KR101214750B1 - Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(여기서, Z는 파장 200 내지 400 nm의 광에 의해 가교 반응 또는 이성화 반응을 발생시키는 감광기이고, X는 수산기, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 1 내지 20의 알콕실기, 또는 다른 반복 단위의 X와 합쳐져서 -O-를 통해 가교를 형성하고 있을 수도 있음). 본 발명은 도포성이 우수하고, 러빙 처리를 행하지 않고서 편광 또는 비편광의 방사선 조사에 의해서 액정 배향능을 부여하는 것이 가능한 액정 배향막의 형성에 이용되는 폴리오르가노실록산을 제공한다. The present invention relates to a polyorganosiloxane having a repeating unit represented by the following formula (1) and having a weight average molecular weight in the range of 1,000 to 100,000.
≪ Formula 1 >

(Wherein Z is a photosensitive group which generates a crosslinking reaction or an isomerization reaction by light having a wavelength of 200 to 400 nm, X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon group having 1 to 20 carbon atoms). May be combined with an alkoxyl group or X of another repeating unit to form a bridge through -O-. This invention provides the polyorganosiloxane which is excellent in applicability | paintability, and is used for formation of the liquid crystal aligning film which can provide liquid crystal aligning ability by irradiating polarized light or non-polarized light, without performing a rubbing process.

Description

Polyorganosiloxane, liquid crystal aligning film, and liquid crystal display element {POLYORGANOSILOXANE, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT}

The present invention relates to novel polyorganosiloxanes, liquid crystal alignment films, and liquid crystal display elements. More specifically, it has polyorganosiloxane used for formation of a liquid crystal aligning film, such a liquid crystal aligning film, and such a liquid crystal aligning film which can provide a liquid crystal aligning ability by irradiating polarized light or non-polarized radiation, without performing a rubbing process. It relates to a liquid crystal display element.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy has a sandwich structure as a substrate with a transparent electrode having a liquid crystal alignment film, and if necessary, the long axis of the liquid crystal molecules is continuously twisted between 0 and 360 degrees between the substrates. Liquid crystal display devices having liquid crystal cells such as twisted nematic (STN) type, super twisted nematic (STN) type, and in plane switching (IPS) type are known (Japanese Patent Laid-Open No. 56-91277 and Japanese Patent Laid-Open See 1-120528.

In such a liquid crystal cell, it is necessary to provide a liquid crystal aligning film on the substrate surface in order to align the liquid crystal in a predetermined direction with respect to the substrate surface. This liquid crystal aligning film is normally formed by the method (rubbing method) which rubs the organic film surface formed in the board | substrate surface in the direction made with cloth members, such as rayon. However, when the liquid crystal aligning film is formed by a rubbing treatment, dust is easily generated or static electricity is generated in the process, and thus, there is a problem that dust adheres to the surface of the alignment film and causes display defects. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there is a problem that circuit breakdown of the TFT element occurs due to the generated static electricity, which causes a decrease in yield. Moreover, in the liquid crystal display element which becomes increasingly high definition in the future, since the unevenness | corrugation arises in the surface of a board | substrate with density increase of a pixel, it becomes a subject to perform a rubbing process uniformly.

As another means for orienting a liquid crystal in a liquid crystal cell, light which imparts liquid crystal alignment capability by irradiating polarized or non-polarized radiation to a photosensitive thin film made of polyvinylcinnamate, polyimide, azobenzene derivative, etc. formed on the surface of a substrate. An orientation method is known. According to this method, it is possible to realize uniform liquid crystal alignment without generating static electricity or dust (Japanese Patent Application Laid-Open No. 6-287453, Japanese Patent Application Laid-open No. Hei 10-251646, Japanese Patent Application Publication ( Japanese Patent Laid-Open No. 11-2815, Japanese Patent Laid-Open No. 11-152475, Japanese Patent Laid-Open No. 2000-144136, Japanese Patent Laid-Open No. 2000-319510, Japanese Patent Laid-Open No. 2000-281724, Japanese Patent Laid-Open No. 9-297313, Japanese Patent Laid-Open No. 2003-307736, Japanese Patent Laid-Open No. 2004-163646 and Japanese Patent Laid-Open No. 2002-250924.

By the way, in liquid crystal cells, such as TN (Twisted Nematic) type and STN (Super Twisted Nematic) type, a liquid crystal aligning film needs to have the pretilt angle characteristic which inclines orients liquid crystal molecules with respect to a board | substrate surface at a predetermined angle. When forming a liquid crystal aligning film by the photo-alignment method, a pretilt angle is normally given by inclining the incidence direction with respect to the board | substrate surface of the radiation to irradiate from a substrate normal line.

Moreover, the vertical (homeotropic) orientation mode which aligns the liquid crystal molecule which has negative dielectric anisotropy perpendicular to a board | substrate as an operation mode of a liquid crystal display element separate from the above is also known. In this operation mode, it is necessary to apply a voltage between the substrates so that when the liquid crystal molecules are inclined in a direction parallel to the substrate, the liquid crystal molecules are inclined in one direction in the substrate surface from the substrate normal direction. As a means for this, for example, a method of providing projections on the surface of the substrate, a method of providing stripes on the transparent electrode, and using a rubbing alignment film to tilt the liquid crystal molecules slightly from the substrate normal direction toward one direction in the substrate surface (free And the like) have been proposed.

It is known that the optical alignment method is also useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell in a vertical alignment mode. That is, it is known that the inclination direction of the liquid crystal molecules at the time of voltage application can be uniformly controlled by using the vertical alignment film which gives the alignment regulating force and the pretilt angle by the photo alignment method (Japanese Patent Laid-Open No. 2003-307736). , Japanese Patent Laid-Open No. 2004-163646, Japanese Patent Laid-Open No. 2004-83810, Japanese Patent Laid-Open No. 9-211468 and Japanese Patent Laid-Open No. 2003-114437.

Thus, the liquid crystal aligning film manufactured by the said photo-alignment method can be effectively applied to various liquid crystal display elements. However, there existed a problem that the conventional photo-alignment film had a large amount of radiation irradiation required in order to obtain a large pretilt angle. For example, in a photoalignment film containing an azobenzene derivative, in order to obtain a sufficient pretilt angle, it is reported that radiation of which the optical axis is inclined from the substrate normal should be irradiated at least 1 J / cm 2 (Japanese Patent Laid-Open No. 2002). -250924, Japanese Patent Laid-Open No. 2004-83810, and J. of the SID 11/3, 2003 p.579).

An object of the present invention is excellent in applicability and electrical properties, and polyorganosiloxane used for the formation of a liquid crystal aligning film capable of imparting liquid crystal alignment ability by irradiation of polarized light or non-polarized light without performing rubbing treatment and its production To provide a way.

Another object of the present invention is to provide a liquid crystal alignment film containing the polyorganosiloxane.

Another object of the present invention is to provide a liquid crystal display device.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above object and advantages of the present invention are firstly polyorganosiloxanes having a repeating unit represented by the following formula (1) and having a weight average molecular weight in the range of 1,000 to 100,000 (hereinafter, of the present invention). A polyorganosiloxane).

(Wherein Z is a photosensitive group which generates a crosslinking reaction or an isomerization reaction by light having a wavelength of 200 to 400 nm, X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon group having 1 to 20 carbon atoms). May be combined with an alkoxyl group or X in another repeating unit represented by the same formula (1) to form a bridge through -O-)

According to the present invention, the above objects and advantages of the present invention are preferred by the polyorganosiloxane, which is a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3) Is achieved.

Here, A ₁ , A ₂ may be the same or different, and may be a monovalent organic group including an alkyl group or an alicyclic group which may be substituted with a fluorine atom having 1 to 40 carbon atoms, and B ₁ , B ₂ may be the same or different. And a fluorine atom or a cyano group, p is an integer of 0 to 4, S ₁ and S ₂ may be the same or different, a divalent organic group having an alkylene group having 1 to 20 carbon atoms, and X ₁ , X ₂ may be the same or different and is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or X ₁ in other repeating units represented by the formula (2) or (3). Alternatively, it may be combined with X ₂ to form a crosslink through -O-.

According to the present invention, the above object and advantage of the present invention, the polyorganosiloxane of the present invention by hydrolyzing and condensing at least one selected from the group consisting of silane compounds represented by the following general formulas (4) and (5) There is provided a method of preparing the same.

Herein, the definitions of A ₁ , A ₂ , B ₁ , B ₂ , S ₁ , S _2, and p are the same as those of Formulas 2 and 3, R ₁ and R ₂ may be the same or different, and include 1 to C. 20 alkyl group or aryl group having 6 to 20 carbon atoms, Y ₁ , Y ₂ may be the same or different, alkoxyl group having 1 to 20 carbon atoms or chlorine atom, and n is 2 or 3)

According to the present invention, the above objects and advantages of the present invention are preferably achieved by a method for producing polyorganosiloxane, in which the catalyst for hydrolysis and condensation is an organic acid.

According to the present invention, the above objects and advantages of the present invention are preferably achieved by a production method in which hydrolysis and condensation are carried out in the coexistence of a silane compound represented by the following formula (7).

(Wherein R ₃ is an alkyl group which may contain an alicyclic group having 1 to 40 carbon atoms or an aryl group of 6 to 20, R ₄ is an alkyl group having 1 to 20 carbon atoms, and t is 0, 1, 2 or 3) being)

According to the present invention, the above objects and advantages of the present invention are sixth achieved by a liquid crystal alignment film obtained by irradiating polarized or non-polarized radiation to a film formed of the polyorganosiloxane.

According to this invention, the said objective and advantage of this invention are 7th achieved by the liquid crystal display element which has the said liquid crystal aligning film.

According to the present invention, it is preferable that the liquid crystal display element uses a negative liquid crystal.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The polyorganosiloxane of the present invention has a repeating unit represented by Chemical Formula 1 and has a weight average molecular weight of 1,000 to 100,000.

In Formula 1, Z is a photosensitive group which generates a crosslinking reaction or an isomerization reaction by light having a wavelength of 200 to 400 nm. X is combined with X in a hydroxyl group, an alkyl group of 1 to 20 carbon atoms, an aryl group of 1 to 20 carbon atoms, an alkoxyl group of 1 to 20 carbon atoms, or similarly represented by the formula (1) to form a bridge through -O- You may be doing it.

Preferred X is a group which is combined with X of a hydroxyl group, a methoxy group, an ethoxy group or another repeating unit to form a crosslinking through -O-.

As a repeating unit represented by the said Formula (1), the repeating unit represented by the said Formula (2) or the repeating unit represented by the said Formula (3) is illustrated as a preferable thing.

In Formulas 2 and 3, A ₁ and A ₂ may be the same or different, and may be a monovalent organic group including an alkyl group or an alicyclic group which may be substituted with a fluorine atom having 1 to 40 carbon atoms. B ₁ and B ₂ may be the same or different and are a fluorine atom or a cyano group. p is an integer of 0-4. S ₁ and S ₂ may be the same or different and are a divalent organic group having an alkylene group having 1 to 20 carbon atoms. X ₁ , X ₂ may be the same or different and may be a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or other repetition represented by the same formula (II) or (3). It may combine with X <_1> or X <_2> in a unit, and may form bridge | crosslinking through -O-.

As a specific example of the group located above the silicon atom in the said Formula (2) and (3), the structure represented by each of Formula (6-1)-(6-14) is mentioned, for example.

(In these formulas, m is an integer of 1-20, l is an integer of 2 m + 1 or less, k is an integer of 1-10, q is an integer of 2-10, m is 3-18, l is 3 To 9, k is 2 to 6, q is more preferably 2 to 6, particularly preferably m is 4 to 10, l is 3 to 7, k is 2 to 4, q is 2 to 4)

The weight average molecular weight of the polyorganosiloxane of the present invention is preferably 1,000 to 50,000.

The polyorganosiloxane of the present invention can be obtained, for example, by hydrolytic condensation of the silane compound of Formula 4 or Formula 5.

In Formulas 4 and 5, A ₁ , A ₂ , B ₁ , B ₂ , S ₁ , S _2, and p have the same definitions as in Formulas 2 and 3 above. As Y <_1> , Y <_2> , a chlorine atom and a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, alkoxyl groups, such as t-butoxy, etc. are mentioned, for example. Can be mentioned. Among these, Preferably they are a chlorine atom, a methoxy group, and an ethoxy group. As R ₁ and R ₂ , for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n- Heptadecyl group, n-octadecyl group, n-nonadecyl group, the alkyl group, such as n-eicosyl group, and the aryl group, such as a phenyl group, etc. are mentioned. Preferred among these are methyl group, ethyl group and phenyl group.

Further, n in the formulas (4) and (5) is preferably 3.

The compound of the formula (4) can be obtained by a known method such as, for example, Schemes 1 to 3 below, but is not limited to these methods. However, r in Reaction Formulas 1-3 is k-2. The compound of formula 5 can also be obtained by the same method.

[Reaction Scheme 1]

Scheme 1: The compound of formula 4 can be obtained by heating, stirring (hydrosilylation reaction) and purifying the precursor of the compound of formula 4 with alkenes and triethoxysilane in the presence of a very small amount of platinum catalyst.

Scheme 2

Scheme 2: The compound of formula 4 is obtained by heating and stirring the precursor of the compound of formula 4 having carboxylic acid and 3-glycidyloxypropyltrimethoxysilane in the presence of a base catalyst such as, for example, triethylamine. Can be.

Scheme 3

Scheme 3: The compound of formula 4 can be obtained by heating and stirring the compound of formula 4 having a hydroxyl group and triethoxysilanylpropyl-isocyanate, for example, in the presence of a tin catalyst such as dibutyltin dilaurate.

Hydrolysis and Condensation Method of Polyorganosiloxanes

The polyorganosiloxane of this invention can be obtained by hydrolyzing and condensing the silane compound represented by the said Formula (4) or (5). At this time, it is preferable that the silane compound represented by the formula (7) coexist to cohydrolytic condensation.

In formula (7), R <_3> is a C1-C40 alkyl group which may contain the alicyclic group, or a C6-C20 aryl group, R <_4> is a C1-C20 alkyl group, t is 0, 1, 2 Or three.

As a silane compound represented by General formula (7), for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec- Butoxysilane, tetra-tert-butoxysilane; Methyltrimethoxysilane, Methyltriethoxysilane, Methyltri-n-propoxysilane, Methyltri-iso-propoxysilane, Methyltri-n-butoxysilane, Methyltri-sec-butoxysilane, Methyltri -tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxy Silane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, phenyltriethoxysilane; Dimethyldimethoxysilane, dimethyldiethoxysilane; Trimethylmethoxysilane, trimethylethoxysilane, and the like. Among them, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and trimethylmethoxysilane And trimethylethoxysilane is preferable.

With respect to 1 mol of the silane compound of Formula 4 or Formula 5, 0 to 100 moles of the silane compound of Formula 7 may be used. It is preferable to use 1-100 mol, and it is more preferable to use 2-20 mol.

Hydrolysis and condensation can be obtained by making a silane compound and water react, and hydrolysis and partial condensation. A silane compound in order to hydrolysis, a condensation part, a siloxane bond (the sum of the formula (4) -Y _1, -Y ₂ of the formula (V) and formula (7) of the OR ₄₎ 1 mol, and preferably used is from 1.0 to 1.5 moles of water do. When the amount of water is 1.0 mol or more, the possibility that the siloxane bonds remain unreacted decreases, and there is no fear that the uniformity of the coating film is lowered, and there is less fear that the storage stability of the liquid crystal aligning agent decreases. Water is added intermittently or continuously in the organic solvent which melt | dissolved the silane compound of this invention. At this time, a reaction catalyst can be used. In that case, the catalyst may be previously added to the organic solvent, or may be dissolved or dispersed in water at the time of water addition. As reaction temperature at this time, Preferably it is 0-100 degreeC, More preferably, it is 15-80 degreeC.

As the organic solvent, preferably an alcohol solvent, a ketone solvent, an amide solvent, an ester solvent or an aprotic solvent is used. These may be used alone or in combination of two or more.

Here, as the alcohol solvent, for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n Octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol monoalcohol solvents such as sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2 Polyhydric alcohol solvents such as ethyl hexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Polyhydric alcohol partial ether solvents such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

These alcohol solvents can also be used 1 type or in combination of 2 or more types.

Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, and ethyl n-butyl. Ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, phenchon, etc. Besides, acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5 -Nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2 (Beta) -diketones, such as a 4-heptanedione, etc. are mentioned.

These ketone solvents can also be used 1 type or in combination of 2 or more types.

As the amide solvent, for example, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N- Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like.

These amide solvents can also be used 1 type or in combination of 2 or more types.

Examples of the ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate and i-propyl acetate. , N-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid Benzyl, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol acetate Monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, ace Acid propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetate glycol, methoxytriglycol acetate, ethyl propionate, N-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc. Can be.

These ester solvents can also be used 1 type or in combination of 2 or more types.

As an aprotic solvent, for example, acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methylmorpholone, N-methylpyrrole, N-ethyl Pyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N -Methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, etc. are mentioned. Can be. In this, a polyhydric alcohol solvent, a polyhydric alcohol partial ether solvent, and an ester solvent are especially preferable.

In the hydrolysis and partial condensation reaction of the silane compound of the present invention, a catalyst is preferably used. Examples of such a catalyst include the following metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, Tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis ( Acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (acetylacetonate) titanium , Di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris (acetylacetonate) titanium, mono-n-propoxy? Tris (acetylacetonate) titanium, mono-i-propoxy-tris (acetylacetonate) titanium, mono-n-part Oxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium,

Triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium, tri-n-butoxy mono (Ethylacetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (ethylacetoacetate) titanium, di- n-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate) titanium, di-sec-butoxy? Bis (ethylacetoacetate) titanium, di-t-butoxy bis (ethylacetoacetate) titanium, monoethoxytris (ethylacetoacetate) titanium, mono-n-propoxytris (ethylacetoacetate) titanium, Mono-i-propoxy tris (ethylacetoacetate) titanium, mono-n-butoxy? Lith (ethylacetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetyl Titanium chelate compounds such as acetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium and the like;

Triethoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri-i-propoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono (Acetylacetonate) zirconium, tri-sec-butoxy mono (acetylacetonate) zirconium, tri-t-butoxy mono (acetylacetonate) zirconium, diethoxy bis (acetylacetonate) zirconium, di- n-propoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di-n-butoxy bis (acetylacetonate) zirconium, di-sec-butoxy? Bis (acetylacetonate) zirconium, di-t-butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonate) zirconium, Mono-i-propoxy tris (acetylaceto Nit) zirconium, mono-n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetra Keith (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy-mono (ethylacetoacetate) zirconium, Tri-n-butoxy mono (ethylacetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate) zirconium, diethoxy bis ( Ethylacetoacetate) zirconium, di-n-propoxy bis (ethylacetoacetate) zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di-n-butoxy bis (ethylacetoacetate) zir nose , Di-sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, mono-n-propoxy? Tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris (ethylacetoacetate Zirconium, mono-t-butoxytris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethyl Zirconium chelate compounds such as acetoacetate) zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium;

Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum

And the like.

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, Butyric acid, melit acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, Trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

As an inorganic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, etc. are mentioned, for example.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine and monomethyl diethanolamine. , Triethanolamine, diazabicyclo oran, diazabicyclononane, diazabicyclo undecene, tetramethylammonium hydroxide, etc. are mentioned.

As an inorganic base, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. are mentioned, for example.

Among these catalysts, metal chelate compounds, organic acids and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable. These can also use together 1 type (s) or 2 or more types.

The amount of the catalyst used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 100 parts by weight of the combination of compounds (4), (5) and compound (7) (completely hydrolyzed condensate). To 1 part by weight.

The liquid crystal aligning agent of the present invention is preferably formed by dissolving or dispersing the hydrolysis and condensate in an organic solvent.

As an organic solvent, the organic solvent represented by each of following General formula (8), 9, and 10 is used.

In Formula 8, R ₃ is hydrogen, a methyl group, an ethyl group or an acetyl group, R ₄ is an alkyl group having 1 to 4 carbon atoms, s is an integer of 1 to 3, and in Formula 9, R ₅ is hydrogen, a methyl group, an ethyl group Or an acetyl group, R ₆ is an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3, and in formula 10, R ₇ is an alkyl group having 2 to 5 carbon atoms)

As a specific example of the organic solvent represented by General formula (8),

1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, Dipropylene glycol dimethyl ether etc. are mentioned. Among these, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are mentioned preferably.

As a specific example of the organic solvent represented by General formula (9),

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve Acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol and the like. Among these, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve) and ethylene glycol monoamyl ether are mentioned preferably.

As a specific example of the organic solvent represented by General formula (10),

N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethyl acetate Butyl, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-pentyl acetate are mentioned preferably.

You may add components, such as surfactant, to the liquid crystal aligning agent obtained by this invention. As surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, etc. are mentioned, for example. Furthermore, silicone surfactant, polyalkylene oxide surfactant, a fluorine-containing surfactant, etc. are mentioned.

In addition, the liquid crystal aligning agent of this invention may contain the functional silane containing compound or the epoxy group containing compound from a viewpoint of improving the adhesiveness to the board | substrate surface. As such a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrier Methoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-tri Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl- 3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-ben Jyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltri Methoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyl Oxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. As the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3, 5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidyl Aminomethyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diamino diphenylmethane, etc. are mentioned as a preferable thing.

Although the ratio of the polyorganosiloxane which is a reaction product in the liquid crystal aligning agent of this invention, and a solvent is selected in consideration of viscosity, volatility, etc., the ratio (solid content concentration) of the polyorganosiloxane in a liquid crystal aligning agent is a polyorganosiloxane. a silicon atom contained in the SiO ₂ concentration in terms of SiO _2, preferably 0.01 to 70% by weight, more preferably 0.05 to 60% by weight, more preferably 1 to 30% by weight. As described later, the liquid crystal aligning agent of the present invention is preferably applied to the surface of the substrate by, for example, a roll coater method, a spinner method, a printing method, and the like, and is then formed as a coating film to be a liquid crystal alignment film by heating and drying it. Is less than 0.01% by weight, the film thickness of this coating film is too small to obtain a good liquid crystal aligning film. When the solid content concentration exceeds 70% by weight, the film thickness of the coating film is excessive to provide a good liquid crystal aligning film. It is hard to obtain, and the viscosity of a liquid crystal aligning agent may increase and inferior to a coating characteristic.

Liquid crystal alignment film

As a method of forming a liquid crystal aligning film using the liquid crystal aligning agent of this invention, the following method is mentioned, for example. First, the liquid crystal aligning agent of this invention is apply | coated to the transparent conductive film side of the board | substrate with a transparent conductive film, for example by the roll coater method, the spinner method, the printing method, the inkjet method, etc., For example, it heats at the temperature of 40-300 degreeC. To form a coating film. At this time, a crosslinking reaction occurs between the polyorganosiloxanes. In order to generate | occur | produce bridge | crosslinking fully, it is preferable to perform processing for 10 minutes-3 hours at 150-250 degreeC. Heating can also be performed in nitrogen in air. The film thickness of a coating film is solid content, Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

As the substrate, for example, a transparent substrate containing a glass film such as float glass, soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone or polycarbonate can be used.

As the transparent conductive film, for example, an NESA film made of SnO ₂ , an ITO film made of In ₂ O ₃ —SnO ₂ , and the like can be used. For the patterning of these transparent conductive films, a photo-etching method, a method of using a mask in advance, and the like are used.

In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate and a transparent conductive film and a coating film further favorable, you may apply | coat a functional silane containing compound, titanate, etc. on a board | substrate and a transparent conductive film previously.

Subsequently, the said coating film is irradiated with linearly or partially polarized radiation or unpolarized radiation, and in some cases, heat treatment is further performed at a temperature of 150 to 250 ° C to impart liquid crystal alignment ability. As the radiation, ultraviolet rays and visible rays having a wavelength of 200 to 400 nm can be used. When the used radiation is linearly polarized or partially polarized, irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed in an inclined direction in order to give a pretilt angle, or may be performed in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be inclined direction.

As the light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. Moreover, the ultraviolet-ray of the said preferable wavelength range can be obtained by a means which uses a filter, a diffraction grating, etc. together with the said light source.

In addition, the "pretilt angle" in this invention shows the inclination angle of the liquid crystal molecule from the direction parallel to a board | substrate surface.

Liquid crystal display element

The liquid crystal display element formed using the liquid crystal aligning agent of this invention is manufactured as follows. The board | substrate with which the said liquid crystal aligning film was formed was prepared, the two sheets are opposed so that the polarization direction of the polarized radiation which irradiated the liquid crystal aligning film may become a predetermined angle, the peripheral part between board | substrates is sealed with a sealing agent, a liquid crystal is filled, It seals and comprises a liquid crystal cell. Next, after heating the liquid crystal cell which used the liquid crystal cell to the temperature which takes an isotropic phase, it is preferable to cool to room temperature and to remove the flow orientation at the time of injection.

And it is set as a liquid crystal display element by bonding a polarizing plate so that the polarization direction of a polarizing plate may make a predetermined angle with the easy axis of alignment of the liquid crystal aligning film of a board | substrate, respectively, on both surfaces. When the liquid crystal alignment film is horizontally aligned, the TN type or STN type liquid crystal cell is adjusted by adjusting the angle between the polarization direction of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate on the two substrates on which the liquid crystal alignment film is formed. The liquid crystal display element which has can be obtained arbitrarily. On the other hand, when a liquid crystal aligning film is vertically oriented, a cell is comprised so that the direction of the easy axis of orientation in two board | substrates with a liquid crystal aligning film may be parallel, and the polarizing plate has a polarization direction whose angle of 45 degree with this polarizing plate on this. It can be bonded so that it may be set as the liquid crystal display element which has a vertically-aligned liquid crystal cell.

As the sealant, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used.

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. can be used, for example. Moreover, in the case of the vertically-aligned liquid crystal cell, it is preferable to have negative dielectric anisotropy which forms a nematic liquid crystal, for example, dicyano benzene type liquid crystal, a pyridazine type liquid crystal, a Schiff base type liquid crystal, a clan clock A liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal etc. are used.

As a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate etc. which made the polarizing film called H film | membrane which absorbed iodine between the cellulose acetate protective film, or the polarizing plate which consists of H film itself etc. are stretched and oriented, and polyvinyl alcohol is mentioned.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1

In a 300 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 11.8 g of a compound represented by the following formula (6-5-1-1), 8.29 g of potassium carbonate, 1.00 g of potassium iodide, and 4-butyl-1-butene 4.46 g and 120 mL of 1-methyl-2-pyrrolidone were added, followed by stirring at 90 ° C. under nitrogen for 3 hours. After completion of the reaction, toluene and water were added for extraction, dried over magnesium sulfate, concentrated, and then recrystallized with methanol to obtain 9 g of the compound represented by the following formula (6-5-1-2).

Synthesis Example 2

In a 100 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 8.0 g of a compound represented by the following formula (6-5-1-2), 5.88 g of triethoxysilane, and 0.2 M chloroplatinic acid hexahydrate and isopropanol solution were prepared. 40 µL was added, degassed, and refluxed under nitrogen for 10 hours. Next, the reaction solution was passed through a short column of silica gel, concentrated, and dried sufficiently to obtain a white, viscous liquid. In addition, this viscous liquid was purified by a silica column to obtain 3.5 g of a compound represented by the following formula (6-5-1).

[Reaction Scheme 4]

Synthesis Example 3, 4

In the same manner as in Scheme 4 for preparing the compound represented by the above (6-5-1), a compound represented by the following formula (6-2-1) and a compound represented by the following formula (6-13-1) were obtained. .

[Weight Average Molecular Weight]

It calculated by polystyrene conversion by GPC.

[Pretilt angle]

T. J. Scheffer et. al. J. Appl. Phys. vo. 19, p. 2013 (1980)], was measured by the crystal rotation method using a He-Ne laser light.

[Orientation of liquid crystals]

The presence or absence of the abnormal domain at the time of turning on / off (or off) the voltage to the liquid crystal display element was observed with the polarization microscope, and the case where there was no abnormal domain was determined as "good".

[Voltage retention rate]

After applying a voltage of 5 V to the liquid crystal display element at an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention after 167 milliseconds from the release of the application was measured. The measurement apparatus used VHR-1 by Toyo Technica. The case where voltage retention is 90% or more was "good", and the case other than that was judged as "defect".

[Printability Evaluation]

A glass substrate of 127 mm (D) x 127 mm (W) x 1.1 mm (H) having an ITO film formed on one side of the whole surface was prepared, and a printing machine (Nihon Shashin Insatsu Co., Ltd. product) for liquid crystal aligning film application was prepared on this glass substrate. After filtration of the liquid crystal aligning agent obtained in the said experiment using the angstromer S-40L) with the microfilter of 0.2 micrometer of pore diameters, it applied to the transparent electrode surface. It dried with the hotplate adhesive predryer set to 80 degreeC, baked at 200 degreeC for 60 minutes, and formed the liquid crystal aligning film on the glass substrate with an ITO film. The nonuniformity of the obtained orientation film was visually evaluated, and the thing which "good" and the nonuniformity showed that there was no nonuniformity was made into "defective."

Example 1

In a 200 mL three-necked flask equipped with a cooling tube, 3.1 g (5 mmol) of the compound represented by the above formula (6-5-1), 12.7 g of tetraethoxysilane (abbreviated as TEOS, 60 mmol), 1- 37.4 g of ethoxy-2-propanol were added and heated to 60 ° C. and stirred. 0.165 g of maleic anhydride and 6.95 g of aqueous maleic anhydride solution were added to a 20 ml volumetric flask, and the mixture was heated and stirred at 60 ° C for further 4 hours. The solvent was distilled off from the obtained polymerization solution, and the weight was 30.2g, and the raw material polymer solution was obtained. Furthermore, the aligning agent coating liquid S-1 of 4 weight% of solid content concentration was obtained by adding butyl acetate. It was 2,200 when the weight average molecular weight was measured by GPC.

Examples 2-4

In the same manner as in Example 1, hydrolytic condensation was carried out using the compositions shown in Table 1 to synthesize an alignment agent coating liquid.

Example 5

The alignment agent coating liquid S-1 was applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film, using a spinner so that the film thickness was 0.1 μm, and then at 200 ° C. in an oven substituted with nitrogen. It dried for 1 hour and formed the thin film.

Next, the surface of this thin film was irradiated with the polarized ultraviolet-ray 0.1 J / cm <2> containing 313 nm bright line in the direction inclined 40 degree | times from the board | substrate normal line using the Hg-Xe lamp and the Glen Taylor prism. Next, after screen-printing the aluminum oxide sphere containing epoxy resin adhesive of 5.5 micrometers in diameter to the surface in which the liquid crystal aligning film was formed, about the pair of board | substrates which performed the ultraviolet irradiation process, the projection direction with respect to the board surface of the optical axis of an ultraviolet-ray is The substrates were overlapped and pressed so as to be anti-parallel, and the adhesive was thermosetted at 150 ° C. over 1 hour. Next, after filling a negative type liquid crystal (MLC-6608 by Merck Corporation) between a pair of board | substrates from a liquid crystal injection hole, the liquid crystal injection hole was sealed with the epoxy adhesive. In addition, in order to remove the flow orientation at the time of liquid crystal injection, after cooling at 150 degreeC, it cooled slowly to room temperature. Next, the polarizing plates were bonded to both outer surfaces of the substrate so that their polarization directions were perpendicular to each other, and the liquid crystal display elements were joined to form an angle of 45 degrees with the projection direction with respect to the substrate surface of the optical axis of the ultraviolet ray of the liquid crystal alignment film. The orientation was shown. When a voltage of 5 V was applied, a change in contrast of the liquid crystal display element was observed in response to ON-OFF of the applied voltage. As a result of evaluating the cell, the pretilt angle was 89.3 °, the liquid crystal alignment property, and the voltage retention were all "good". Moreover, it was "good" when the printability of the said aligning agent coating liquid S-1 was evaluated.

Examples 6-8

Evaluation was performed about alignment agent coating liquids S-2 to S-4 in the same manner as in Example 5. The results are shown in Table 2.

From these, the polyorganosiloxane of this invention is excellent in applicability | paintability, a sensitivity, liquid crystal aligning property, and an electrical property, and it turns out that it can use very usefully for a liquid crystal display element.

[Effects of the Invention]

When the polyorganosiloxane of this invention is used, a liquid crystal aligning film can be obtained with a little radiation dose compared with the case by the conventional photo-alignment method. Therefore, when this liquid crystal aligning film is applied to a liquid crystal display element, a liquid crystal display element can be manufactured more inexpensively than before. Therefore, these liquid crystal display elements can be effectively applied to various devices, and are preferably used for devices such as a table calculator, a wrist watch, a table clock, a counting plate, a word processor, a personal computer, or a liquid crystal television.

Claims (7)

It is characterized by hydrolyzing and condensing at least one selected from the group consisting of silane compounds represented by the following formula (1 '), having a repeating unit represented by the following formula (1) and having a weight average molecular weight in the range of 1,000 to 100,000 Process for preparing polyorganosiloxane.
&Lt; Formula 1 >

(Wherein Z is a photosensitive group which generates a crosslinking reaction or an isomerization reaction by light having a wavelength of 200 to 400 nm, and is any one of structures represented by the following general formulas (6-1) to (6-14), X is combined with X in a hydroxyl group, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkoxyl group of 1 to 20 carbon atoms, or similarly represented by the general formula (1) to form a bridge through -O- May be

(Wherein m is an integer of 1 to 20, l is an integer of 2m + 1 or less, k is an integer of 1 to 10, q is an integer of 2 to 10) in formulas (6-1) to (6-14)
<Formula 1 '>

(Wherein the definition of Z is the same as that of Formula 1, R ₁ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, Y ₁ is an alkoxyl group having 1 to 20 carbon atoms or a chlorine atom, and n is 2 or 3) The production method according to claim 1, wherein the catalyst for hydrolysis and condensation is an organic acid. The production method according to claim 1 or 2, wherein the hydrolysis and condensation are performed in the presence of a silane compound represented by the following formula (7).
&Lt; Formula 7 >

(Wherein R ₃ is an alkyl group which may contain an alicyclic group having 1 to 40 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ₄ is an alkyl group having 1 to 20 carbon atoms, t is 0, 1, 2 or 3) delete delete delete delete