9項或第10項之液晶配向劑之製造方法，其中聚矽氧烷(B)之溶液係將含有式(2)所表示之四烷氧基矽烷之烷氧基矽烷，進行水解.縮聚合所得之聚矽氧烷。The method for producing a liquid crystal alignment agent according to claim 9 or 10, wherein the solution of the polyoxyalkylene (B) is an alkoxysilane having a tetraalkoxydecane represented by the formula (2). The polyoxyalkylene obtained by hydrolysis and polycondensation is carried out.
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