JP3330217B2 - Liquid crystal display spacer and liquid crystal display device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid crystal display spacer and a liquid crystal display device, and more particularly to a liquid crystal display spacer capable of preventing a liquid crystal alignment abnormality around or between spacers at the time of energization and enabling a uniform display. The present invention relates to a liquid crystal display spacer and a liquid crystal display device.

[0002]

2. Description of the Related Art A liquid crystal display has a structure as shown in FIG. A transparent electrode 3 patterned in a predetermined shape and an alignment film 4 covering the transparent electrode 3 are provided on the upper and lower glass substrates 2, and a liquid crystal material 5 is injected between the two glass substrates 2. The periphery of the glass substrate is sealed with a sealant 6. In order to keep the distance between the liquid crystal cells constant, the liquid crystal display spacer 7 is used.
Are uniformly dispersed, and the distance between the liquid crystal cells is generally 1 to 30 μm. Finally, the polarizing plates 1 are provided on both outer sides of the glass substrate 2 to complete a liquid crystal display cell.

Incidentally, in a TN (twisted nematic) or STN (super twisted nematic) liquid crystal panel, static electricity is easily generated when the protective film is removed at the time of manufacturing the liquid crystal panel, which causes abnormal alignment of liquid crystal molecules around a spacer. There is a problem that occurs. Furthermore, there is a problem that during the energization of the panel, abnormal alignment of the liquid crystal occurs around the spacers or between the spacers, and the region expands with the energization time.

[0004] Regarding these, abnormal blending due to static electricity can be eliminated by realigning the liquid crystal by a so-called aging operation (annealing step) of the liquid crystal panel in the production of the liquid crystal panel, but there is a problem that the production efficiency is lowered. there were. On the other hand, the current state is that there is no countermeasure for abnormal orientation occurring during energization.

[0005]

Means for Solving the Problems The present inventors have been keen to solve the above-mentioned drawbacks of the prior art, and to provide a liquid crystal display spacer and a liquid crystal display device in which alignment abnormality of liquid crystal does not occur between liquid crystal spacers. As a result of repeated studies, the present invention has been completed. That is, the present invention, at least on the surface of the following formula (1)

[0006]

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Wherein R is at least one fluorine atom and has 1 to 18 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an acyl group, an alkylcarbamoyl group, an acylcarbamoyl group or an aryl group. R ₁ represents a linear or branched alkylene group having 2 to 4 carbon atoms, which may be substituted with a hydroxy group, m represents an integer of 1 to 100, and m R ₁
May be the same or different. A) a liquid crystal display spacer comprising fine particles containing a fluorine atom and containing a nonionic hydrophilic unit represented by formula (1), and fluorine represented by the above formula (1) as the liquid crystal display spacer. It is an object of the present invention to provide a liquid crystal display device characterized by using fine particles having atoms and containing a nonionic hydrophilic unit.

The fine particles containing a fluorine atom and having a nonionic hydrophilic unit represented by the above formula (1) used in the present invention can be produced by, for example, the following production methods 1 to 3.
Can be manufactured. Production method 1 The following formula (2)

[0009]

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(Wherein, R, R ₁ and m have the same meanings as described above, and X represents a hydrogen atom or a methyl group). Production method 2 The following formula (3) or (4)

[0011]

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[0012] (wherein, R, R ₁ and m .n which as defined above is an integer of 0 to 100 inclusive, n pieces of R ₁ may be be the same or different .Z represents a hydrogen atom A metal atom such as an alkali metal, an alkaline earth metal, aluminum and titanium; an aminoalkyl group, preferably an aminoalkyl group having 1 to 5 carbon atoms in the alkyl group; or a carboxyalkyl group, preferably having 1 carbon atom in the alkyl group. A carboxyalkyl group represented by formulas (1) to (5): surface treatment of fine particles having a substituent capable of reacting with this compound on the surface. Manufacturing method 3 At least the following formula (5)

[0013]

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(Wherein, R ₁ and m have the same meanings as described above). The fine particles having a nonionic hydrophilic unit represented by the formula ( ₁ ) have at least one fluorine atom and have 1 to 1 carbon atoms. An acid halide or an acid anhydride having an acyl group of 18, an epoxy compound represented by the above formula (4), an α-amine having at least one fluorine atom and having 3 to 18 carbon atoms;
A method of modifying the surface with an olefin epoxide or an isocyanate compound having at least one fluorine atom and having an alkyl group, an acyl group or an aryl group having 1 to 18 carbon atoms. Hereinafter, each manufacturing method will be described in detail.

<Production Method 1> Examples of the compound represented by the formula (2) that can be used in the present method include hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and polyoxyethylene mono (meth) acrylate. A) acrylate, glycerol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate and other (meth) acrylate monomers such as (per) C1-C18 (per) fluoroalkyl groups such as fluoromethyl, (per) fluoropropyl, (per) fluoroisopropyl, (per) fluorobutyl, (per) fluorostearyl, and carbon number such as (per) fluoropropenyl 2
C18 such as (per) fluoroalkenyl group, (per) fluorophenyl, (per) fluorobiphenyl, etc.
(Per) fluoroalkylaryl group having 7 to 18 carbon atoms such as (per) fluoroaryl group, (per) fluorononylphenyl, (per) fluorotolyl, (per) fluoroxylyl, etc., (per) fluoroformyl , (Per) fluoroacetyl, (per) fluoropropionyl, (per) fluorobutyryl, (per) fluorostearoyl, (per) fluorobenzoyl, etc.
18 (per) fluoroacyl group, (per) fluoromethylcarbamoyl, (per) fluoropropylcarbamoyl, (per) fluorobutylcarbamoyl, etc.
(C) 2-18 (per) fluoroacylcarbamoyl groups such as (per) fluoroalkylcarbamoyl group, (per) fluoropropionylcarbamoyl and (per) fluorobenzoylcarbamoyl, or carbon such as (per) fluorophenylcarbamoyl Mono (meth) acrylate monomers of polyhydric alcohols substituted with (per) fluoroarylcarbamoyl groups of the formulas 7 to 18 are exemplified. These compounds can be used alone or in combination of two or more.

The compound represented by the above formula (2) (hereinafter referred to as compound
(Abbreviated as (2)) using at least the formula
Methods for obtaining fine particles having at least one fluorine atom represented by (1) and having a nonionic hydrophilic unit include the following three methods.

As a first method, compound (2) is mixed with styrene, p-methylstyrene, p-chlorostyrene, pt
Styrene monomers such as butoxystyrene, (meth) acrylate monomers such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl monomers such as vinyl acetate and vinyl chloride; Cross-linkable monomer such as divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, methylenebisacrylamide, divinyloxybutane, etc. The monomer can be obtained by polymerizing the monomer by a method such as suspension polymerization or seed polymerization, but it is not limited to these monomers, and two or more monomers can be used in combination.

As a second method, styrene-based crosslinked polymers such as styrene / divinylbenzene, styrene / ethylene glycol dimethacrylate, and styrene / butadiene;
(Meth) acrylate-based crosslinked copolymers such as methyl (meth) acrylate / divinylbenzene, methyl (meth) acrylate / ethylene glycol dimethacrylate, and methyl (meth) acrylate / methylenebisacrylamide; ethylene / butadiene, methyl vinyl ether / When polymerizing polymer fine particles made of a copolymer such as an olefin-based crosslinked copolymer such as divinyloxybutane, vinyl acetate / divinyloxybutane, and vinyl chloride / divinylbenzene, the polymerization rate is 10% or more and 90% or more. %, The compound (2) and a polymerization initiator are added to obtain a copolymer. At this time, as a crosslinkable monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinyloxybutane, etc. The copolymerization may be performed by adding a functional monomer.

Even if the above compound (2) is added at a time when the polymerization rate of the polymer fine particles exceeds 90%, the effect of the present invention is hardly obtained, and depending on the addition amount, irregular shaped particles may be produced. Is not preferred. The conversion was determined by the following gravimetric method. That is, a certain weight of a dispersion was sampled from a polymerization tank during the synthesis of crosslinked polymer fine particles, and a large amount of methanol (hydroquinone monomethyl ether 1000 ppm) was sampled.
Containing). The obtained precipitate was isolated by a method such as filtration or centrifugation and dried under reduced pressure, and the polymerization rate was determined by the following formula.

[0020]

(Equation 1)

The weight of the monomer in the polymerization dispersion (g) is the weight of the sampled dispersion (g) × the concentration of the charged monomer (%). As a method for adding the compound (2), these compounds may be added as they are, or may be added using an emulsion dispersed in a surfactant aqueous solution such as sodium lauryl sulfate using a homomixer or the like.

As a third method, styrene-based crosslinked polymers such as styrene / divinylbenzene, styrene / ethylene glycol dimethacrylate, and styrene / butadiene;
(Meth) acrylate-based crosslinked copolymers such as methyl (meth) acrylate / divinylbenzene, methyl (meth) acrylate / ethylene glycol dimethacrylate, and methyl (meth) acrylate / methylenebisacrylamide; ethylene / butadiene, methyl vinyl ether / Compound (2), a cross-linkable monomer, and a polymer fine particle made of a copolymer such as an olefin cross-linked copolymer such as divinyloxybutane, vinyl acetate / divinyloxybutane, and vinyl chloride / divinylbenzene. Further, the liquid crystal display spacer of the present invention can be obtained by a method of further performing polymerization after impregnation with the initiator.

In the third method, the addition amount of the compound (2) and the crosslinkable monomer to the crosslinked polymer fine particles is as follows:
Depending on the solubility of these monomers in water and the liquid crystal material used for the liquid crystal panel, generally 5 to 500 parts by weight based on 50 parts by weight of the crosslinked polymer fine particles due to problems such as the occurrence of aggregation of the polymerization system. Parts is preferred. If the amount is less than 5 parts by weight, polymer fine particles having a sufficient effect of preventing abnormal liquid crystal alignment cannot be obtained. If the amount is more than 500 parts by weight, problems such as aggregation of the polymerization system tend to occur, which is not preferable.

The solvent used for the impregnation may be a solvent in which these monomers are soluble and in which the crosslinked polymer fine particles are not dissolved. Among them, a solvent that swells the crosslinked polymer fine particles is more preferable. For example, tetrachloroethane, dichloroethane, toluene, DMF (dimethylformamide), DM
Solvents such as SO (dimethylsulfoxide) and THF (tetrahydrofuran) are more preferably used, and the impregnation is performed at a temperature of about room temperature to about 40 ° C. In addition, a crosslinked polymer, compound (2) and an initiator are dispersed in a solvent such as methanol or ethanol.
Dissolve, at room temperature ~ about 40 ℃, the solvent is distilled off under reduced pressure,
An impregnation treatment may be performed.

In the above method of mixing a polymerization initiator and a monomer and impregnating the crosslinked polymer fine particles, a known polymer soluble in these solvents, for example, polyvinyl alcohol, polytetrahydrofuran, polyethylene oxide, Polypropylene oxide, polyethylene imine, polyvinyl pyrrolidone and the like may be added.

The solvent used for the polymerization after the impregnation treatment is as follows:
There is no particular limitation as long as the polymerizable monomer and the crosslinkable monomer are insoluble. For example, water to which inorganic salts are added, or an aliphatic hydrocarbon solvent such as hexane or cyclohexane is used. In the polymerization step, various surfactants or protective colloids may be used to improve the dispersion stability of the polymer particles.

In the three methods exemplified above, the monomers serving as constituent units of the crosslinked polymer fine particles can be used alone or in combination of two or more. The optimal weight ratio of the compound (2) to the polymerizable monomer and the crosslinkable monomer is not particularly limited as long as the effects of the present invention are exerted, since the optimal weight ratio varies depending on the liquid crystal material used for the liquid crystal panel. Is 1 /
It is preferably from 99 to 70/30. When the proportion of the compound (2) is less than 1% by weight, the hydrophilicity is reduced and the effect of the present invention is reduced. When the proportion exceeds 70% by weight, the crosslinkable monomer occupying the crosslinked polymer fine particles is reduced. As a result, the particle strength is not sufficient, and when incorporated into a liquid crystal display panel, it causes color unevenness during display, which is not preferable.

As the polymerization initiator that can be used in the above three methods, generally used oil-soluble polymerization initiators can be used. For example, benzoyl peroxide,
Lauroyl peroxide, o-chlorobenzoyl peroxide, o-
Peroxide initiator such as methoxybenzoyl peroxide, 2,2
-Azobisisobutyronitrile, 2,2-azobis (2,4-
An azo initiator such as dimethylvaleronitrile) can be used.

<Production Method 2> Compounds represented by the above formula (3) which can be used in the present method include polyethylene glycol, polyethylene glycol monoaminopropyl ether, polyethylene glycol monocarboxymethyl ether, and polyethylene glycol monocarboxyethyl. A hydrogen atom of one end hydroxyl group such as ether is converted to (per) fluoromethyl, (per) fluoropropyl, (per) fluoroisopropyl, (per) fluorobutyl,
A (per) fluoroalkyl group having 1 to 18 carbon atoms such as (per) fluorostearyl, a (per) fluoroalkenyl group having 2 to 18 carbon atoms such as (per) fluoropropenyl,
(Per) fluorophenyl groups having 6 to 18 carbon atoms, such as (per) fluorophenyl and (per) fluorobiphenyl,
(Per) fluorononylphenyl, (per) fluorotolyl, (per) fluoroxylyl, etc., a (per) fluoroalkylaryl group having 7 to 18 carbon atoms, (per) fluoroformyl, (per) fluoroacetyl, (per) C1-C18 (per) fluoroacyl groups such as fluoropropionyl, (per) fluorobutyryl, (per) fluorostearoyl, (per) fluorobenzoyl, (per) fluoromethylcarbamoyl, (per) fluoropropylcarbamoyl, A (per) fluoroalkylcarbamoyl group having 2 to 18 carbon atoms such as (per) fluorobutylcarbamoyl, and a (per) fluoroacylcarbamoyl group having 2 to 18 carbon atoms such as (per) fluoropropionylcarbamoyl and (per) fluorobenzoylcarbamoyl. Or (per) fluoroph A compound substituted with a (per) fluoroarylcarbamoyl group having 7 to 18 carbon atoms such as nilcarbamoyl, and a terminal hydroxyl group of a polyethylene glycol mono (per) fluoroalkyl (1 to 18 carbon atoms of (per) fluoroalkyl group) ether Alkoxides in which a hydrogen atom has been substituted with a metal such as an alkali metal, an alkaline earth metal, aluminum, and titanium can be given.

The compound represented by the above formula (4) has at least one fluorine atom and has 1 carbon atom.
Glycidyl ethers of monohydric alcohols having a carbon number of 18 to 18 and hydrogen atoms of terminal hydroxyl groups of polyethylene glycol monoglycidyl ether are substituted with (per) fluoroalkyl group having 1 to 18 carbon atoms, (per) fluoroalkenyl group, (per)
Compounds substituted with a fluoroaryl group, a (per) fluoroalkylaryl group, or a (per) fluoroacyl group are exemplified. These compounds can be used alone or in combination of two or more.

The fine particles having a substituent capable of reacting with the compound represented by the above formula (3) or (4) on the surface thereof include:
For example, curing of inorganic polymer particles such as silica, vinyl polymer particles such as divinylbenzene / methacrylic acid copolymer, divinylbenzene / glycidyl methacrylate copolymer, divinylbenzene / vinyl isocyanate copolymer, benzoguanamine and melamine resin Examples include polycondensation polymer particles such as a resin. These fine particles are represented by formula (3) or
Examples of the method of surface treatment with the compound represented by (4) include a method in which the fine particles are dispersed in a solvent, and then the compound represented by the formula (3) or (4) is added and reacted. Can be

<Production Method 3> In this method, at least the fine particles having a nonionic hydrophilic unit represented by the above formula (5) on at least the surface thereof and a (per) fluoroacyl group having 1 to 18 carbon atoms are provided. An esterification reaction is carried out by reacting an acid halide or an acid anhydride, or a (per) fluoroepoxy compound represented by the formula (4) or a (per) fluoro α-olefin epoxide having 3 to 18 carbon atoms is reacted. An etherification reaction is performed, or a carbamate reaction is performed by reacting an isocyanate compound having a (per) fluoroalkyl group, a (per) fluoroacyl group or a (per) fluoroaryl group having 1 to 18 carbon atoms. The surface of the fine particles is modified.

At least the surface used in the present method has the formula
Fine particles having a nonionic hydrophilic unit represented by (5) include, for example, hydroxyethyl (meth) acrylate,
Diethylene glycol mono (meth) acrylate, polyoxyethylene mono (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate,
(Meth) such as butanediol mono (meth) acrylate
It is obtained by copolymerizing an acrylate-based monomer with another polymerizable monomer and a crosslinkable monomer in the same manner as in Production Method 1.

The acid halide or acid anhydride having a (per) fluoroacyl group having 1 to 18 carbon atoms used in the present method includes n- (per) fluoropropionyl chloride and n- (per) fluorobutyryl chloride. Acid halides such as n- (per) fluoroheptadecanoyl chloride and (per) fluorovaleryl bromide; and acid anhydrides such as (per) fluoroacetic anhydride and (per) fluorobutyric anhydride. Further, as the epoxy compound represented by the above (4),
(Per) fluoro 2-ethylhexyl glycidyl ether, (per) fluorolauryl glycidyl ether,
(Per) fluorophenyl glycidyl ether, (per) fluoro-pt-butylphenyl glycidyl ether, (per) fluorophenol (EO) ₅ glycidyl ether, (per) fluorolauryl alcohol (EO) ₁₅
Glycidyl ether and the like. Examples of the (per) fluoro α-olefin epoxide having 3 to 18 carbon atoms include (per) fluoro-1-heptene oxide, (per) fluoro-1-decene oxide, (per) fluoro-1-petadecene oxide and the like. No. Also,
C1-C18 (per) fluoroalkyl group, (per)
Examples of the isocyanate compound having a fluoroaryl group or a (per) fluoroacyl group include (per) fluoromethyl isocyanate, (per) fluoroethyl isocyanate, (per) fluoroisopropyl isocyanate, (per) fluoroisobutyl isocyanate,
(Per) fluorophenyl isocyanate, (per) fluorotolyl isocyanate, (per) fluoro-α-
(Β-) naphthyl isocyanate, (per) fluoropropionyl isocyanate, (per) fluorobutyryl isocyanate, (per) fluorobenzoyl isocyanate and the like.

The liquid crystal display of the present invention uses the fine particles obtained as described above as a spacer for liquid crystal display.
The average particle diameter of the fine particles used as the spacer varies depending on the purpose and the type of the liquid crystal display panel, but is usually 2 to 2.
It is about 10 μm. When a fine particle having a wide particle size distribution is incorporated in a liquid crystal display panel, the distance between two transparent electrodes in the panel cannot be kept constant, which causes color unevenness during display. It is preferable that the standard deviation of the particle size distribution is not more than 20% of the particle size.

[0036]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, in an Example, a part shows a weight part. The particle size was measured with a Coulter counter (Coulter Multisizer, manufactured by Coulter Electronics Co., Ltd.).

Synthesis Example of Compound (2) Polyethylene glycol monomethacrylate (manufactured by NOF Corporation, Blemmer PE-350, average number of moles of EO added m =
8) 44 parts were dissolved in 500 parts of chloroform, and 13 parts of pyridine was added and stirred. Under ice-cooling, 3H-tetrafluoropropionyl chloride (manufactured by Daikin Fine Chemical Laboratory)
20 parts were added dropwise, and the mixture was further reacted at room temperature for 5 hours to complete the esterification reaction. After methanol was added to the reaction mixture to decompose excess 3H-tetrafluoropropionic acid chloride, ion-exchanged water was added to carry out a liquid separation operation to separate an aqueous layer. Further, an aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate, and polyethylene glycol monomethacrylate 3H-tetrafluoropropionate was isolated. Compound (2) used in the following Examples was synthesized according to the above-mentioned method.

Example 1 Divinylbenzene (purity 55%, manufactured by Nippon Steel Chemical Co., Ltd., D
VB-570) 60 parts and polyethylene glycol monomethacrylate (manufactured by NOF Corporation, Blemmer PE-200)
Average EO addition mole number m = 4-5) and 40 parts of polyethylene glycol monomethacrylate 3H-tetrafluoropropionate synthesized from 3H-tetrafluoropropionyl chloride according to the above synthesis example, 2,2-azobisisobutyro Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., GH-17; saponification degree: 86.5)
~ 89 mol%) 3 parts aqueous solution 800 parts and finely disperse,
Suspension polymerization was performed at 80 ° C. for 15 hours in a nitrogen stream, and classification was performed to obtain crosslinked polymer fine particles having an average particle size of 8.5 μm and a standard deviation of 1.6 μm. The obtained crosslinked polymer fine particles were washed with ion-exchanged water and a solvent, then isolated and dried to obtain a liquid crystal display spacer. Using the spacer obtained by the above method, the cell size is about 10 inches diagonally, the number of dots is 640 × 480,
A super twist type liquid crystal display with a cell gap of 8.2μm was fabricated. When a display voltage was observed by applying a scanning voltage to this display device, a high-quality display without display unevenness was obtained over the entire surface. I was not able to admit.

Example 2 20 parts of styrene and 66 parts of divinylbenzene were used as monomers.
Parts, polyethylene glycol monomethacrylate 3H-tetrafluoropropionate (average number of moles of EO added)
m = 4-5) Except for using 14 parts, crosslinked polymer fine particles having an average particle size of 6.6 μm and a standard deviation of 1.1 μm were obtained in the same manner as in Example 1. The obtained crosslinked polymer fine particles were washed with ion-exchanged water and a solvent, then isolated and dried to obtain a liquid crystal display spacer. A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Example 3 As a monomer, 20 parts of styrene and 78 of divinylbenzene were used.
Parts, polyethylene glycol monomethacrylate 3H-tetrafluoropropionate (average number of moles of EO added)
m = 4-5) Except for using 2 parts, crosslinked polymer fine particles having an average particle size of 7.8 μm and a standard deviation of 1.5 μm were obtained in the same manner as in Example 1. The obtained crosslinked polymer fine particles were washed with ion-exchanged water and a solvent, then isolated and dried to obtain a liquid crystal display spacer. A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Example 4 20 parts of styrene and 60 parts of divinylbenzene were used as monomers.
Part, polyethylene glycol monoacrylate 5H-octafluoropentanoic acid ester synthesized in advance (average number of moles of EO added: m = 8), and 4 parts of benzoyl peroxide as an initiator were suspended in the same manner as in Example 1. Polymerization was carried out to obtain crosslinked polymer fine particles having an average particle size of 7.9 μm and a standard deviation of 1.4 μm. The obtained crosslinked polymer fine particles were washed with ion-exchanged water and a solvent, then isolated and dried to obtain a liquid crystal display spacer. A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Example 5 40 parts of styrene, 60 parts of divinylbenzene (purity 55%),
To a mixture of 1.0 part of 2,2-azobisisobutyronitrile,
3% aqueous solution of polyvinyl alcohol (GH-17, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 86.5 to 89 mol%) 800
The polymerization was carried out at 80 ° C. for 1 hour under a nitrogen stream while stirring. When the polymerization rate at this time was determined by a gravimetric method,
38.0%. To this polymerization system, 1.0 part of 2,2-azobisisobutyronitrile, 10 parts of ethylene glycol dimethacrylate, polyethylene glycol monoacrylate 11H-eicosafluoroundecanoic acid ester synthesized in advance (average number of moles of EO added m = 8) 40 , A mixture of 1.5 parts of sodium lauryl sulfate and 200 parts of ion-exchanged water was added to the emulsion obtained by sonication, and the mixture was stirred and stirred under a stream of nitrogen 80.
Polymerization was further performed at 12 ° C. for 12 hours. The obtained fine particles were washed with ion-exchanged water and a solvent, subjected to a classification operation, and further isolated and dried to obtain a liquid crystal display spacer having an average particle diameter of 6.1 μm and a standard deviation of 1.0 μm. A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and its display characteristics were observed, high-quality display without display unevenness was obtained over the entire surface.
No abnormal alignment of the liquid crystal around the spacers or between the spacers was observed.

Example 6 The same operation as in Example 1 was carried out except that 20 parts of styrene and 80 parts of divinylbenzene (purity: 55%) were used as monomers.
Crosslinked polymer fine particles having an average particle size of 8.5 μm and a standard deviation of 1.5 μm were obtained. 10 parts of the obtained crosslinked polymer fine particles were added to DM
F20, dispersed in 2,20-azobisisobutyronitrile
0.2 parts, ethylene glycol dimethacrylate 2 parts, previously synthesized polyethylene glycol monomethacrylate trifluoroacetate (average number of moles of EO added m = 2)
10 parts were added and stirred at 35 ° C. for 15 hours to impregnate the initiator, the polymerizable monomer, and the crosslinkable monomer. This solution was filtered, and the obtained polymer was redispersed in 500 parts of cyclohexane, and 0.45 part of Rheodol SP-S10 (manufactured by Kao Corporation, nonionic surfactant) was added. The monomers were polymerized. The obtained fine particles were washed with ion-exchanged water and a solvent, and then isolated and dried to obtain a liquid crystal display spacer. A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Example 7 Example 1 was repeated except that 20 parts of styrene, 60 parts of divinylbenzene (purity: 55%), and 20 parts of polyethylene glycol monomethacrylate (average number of moles of EO added: m = 4 to 5) were used as monomers. In the same manner, crosslinked polymer fine particles having an average particle size of 8.5 μm and a standard deviation of 1.5 μm were obtained. 30 parts of the obtained crosslinked polymer fine particles were dispersed in 90 parts of chloroform,
50 parts of pyridine was added, and 50 parts of 3H-tetrafluoropropionic acid chloride was added dropwise under ice cooling, and the mixture was further reacted at room temperature for 5 hours to complete the esterification reaction. Methanol was added to the reaction mixture to decompose excess 3H-tetrafluoropropionyl chloride, followed by filtration and purification, washing with methanol and ion-exchanged water to isolate a liquid crystal spacer. A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Example 8 As a monomer, 20 parts of styrene, 77 parts of divinylbenzene (purity 81%, DVB-810, manufactured by Nippon Steel Chemical Co., Ltd.), polyethylene glycol monomethacrylate (Nippon Oil & Fats Co., Ltd.)
Manufactured by Blemmer PE-350, average number of moles of EO added m = 8) 3
In the same manner as in Example 1, except that 5 parts of benzoyl peroxide were used as the initiator, to obtain crosslinked polymer fine particles having an average particle size of 5.9 μm and a standard deviation of 1.1 μm. 30 parts of the obtained crosslinked polymer fine particles were dispersed in 90 parts of chloroform, 80 parts of triethylamine was added, and 50 parts of 9H-hexadecafluorononanoic acid chloride was added dropwise under ice-cooling, and further reacted at room temperature for 5 hours to give an ester. The reaction was completed. Methanol was added to the reaction mixture to decompose excess 9H-hexadecafluorononanoic acid chloride, followed by filtration and purification, washing with methanol and ion-exchanged water to isolate a liquid crystal spacer.

A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Example 9 As a monomer, 20 parts of styrene, 75 parts of divinylbenzene (purity: 55%) and polypropylene glycol monoacrylate (manufactured by NOF Corporation, Blemmer AP-400,
Average PO addition mole number m = 6) and polypropylene glycol monoacrylate synthesized from 5H-octafluoropentanoic acid chloride, and 5 parts of 5H-octafluoropentanoic acid ester were used.
Crosslinked polymer fine particles having a size of 5.5 μm and a standard deviation of 1.0 μm were obtained. The obtained crosslinked polymer fine particles were washed with ion-exchanged water and a solvent, then isolated and dried to obtain a liquid crystal display spacer.

A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Example 10 The average particle size was determined in the same manner as in Example 7 except that o-fluorobenzoic acid chloride (manufactured by Hoechst Co.) was used in place of 3H-tetrafluoropropionic acid chloride. Crosslinked polymer fine particles having a diameter of 6.5 μm and a standard deviation of 1.2 μm were obtained. The obtained crosslinked polymer fine particles were washed with ion-exchanged water and a solvent, then isolated and dried to obtain a liquid crystal display spacer. A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Example 11 10 parts of silica particles (average particle diameter: 6.5 μm) were dispersed in 50 parts of dioxane, and 30 parts of 3-perfluorohexyl-1,2-epoxypropane (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.) was added. It was added, dissolved, and reacted under reflux for 48 hours.
After the reaction, the mixture was purified by filtration and washed with methanol and ion-exchanged water to isolate a spacer for liquid crystal display. A liquid crystal display device using the obtained spacer was prepared in the same manner as in Example 1. When a scanning voltage was applied to the obtained display device and the display characteristics were observed, a high-quality display without display unevenness was obtained over the entire surface, and the alignment of the liquid crystal around the spacers and between the spacers was obtained. No abnormalities were observed.

Comparative Example 1 A suspension polymerization was carried out using 40 parts of styrene and 60 parts of divinylbenzene (purity: 55%), and a classification operation was carried out to obtain an average particle size of 6.2 μm.
m and a standard deviation of 1.2 μm were obtained. The obtained crosslinked polymer fine particles were washed with ion-exchanged water and a solvent, then isolated and dried to obtain a liquid crystal display spacer. In the case of a liquid crystal display device using the obtained spacer,
A liquid crystal display device was manufactured in the same manner as in Example 1 and the display characteristics were observed. As a result, abnormal liquid crystal alignment occurred around the spacers or between the spacers, and no deterioration in display quality was observed.

Next, embodiments of the present invention and related matters will be listed. Radical polymerizable monomers such as styrene-based monomers, (meth) acrylate-based monomers, olefin-based monomers, and cross-linkable monomers are copolymerized with the compound represented by formula (2). A method for producing a liquid crystal display spacer having a fluorine unit containing a fluorine atom represented by the formula (1) and having a nonionic hydrophilic unit.

First, a radical polymerizable monomer and / or a cross-linkable monomer such as a styrene monomer, a (meth) acrylate monomer, and an olefin monomer are polymerized. A liquid crystal having a fluorine unit-containing nonionic hydrophilic unit represented by the formula (1), wherein the compound represented by the formula (2) is added and copolymerized in an amount of 10% or more and less than 90%. Manufacturing method of display spacer.

With respect to polymer fine particles comprising a copolymer such as a styrene-based crosslinked polymer, a (meth) acrylate-based crosslinked copolymer, and an olefin-based crosslinked copolymer,
A liquid crystal display having a fluorine unit containing a fluorine atom represented by the formula (1) and a nonionic hydrophilic unit, which is subjected to polymerization after impregnating the compound represented by the formula (2), a crosslinkable monomer and an initiator. Method of manufacturing spacers.

A fluorine-containing compound represented by the formula (1) for treating a fine particle having a substituent capable of reacting with the compound with the compound represented by the formula (3) or (4) on the surface. A method for producing a liquid crystal display spacer having a nonionic hydrophilic unit.

Fine particles having a nonionic hydrophilic unit represented by the formula (5) on at least the surface thereof are obtained by acid-halide having at least one fluorine atom and having an acyl group having 1 to 18 carbon atoms or An acid anhydride, an epoxy compound represented by the formula (4), an α-olefin epoxide having at least one fluorine atom and having 3 to 18 carbon atoms, or having at least one fluorine atom, and The surface is modified with an isocyanate compound having an alkyl group, an acyl group or an aryl group of the formulas 1 to 18,
A method for producing a liquid crystal display spacer having a fluorine unit and a nonionic hydrophilic unit represented by (1).

[0057]

As is evident from the results of the above embodiments, the liquid crystal display spacer obtained by the present invention has an excellent effect of preventing abnormal alignment, and is suitable as a liquid crystal display spacer.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a liquid crystal display device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polarizer 2 Glass substrate 3 Transparent electrode 4 Alignment film 5 Liquid crystal material 6 Sealant 7 Spacer

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-6-11719 (JP, A) JP-A-4-27917 (JP, A) JP-A-3-96920 (JP, A) JP-A-61- 283607 (JP, A) Japanese Utility Model Hei 3-80417 (JP, U) (58) Fields surveyed (Int. Cl. ⁷ , DB name) G02F 1/1339

Claims (5)

(57) [Claims] 1. A spacer for a liquid crystal display having at least a surface of the following formula (1): (Wherein, R represents an alkyl group, alkenyl group, aryl group, alkylaryl group, acyl group, alkylcarbamoyl group, acylcarbamoyl group or arylcarbamoyl group having at least one fluorine atom and having 1 to 18 carbon atoms) R ₁ represents a linear or branched alkylene group having 2 to 4 carbon atoms, which may be substituted with a hydroxy group.
Represents an integer of 1 or more and 100 or less, and m R _{1 s} may be the same or different. A liquid crystal display device comprising fine particles containing a fluorine unit and containing a nonionic hydrophilic unit represented by the formula (1). 2. Fine particles having a fluorine unit containing a fluorine atom represented by the formula (1) and having a nonionic hydrophilic unit,
The following formula (2) (Wherein, R, R ₁ and m have the same meanings as described above, and X represents a hydrogen atom or a methyl group). Display device. 3. Fine particles having a fluorine unit containing a fluorine atom represented by the formula (1) and having a nonionic hydrophilic unit,
The following formula (3) or (4) (Wherein, R, R ₁ and m have the same meaning as described above.)
n represents an integer of 0 or more and 100 or less, and n pieces of R ₁ may be the same or different. Z represents a hydrogen atom, a metal atom, an aminoalkyl group or a carboxyalkyl group. 2. The liquid crystal display device according to claim 1, which is obtained by subjecting fine particles having a substituent capable of reacting with the compound to the surface with the compound represented by the formula (1). 4. A fine particle containing a fluorine unit containing a fluorine atom represented by the formula (1) and having a nonionic hydrophilic unit,
At least on the surface, the following formula (5) (Wherein, R ₁ and m have the same meanings as described above). The fine particles having a nonionic hydrophilic unit represented by the formula: are acyl having at least one fluorine atom and having 1 to 18 carbon atoms. An acid halide or anhydride having a group,
(4) an epoxy compound represented by the formula, having at least one fluorine atom, and having at least one α-olefin epoxide having 3 to 18 carbon atoms, or having at least one fluorine atom, and having 1 to 18 carbon atoms The liquid crystal display device according to claim 1, which is obtained by surface modification with an isocyanate compound having an alkyl group, an acyl group, or an aryl group. 5. At least a surface of the following formula (1): (Wherein, R, R ₁ and m have the same meanings as described above) comprising fine particles containing a fluorine unit and having a nonionic hydrophilic unit represented by the formula: Spacer.