JP4420969B2 - Spacer particle dispersion, liquid crystal display manufacturing method, and liquid crystal display - Google Patents

Description

The present invention relates to a spacer particle dispersion capable of continuously and stably arranging spacer particles on a substrate by an ink jet device and obtaining a liquid crystal display device excellent in display quality. The present invention also relates to a method for manufacturing a liquid crystal display device using the spacer particle dispersion and a liquid crystal display device.

Liquid crystal display devices are currently widely used in personal computers, portable electronic devices, and the like. The liquid crystal display device generally has a structure in which liquid crystal is sandwiched between two substrates on which a color filter, a black matrix, a linear transparent electrode, an alignment film, and the like are formed. Here, it is the spacer particles that regulate the distance between the two substrates and maintain the proper thickness of the liquid crystal layer.

In the conventional method for manufacturing a liquid crystal display device, spacer particles are arranged by a wet spraying method in which spacer particles are sprayed on a substrate using a solvent such as isopropanol, or by applying air pressure without using a solvent. A dry spraying method or the like in which spacer particles are sprayed on a substrate by use has been used.
However, in such a method, spacer particles are randomly and uniformly distributed on the substrate on which the pixel electrode is formed. Therefore, the spacer particles are arranged on the pixel electrode, that is, on the display unit (pixel region) of the liquid crystal display device. It was easy.
Since general spacer particles are made of synthetic resin, glass, or the like, when the spacer particles are arranged on the pixel electrode, a phenomenon in which the polarization is disturbed and the polarization property is lost, so-called depolarization phenomenon occurs. There was a problem that the part leaked light. Further, the alignment of the liquid crystal on the surface of the spacer particles may cause a problem that light is lost and the contrast and color tone are lowered to deteriorate the display quality.
Furthermore, in the TFT liquid crystal display device, the TFT element is disposed on the substrate. However, when spacer particles are disposed on the TFT element, the element may be damaged if pressure is applied to the substrate. .

In order to solve the problems associated with random dispersion of spacer particles, various attempts have been made to arrange the spacer particles in the non-pixel region.
As a method of arranging spacer particles only in a non-pixel region, that is, a specific position, for example, in Patent Document 1, after aligning an opening of a mask with a portion where spacer particles are arranged, the spacer particles are dispersed through the mask. A method is disclosed. For example, Patent Document 2 discloses a method in which spacer particles are electrostatically adsorbed to a photoreceptor and then transferred to a transparent substrate. Furthermore, Patent Document 3 discloses a method for manufacturing a liquid crystal display device in which spacer particles are arranged at specific positions by electrostatic repulsion by applying a voltage to pixel electrodes on a substrate and dispersing charged spacer particles. Is disclosed.

However, in the methods disclosed in Patent Documents 1 and 2, since the mask or the photoconductor is brought into direct contact with the substrate surface, the alignment film formed on the substrate surface may be damaged. May decrease. On the other hand, in the method disclosed in Patent Document 3, it is necessary to configure the electrodes according to the arrangement pattern of the spacer particles. Therefore, it is difficult to arrange the spacer particles at an arbitrary position.

With respect to this problem, Patent Document 4 discloses a method of arranging spacer particles on a substrate using an ink jet apparatus. In the method disclosed in Patent Document 4, since a mask or a photoconductor is not directly contacted on the substrate, the alignment film formed on the substrate surface is not damaged, and a specific pattern is formed at a specific position. Since spacer particles can be arranged, it can be said that this is an effective method.

In the method of disposing spacer particles on a substrate using an ink jet device, a spacer particle dispersion liquid containing spacer particles and a dispersion solvent for dispersing the spacer particles is filled into the ink jet device, and the spacer particle dispersion liquid is discharged from a nozzle. Droplets are discharged toward the substrate. However, when the spacer particle dispersion is actually discharged using an ink jet apparatus, various problems have occurred.

That is, the spacer particles to be dispersed in the spacer particle dispersion usually have a particle size of about 1 to 20 μm, but the pigment contained in the ink used in a normal inkjet printer or the like is about 1 μm at most. It was not assumed that a dispersion liquid in which large particles were dispersed was discharged.
Moreover, in the case of an ink in which a normal pigment or the like is dispersed, the dispersion stability is improved by using a dispersant. However, the spacer particle dispersion liquid to which the dispersant is added has high wettability with respect to the substrate and the like. When the liquid is discharged, the liquid spreads and cannot be selectively discharged to a minute region. In addition, the dispersing agent absorbs moisture, and therefore the drying process takes time, or the alignment film is contaminated by the dispersing agent and the image quality is deteriorated. I could not.

When trying to discharge such a spacer particle dispersion liquid in which spacer particles, which are large particles having extremely poor dispersibility, are dispersed with a conventional ink jet device, clogging of the spacer particles, defective discharge, etc. occur, and accurate discharge is caused. Was impossible.

As a means for solving clogging of spacer particles, ejection failure, and the like, for example, a method is known in which surface treatment is applied to spacer particles to impart dispersibility with respect to a dispersion solvent and improve ejection properties.
However, when a spacer particle dispersion containing spacer particles subjected to such a surface treatment is to be ejected by an ink jet apparatus, the ejection stability often decreases during ejection, or spacer particles are contained in the ejected droplets. There was a problem that may not be included.
Japanese Patent Laid-Open No. 4-198919 JP-A-6-258647 JP-A-10-339878 JP-A-57-58124

An object of the present invention is to provide a spacer particle dispersion which can continuously and stably dispose spacer particles on a substrate by an ink jet device and can obtain a liquid crystal display device excellent in display quality. To do. It is another object of the present invention to provide a method for manufacturing a liquid crystal display device using the spacer particle dispersion and a liquid crystal display device.

The present invention relates to a spacer particle dispersion for disposing spacer particles at an arbitrary position on a substrate using an ink jet apparatus, and includes spacer particles having a negative charge on the surface, a cationic compound, and a solvent. It is a spacer particle dispersion containing.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have found that when discharging a spacer particle dispersion containing spacer particles having a negative charge on the surface with an ink jet apparatus, the discharge stability is reduced or the discharged droplets It has been found that the reason why the spacer particles are not included is clogging of the SUS filter installed in the flow path of the ink jet apparatus.
As a method of maintaining a state where particles such as spacer particles are dispersed as a single particle without causing aggregation between particles, a method of performing a surface treatment so that the surfaces of all the particles are usually the same charge Is well known. As the surface treatment, it is common to introduce a hydrophilic group such as a carboxyl group into the surface of the spacer particle so as to be negatively charged and to impart dispersibility by the electrostatic repulsion force. On the other hand, SUS filters are usually positively charged. Therefore, it is considered that clogging of the filter is likely to occur because the negatively charged spacer particles adhere to the positively charged SUS filter and cannot be removed.

Therefore, as a result of further diligent investigations, the inventors of the present invention have made spacer particles excellent by adding a small amount of a cationic compound to a spacer particle dispersion containing spacer particles having a negative charge on the surface. Since clogging of the filter can be prevented while ensuring self-dispersibility, the spacer particle dispersion can be discharged continuously and stably, and a liquid crystal display device with excellent display quality can be manufactured. As a result, the present invention has been completed.
In addition to the above-mentioned filter, the liquid contact part in contact with the spacer particle dispersion such as the flow path of the ink jet device or the ink chamber is usually made of SUS. Conventionally, spacer particles may adhere to the liquid contact part. However, according to the spacer particle dispersion liquid of the present invention, the adhesion of the spacer particles to the SUS wetted part can also be prevented.

The spacer particle dispersion of the present invention contains spacer particles having a negative charge on the surface.
As the spacer particles having a negative charge on the surface, spacer particles that have a negative charge or spacer particles that have been subjected to a surface treatment that imparts a negative charge to the surface can be used.

The spacer particles are not particularly limited, and may be inorganic particles such as silica particles or organic particles made of an organic polymer. In particular, it has an appropriate hardness that does not damage the alignment film formed on the substrate of the liquid crystal display device, can easily follow a change in thickness due to thermal expansion and contraction, and the movement of the spacer particles inside the cell. Organic particles are preferred because they are relatively few.

Although it does not specifically limit as said organic type particle | grains, Since the intensity | strength etc. can be adjusted to a suitable range, the copolymer of a monofunctional monomer and a polyfunctional monomer is suitable.
The monofunctional monomer is not particularly limited, and examples thereof include styrene derivatives, vinyl chloride, vinyl esters, unsaturated nitriles, (meth) acrylic acid ester derivatives, and the like.

It does not specifically limit as said styrene derivative, For example, styrene, (alpha) -methylstyrene, p-methylstyrene, p-chlorostyrene, chloromethylstyrene etc. are mentioned.
The vinyl esters are not particularly limited, and examples thereof include vinyl acetate and vinyl propionate.
The unsaturated nitriles are not particularly limited, and examples thereof include acrylonitrile.
The (meth) acrylic acid ester derivative is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, ethylene Examples include glycol (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, and cyclohexyl (meth) acrylate.
These monofunctional monomers may be used independently and 2 or more types may be used together.

The polyfunctional monomer is not particularly limited. For example, divinylbenzene, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylol. Propanetetra (meth) acrylate, diallyl phthalate and isomers thereof, triallyl isocyanurate and derivatives thereof, trimethylolpropane tri (meth) acrylate and derivatives thereof, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Polyethylene glycol di (meth) acrylates such as dipentaerythritol hexa (meth) acrylate and ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate Polypropylene glycol di (meth) acrylate such as relate, polytetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2,2-bis [4- (Methacryloxyethoxy) phenyl] propanedi (meth) acrylate, 2,2-hydrogenated bis [4- (acryloxyethoxy) phenyl] propanedi (meth) acrylate, 2,2-bis [4- (acryloxyethoxypropoxy) Phenyl] propane di (meth) acrylate and the like.
These polyfunctional monomers may be used independently and 2 or more types may be used together.

The monofunctional monomer or polyfunctional monomer may have a hydrophilic group. The hydrophilic group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a sulfonyl group, a phosphonyl group, an amino group, an amide group, an ether group, a thiol group, and a thioether group.

The monofunctional monomer or polyfunctional monomer having a hydrophilic group (hereinafter, also simply referred to as a monomer having a hydrophilic group) is not particularly limited, and examples thereof include a monomer having a hydroxyl group and a carboxyl group. Monomer, monomer having sulfonyl group, monomer having phosphonyl group, monomer having amino group, monomer having both hydroxyl group and ether group, monomer having ether group, amide group And the like.
The monomer having a hydroxyl group is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 1,4-hydroxybutyl (meth) acrylate, (poly) caprolactone-modified hydroxyethyl (meth) acrylate, glycerin mono (Meth) acrylate, allyl alcohol, glycerin monoallyl ether and the like can be mentioned.
The monomer having a carboxyl group is not particularly limited, and examples thereof include acrylic acid such as (meth) acrylic acid, α-ethylacrylic acid, and crotonic acid, and α- or β-alkyl derivatives thereof, fumaric acid. And unsaturated dicarboxylic acids such as maleic acid, citraconic acid and itaconic acid, and mono 2- (meth) acryloyloxyethyl ester derivatives of these unsaturated dicarboxylic acids.
The monomer having a sulfonyl group is not particularly limited, and examples thereof include t-butyl acrylamide sulfonic acid, styrene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid.
The monomer having the phosphonyl group is not particularly limited, and examples thereof include vinyl phosphate and 2- (meth) acryloyloxyethyl phosphate.
The monomer having an amino group is not particularly limited, and examples thereof include amines having an acryloyl group such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
The monomer having both the hydroxyl group and the ether group is not particularly limited, and examples thereof include (poly) ethylene glycol (meth) acrylate and (poly) propylene glycol (meth) acrylate.
The monomer having an ether group is not particularly limited. For example, a terminal alkyl ether of (poly) ethylene glycol (meth) acrylate, a terminal alkyl ether of (poly) propylene glycol (meth) acrylate, tetrahydrofurfuryl (meta) ) Acrylate and the like.
The monomer having an amide group is not particularly limited, and examples thereof include (meth) acrylamide, methylol (meth) acrylamide, and vinylpyrrolidone.

The method for producing the organic particles is not particularly limited, and examples thereof include various polymerization methods such as a suspension polymerization method using a polymerization initiator, a seed polymerization method, and a dispersion polymerization method.
In the suspension polymerization method, the particle size distribution of the obtained particles is relatively wide and polydispersed particles can be obtained. Therefore, when used as spacer particles, classification operation is performed to obtain the desired particle size and particle size distribution. It is suitably used when obtaining various types of particles having
On the other hand, the seed polymerization method and the dispersion polymerization method are suitable for producing a large amount of particles having a specific particle size because monodispersed particles can be obtained without going through a classification step.

The polymerization initiator used in the suspension polymerization method, seed polymerization method, dispersion polymerization method and the like is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3, Organic peroxides such as 5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-t-butyl peroxide, azobisisobutyronitrile, azobiscyclohexacarbonitrile And azo compounds such as azobis (2,4-dimethylvaleronitrile).

In the spacer particle dispersion of the present invention, the spacer particles have a negative charge on the surface. By containing such spacer particles, the dispersibility and dispersion stability of the spacer particles in the spacer particle dispersion liquid of the present invention can be improved, or the spacers can be located near the wiring portion (step) portion by the electrophoretic effect when sprayed. Effects such as particles becoming easier to gather together. The surface charge of the spacer particles can be measured using a zeta potential measuring device such as a laser / rotating prism type zeta potential measuring device (manufactured by Nippon Luft Co., Ltd.).

Examples of the surface treatment for imparting a negative charge to the surface of the spacer particles include a method of containing a charge control agent in the spacer particles, a method of performing a surface treatment that can be negatively charged on the spacer particles, and the like. In addition, when the spacer particles are made of organic particles, the spacer particles can be obtained by a method of manufacturing spacer particles using a monomer containing a monomer that is easily negatively charged as a raw material.

The preferable lower limit of the negative charge on the spacer particle surface is −60 mV, and the preferable upper limit is −0.1 mV. When the negative charge on the surface of the spacer particles is less than −60 mV, the dispersion of the electric potential of each particle becomes large and the dispersibility may become unstable. When the negative charge on the surface of the spacer particles exceeds −0.1 mV, the repulsive force of each particle becomes small and the particles tend to coalesce and the dispersibility may become unstable. The more preferable lower limit of the negative charge on the surface of the spacer particles is −40 mV, and the more preferable upper limit is −1.0 mV.

As a method of performing a negatively chargeable surface treatment on the spacer particles, a method of physically attaching and / or chemically bonding the above-described coating layer made of a monomer having a hydrophilic group to the surface of the spacer particles. Etc. The coating layer may cover the spacer particles uniformly, or may partially cover the spacer particles.
Examples of a method for providing a coating layer on the spacer particles by surface treatment include, for example, a method in which a resin is deposited on the surface of spacer particles as disclosed in JP-A-1-247154, and a method for modifying the spacer particles. JP-A-11-223821, JP-A-2003-295198, a method of modifying by acting a compound that reacts with a functional group on the surface of spacer particles, as disclosed in JP-A No. 7-3000587. As disclosed in the publication, there may be mentioned a method in which surface modification is performed by graft polymerization on the surface of spacer particles.

Among them, since there is little problem that the coating layer peels off in the cell of the liquid crystal display device and elutes into the liquid crystal, a method of forming a coating layer chemically bonded to the surface of the spacer particles is preferable. A method for carrying out graft polymerization disclosed in JP-A-9-113915 is preferred.
In the method of performing graft polymerization, particles having a reducing group on the surface of spacer particles are reacted with an oxidizing agent, radicals are generated on the surfaces of spacer particles, and the surface is graft-polymerized. When the graft polymerization is performed, the density of the coating layer of the spacer particles can be increased, and a coating layer having a sufficient thickness can be formed. Therefore, the graft-polymerized spacer particles are excellent in dispersibility in the spacer particle dispersion of the present invention. Furthermore, when the spacer particle dispersion of the present invention is discharged onto the substrate, the spacer particles are excellent in adhesion to the substrate. In this method, when graft polymerization is performed, the surface charge of the spacer particles can be made negative by using a monomer having the above-mentioned hydrophilic group as a monomer in combination. Further, if the monomer to be used is appropriately selected, there is an effect that the alignment of the liquid crystal in the liquid crystal display device is not disturbed.

In the method for producing spacer particles using a monomer containing a monomer that is easily negatively charged as a raw material, the monomer that is easily negatively charged is not particularly limited. Among them, monomers having a hydrophilic group excluding an amino group and an amide group are exemplified.

In the case where the spacer particles having a negative charge are organic particles made of an organic polymer or the like, a method for producing the above-mentioned organic particles by using a polymerizable monomer capable of imparting a negative charge. And a method using a dispersion stabilizer having a negative charge or a surfactant having a negative charge as a dispersion stabilizer or surfactant used for polymerizing organic particles. it can.

As the polymerizable monomer capable of imparting a negative charge, a monomer that is easily negatively charged can be used. For example, among the above monomers, a hydrophilic group excluding an amino group and an amide group can be used. The monomer which has is mentioned.

The blending amount of the negatively charged monomer is not particularly limited, but a preferable lower limit is 0.01% by weight and a preferable upper limit is 50% by weight. If the amount of the monomer is less than 0.01% by weight, it may not be possible to impart a negative charge to the spacer particles. If the amount of the monomer exceeds 50% by weight, it may be difficult to form particles. A more preferable lower limit of the amount of the monomer is 0.1% by weight, and a more preferable upper limit is 20% by weight.

The dispersion stabilizer having a negative charge is not particularly limited, and examples thereof include a dispersion stabilizer having a hydroxyl group, a carboxyl group, a sulfonyl group, and the like.
The dispersant having a hydroxyl group is not particularly limited, and examples thereof include polyethylene glycol monoalkyl ethers such as polyvinyl alcohol, polyethylene glycol, and polyethylene glycol monomethyl ether.
It does not specifically limit as a dispersing agent which has the said carboxyl group, Poly (meth) acrylic acid etc. are mentioned.
Examples of the dispersant having a sulfonyl group include polystyrene sulfonic acid.
These negatively charged dispersion stabilizers may be used alone or in combination of two or more.

The blending amount of the negatively charged dispersion stabilizer is not particularly limited, but a preferred lower limit is 0.01% by weight and a preferred upper limit is 30% by weight. If the amount of the dispersion stabilizer is less than 0.01% by weight, a negative charge cannot be imparted and it may be difficult to form particles. If the amount of the dispersion stabilizer exceeds 30% by weight, it may be difficult to form particles. The more preferable lower limit of the blending amount of the dispersion stabilizer is 0.1% by weight, and the more preferable upper limit is 10% by weight.

The surfactant having a negative charge is not particularly limited, and examples thereof include surfactants having a carboxyl group, a sulfonyl group, a phosphonyl group, and the like.
The surfactant having a carboxyl group is not particularly limited, and examples thereof include dicarboxylic acid monoalkyl esters such as lauryl succinate.
The surfactant having a sulfonyl group is not particularly limited, and styrene sulfonic acid derivatives such as sodium styrene sulfonate, alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate, and alkyl polyoxy such as sodium dodecyl polyoxyethylene glycol. Examples thereof include alkyl sulfate derivatives such as ethylene sulfates and sodium lauryl sulfate.
The surfactant having a phosphonyl group is not particularly limited, and examples thereof include monoalkyl phosphates.
These negatively charged surfactants may be used alone or in combination of two or more.

The blending amount of the negatively charged surfactant is not particularly limited, but a preferable lower limit is 0.01% by weight and a preferable upper limit is 30% by weight. If the amount of the surfactant is less than 0.01% by weight, a negative charge cannot be imparted and it may be difficult to form particles. When the amount of the surfactant exceeds 30% by weight, it may be difficult to form particles. A more preferable lower limit of the compounding amount of the surfactant is 0.1% by weight, and a more preferable upper limit is 10% by weight.

The spacer particles may be colored to improve the contrast of the display element. Colored spacer particles include, for example, particles treated with carbon black, disperse dyes, acid dyes, basic dyes, metal oxides, etc., and organic films are formed on the surface of the particles to decompose or carbonize at high temperatures. And colored particles. In addition, when the material itself which forms particle | grains has a color, you may use as it is, without coloring.

The particle diameter of the spacer particles may be appropriately selected depending on the type of the liquid crystal display element, but the preferred lower limit is 1 μm and the preferred upper limit is 20 μm. If the particle size of the spacer particles is less than 1 μm, the opposing substrates may come into contact with each other and may not function sufficiently as spacer particles for the liquid crystal display element. When the particle size of the spacer particles exceeds 20 μm, it tends to protrude from the light shielding region on the substrate on which the spacer particles are to be arranged, and the distance between the opposing substrates is increased, resulting in a recent downsizing of liquid crystal display elements, etc. It will not be possible to fully respond to the request.

The spacer particles have a preferable lower limit of 2000 MPa and a preferable upper limit of 15000 MPa for the compression elastic modulus (10% K value) when the particle diameter is displaced by 10%. When the compression elastic modulus is less than 2000 MPa, the spacer particles may be deformed by a press pressure when assembling the liquid crystal display element, and an appropriate gap may not be obtained. When the compression elastic modulus exceeds 15000 MPa, when incorporated in a liquid crystal display element, the alignment film on the substrate may be damaged to cause display abnormality.
The 10% K value is obtained from a load for distorting the particles by 10% on a smooth end face of a diamond cylinder having a diameter of 50 μm using, for example, a micro compression tester (PCT-200, manufactured by Shimadzu Corporation). Can be sought.

The spacer particles are preferably dispersed in the form of single particles in the spacer particle dispersion of the present invention. If aggregates are present in the dispersion, not only the discharge accuracy is lowered, but in the case of remarkable, the nozzles of the ink jet apparatus may be clogged.

In the spacer particle dispersion of the present invention, the preferable lower limit of the concentration of the spacer particles is 0.01% by weight, and the preferable upper limit is 8% by weight. When the concentration of the spacer particles is less than 0.01% by weight, the probability that the discharged droplets do not contain spacer particles increases. If the spacer particle concentration exceeds 8% by weight, the nozzles of the ink jet device may be clogged or the number of spacer particles contained in the landed droplets will increase so much that the spacer particles move (concentrate) during the drying process. May be difficult to occur. A more preferable lower limit of the concentration of the spacer particles is 0.1% by weight, and a more preferable upper limit is 6% by weight.

The spacer particle dispersion of the present invention contains a cationic compound.
The cationic compound prevents the spacer particles from adhering to the SUS filter of the ink jet device due to electrostatic interaction and causing clogging. That is, the cationic compound is coordinated as a counter cation to the hydrophilic group on the surface of the spacer particle, thereby weakening the electrostatic interaction of the spacer particle with the SUS filter of the inkjet device, and the spacer particle is made of the SUS filter. It prevents it from adhering to. Furthermore, the dissociation of the acid on the surface of the spacer particles is promoted, the hydrophilicity is improved, and the hydrophobic interaction is weakened.

The cationic compound refers to a compound that can lower the hydrogen ion concentration (increase the pH) of the solvent when dissolved in the solvent used in the spacer particle dispersion.

The cationic compound is not particularly limited, and examples thereof include amine derivatives, alkali metal salts such as sodium hydroxide, potassium hydroxide, and sodium iodide, and quaternary phosphonium such as tetraphenylphosphine. Of these, amine derivatives are preferably used.
These cationic compounds may be used independently and 2 or more types may be used together.

The amine derivative is not particularly limited, and examples thereof include inorganic compounds such as ammonia and hydroxyamine, primary amines that are water-soluble or soluble in alcohols, and water-soluble or secondary amines that are soluble in alcohols. Examples include tertiary amines, tertiary amines that are water-soluble or soluble in alcohols, and quaternary amines in which an alkyl group is bonded to the tertiary amine.

Examples of the primary amines having water solubility or solubility in alcohols include compounds represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrophilic functional group such as a hydrocarbon or a hydroxyl group.

Specific examples of the compound represented by the general formula (1) include methylamine, ethylamine, methanolamine, ethanolamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, and sec-butylamine. , Tert-butylamine, cyclohexylamine, aniline, aniline derivatives, benzylamine, toluidine and the like.

Examples of the secondary amine having water solubility or solubility in alcohols include compounds represented by the following general formula (2) or (3).

In the general formula (2), R ² represents a hydrophilic functional group such as a hydrocarbon or a hydroxyl group. In the general formula (3), R ³ and R ⁴ are hydrocarbon or a carbon having a hydrophilic functional group. Represents hydrogen or a hydrophilic functional group.

Specific examples of the compound represented by the general formula (2) include dimethylamine, diethylamine, diethanolamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, Examples include di-tert-butylamine and pyridine.
Specific examples of the compound represented by the general formula (3) include N-methylethylamine, N-methylisopropylamine, N-methylbutylamine, N-ethylpropylamine, N-ethylbutylamine, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (propylamino) ethanol, 2- (butylamino) ethanol, (methylamino) methanol, (ethylamino) methanol, (propylamino) methanol, (Butylamino) methanol and the like.

Examples of the tertiary amine having water solubility or solubility in alcohols include compounds represented by the following general formula (4), (5) or (6).

In the general formulas (4) to (6), R ^{5 to} R ¹⁰ represent a hydrocarbon or a hydrocarbon having a hydrophilic functional group, or a hydrophilic functional group.

Specific examples of the compound represented by the general formula (4) include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-sec-butylamine, tri- Examples include tert-butylamine, triethanolamine, trimethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, tri-sec-butanolamine, and tri-tert-butanolamine.

Specific examples of the compound represented by the general formula (5) include dimethylethylamine, dimethylpropylamine, dimethylbutylamine, diethylmethylamine, diethylpropylamine, diethylbutylamine, dipropylmethylamine, dipropylethylamine. , Dipropylbutylamine, dibutylmethylamine, dibutylethylamine, dibutylpropylamine, dibenzylmethylamine, dibenzylpropylamine, dibenzylbutylamine, diethylaminoethanol, dimethylaminoethanol, diethylaminomethanol, dimethylaminomethanol, N-methyldimethanolamine N-methyldiethanolamine, N-methyldipropanolamine, N-methyldibutanolamine, N-ethyldimethanolamine N-ethyldiethanolamine, N-ethyldipropanolamine, N-ethyldibutanolamine, N-propyldimethanolamine, N-propyldiethanolamine, N-propyldipropanolamine, N-propyldibutanolamine, N-butyldimethanol Amine, N-butyldiethanolamine, N-butyldipropanolamine, N-butyldibutanolamine, dimethylbenzylamine, diethylbenzylamine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dipropylaniline N, N-dibutylaniline, N-phenyl-N-methylaniline, N-phenyl-N-ethylaniline and the like.

Specific examples of the compound represented by the general formula (6) include, for example, methylethylpropylamine, ethylpropylbutylamine, ethylmethylaniline, ethylmethylbenzylamine, ethylmethylaminomethanol, methylpropylaminomethanol, methyl Examples include butylaminomethanol, ethylmethylaminoethanol, ethylpropylaminoethanol, and ethylbutylaminoethanol.

The cationic compound may be a salt of the above-described amine derivative.
The salt is not particularly limited, and examples thereof include halides such as chloride, bromo and iodo, and acids having counter anions such as nitric acid, acetic acid and phosphoric acid. These salts may be high molecular weight as well as low molecular weight.

As the above-mentioned amine derivative, those having good solubility in a solvent described later and low reactivity are preferable, and those not contaminating the alignment film are preferable. As such an amine derivative, a tertiary amine derivative is suitable.

The cationic compound preferably has a boiling point of less than 200 ° C. When the boiling point is 200 ° C. or higher, the cationic compound may remain on the substrate when droplets discharged onto the substrate are dried, which may cause liquid crystal contamination. The upper limit with the more preferable boiling point of the said cationic compound is 100 degreeC. In addition, when performing the washing | cleaning process after drying the droplet formed on the board | substrate, you may use the cation compound whose boiling point is 200 degreeC or more.

Although it does not specifically limit as a density | concentration of the said cationic compound in the spacer particle dispersion liquid of this invention, A preferable minimum is 0.1 mmol / kg and a preferable upper limit is 10 mol / kg. When the concentration of the cationic compound is less than 0.1 mmol / kg, the effect of inhibiting the adhesion of the spacer particles to the SUS filter is reduced, and the SUS filter may be clogged. When the concentration of the cationic compound exceeds 10 mol / kg, the alignment film on the portion where the spacer particle dispersion of the present invention has landed may be contaminated, or the basic resistance used in the head and flow path of the inkjet apparatus may be increased. The weak member may be deteriorated. The more preferable lower limit of the concentration of the cationic compound is 0.3 mmol / kg, the more preferable upper limit is 5.0 mol / kg, the still more preferable lower limit is 0.5 mmol / kg, and the still more preferable upper limit is 1.0 mol / kg. .

The cationic compound may be fine particles having a cationic functional group on the surface (hereinafter also referred to as cationic fine particles) or an emulsion having a cationic functional group on the surface (hereinafter also referred to as cationic emulsion).

The monomer constituting the cationic fine particles is not particularly limited, and the same material as the organic material constituting the spacer particles can be used.

The method for producing the cationic fine particles is not particularly limited, and a conventionally known method can be used. Examples thereof include a mini-emulsion polymerization method, an emulsion polymerization method, a phase inversion emulsion polymerization method, a micro suspension polymerization method, a suspension polymerization method, a dispersion polymerization method, and a soap-free (precipitation) polymerization method. Among these, a dispersion polymerization method, a soap-free (precipitation) polymerization method and the like are preferably used because of excellent control of the particle diameter.

The method for imparting cationicity to the surface of the cationic fine particles is not particularly limited, and a method similar to the method for imparting a negative charge to the surface of the spacer particles can be used.

Further, in the method for producing the cationic fine particles, examples of the monomer that imparts cationicity include amines having a polymerizable group such as dimethylaminomethyl methacrylate and diethylaminoethyl methacrylate, and polymerizable groups such as vinylpyridine. And nitrogen-containing aromatic compounds, sulfonium having a polymerizable group such as phenyldimethylsulfonium methacrylate, and the like.

The average particle size of the cationic fine particles is not particularly limited, but is preferably 10% or less of the average particle size of the spacer particles. When the average particle size of the cationic fine particles exceeds 10% of the average particle size of the spacer particles, the coverage of the cationic fine particles on the spacer particles is lowered, and the effect of inhibiting the adhesion of the spacer particles to the SUS filter is obtained. The cell gap may become small or the cell gap may become non-uniform because the cationic fine particles are too large.

The particle size of the cationic fine particles may not be uniform. However, in the case where the gap accuracy is strictly controlled or the coverage is uniform so as to eliminate display defects as a liquid crystal display device, particles representing a particle size distribution are used. The diameter variation coefficient (CV value: a value obtained by dividing the standard deviation value of the particle size distribution by the average particle size as a percentage) is preferably 20% or less. A more preferable range of the coefficient of variation of the particle diameter is 1 to 10%.

In the method for producing the cationic emulsion, examples of the emulsifier imparting cationicity include aliphatic amines, pyridine derivatives, and imidazole derivatives.

The dispersion droplet component constituting the cationic emulsion is not particularly limited as long as it is not mixed with the solvent constituting the spacer dispersion liquid. However, since it easily evaporates in the drying process, it has a low molecular weight with a low boiling point and high hydrophobicity. Saturated hydrocarbon compounds are preferably used.

The cationic fine particles and the cationic emulsion prevent the spacer particles from adhering to the SUS filter of the ink jet device and causing clogging, but are heated when manufacturing a liquid crystal display device. It is even better if it has a role of melting and solidly adhering and fixing the spacer particles to the substrate.

The material constituting the cationic fine particles or cationic emulsion having adhesiveness is not particularly limited as long as it can be melted or softened by heating and can adhere the spacer particles to the substrate. A thermoplastic resin is preferably used because it is softened and deformed, and an adhesion area between the substrate and the spacer particles is increased, resulting in an increase in adhesion.

Although it does not specifically limit as a softening point of the material which comprises the cationic fine particle or cationic emulsion which has the said adhesiveness, A preferable minimum is 40 degreeC and a preferable upper limit is 120 degreeC. When the softening point is less than 40 ° C., the adhesive fine particles or the emulsion component may be softened due to heat generation or the like when the liquid crystal panel is used for a long period of time, and the adhesion of the spacer may be impaired. When the softening point exceeds 120 ° C., the heating temperature for fixing the spacer becomes high, the burden on the hardened film and the glass substrate is large, and this may cause orientation failure and distortion.

The blending amount of the cationic fine particles and the cationic emulsion in the spacer particle dispersion of the present invention is not particularly limited, but a preferred lower limit is 0.1 parts by weight and a preferred upper limit is 200 parts by weight with respect to 100 parts by weight of the spacer particles. Part. When the amount of the cationic fine particles and the cationic emulsion is less than 0.1 part by weight, the effect of inhibiting the adhesion of the spacer particles to the SUS filter is reduced, and the SUS filter is clogged. There is. When the blending amount of the cationic fine particles and the cationic emulsion exceeds 200 parts by weight, the cationic fine particles and the cationic emulsion remain in the portion of the alignment film where the spacer particle dispersion of the present invention has landed when the ink is dried. May cause deterioration in display quality due to a decrease in contrast and color tone. The more preferable lower limit of the blending amount of the cationic fine particles and the cationic emulsion is 1 part by weight, and the more preferable upper limit is 100 parts by weight.

The spacer particle dispersion of the present invention contains a solvent.
The solvent is not particularly limited, but a water-soluble or hydrophilic solvent is preferable. A nozzle for an aqueous medium may be used in an ink jet apparatus. When a nozzle for an aqueous medium is used, if a highly hydrophobic solvent is used as the solvent, the solvent penetrates into the member constituting the nozzle or a part of the adhesive bonding the member becomes the solvent. May dissolve. Therefore, when a nozzle for an aqueous medium is used, the spacer particle dispersion of the present invention preferably contains a water-soluble or hydrophilic solvent.
In addition, the said solvent may be used independently and 2 or more types may be used together.

Examples of the water-soluble or hydrophilic solvents include water, monoalcohols, ethylene glycol multimers, propylene glycol multimers, monomethyl ethers and monoethyl ethers of glycols (referring to ethylene glycol and propylene glycol). Lower monoalkyl ethers such as monoisopropyl ether, monopropyl ether, monobutyl ether, lower dimethyl ethers such as glycol dimethyl ether, diethyl ether, diisopropyl ether, dipropyl ether, etc., glycol monoacetates, diacetates, etc. Examples include alkyl esters, diols, ether derivatives of diols, acetate derivatives of diols, polyhydric alcohols or ether derivatives or acetate derivatives thereof, esters, etc. It is.

The monoalcohols are not particularly limited, and examples thereof include ethanol, n-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-hexanol, 1-methoxy-2-propanol, and furfuryl alcohol. And tetrahydrofurfuryl alcohol.
The ethylene glycol multimer is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol.
The propylene glycol multimer is not particularly limited, and examples thereof include propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.
The diols are not particularly limited, and examples thereof include 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 3-methyl-1,5-pentanediol. 3-hexene-2,5-diol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 1,6-hexanediol, Neopentyl glycol and the like can be mentioned.
The polyhydric alcohols or ether derivatives or acetate derivatives thereof are not particularly limited. For example, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,5-pentanetriol, Examples include trimethylolpropane, trimethylolethane, pentaerythritol and the like.
The esters are not particularly limited, and examples thereof include methyl acetate and ethyl acetate.
In addition to these, the water-soluble or hydrophilic solvents include dimethyl sulfoxide, thiodiglycol, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl- 2-Imidazolidine, sulfolane, formamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylformamide, acetamide, N-methylacetamide, α-terpineol, ethylene carbonate, propylene carbonate, bis-β-hydroxy Examples include ethyl sulfone, bis-β-hydroxyethyl urea, N, N-diethylethanolamine, abiethinol, diacetone alcohol, urea and the like.
These water-soluble or hydrophilic solvents may be used alone or in combination of two or more.
Among these, the solvent preferably contains at least one selected from the group consisting of water, isopropanol, ethylene glycol, ethylene glycol monoethyl ether, propylene glycol, and glycerin.

The solvent is preferably a mixed solvent obtained by combining two or more of the above water-soluble or hydrophilic solvents. The viscosity and surface tension of the spacer particle dispersion of the present invention to be described later can be adjusted, and when the liquid droplets discharged onto the substrate are dried, they shrink toward the landing center and the liquid This is because one or more spacer particles contained in the droplet can gather near the center of the droplet.
As such a mixed solvent, it is preferable to mix a low boiling point low surface tension solvent and a high boiling point high surface tension solvent. Specifically, for example, the boiling point is less than 150 ° C. and the surface tension is 28 mN / Preferable examples include a solvent having a boiling point of 150 ° C. or higher, a surface tension of 30 mN / m or higher, and a mixed solvent (1) containing water.

Although it does not specifically limit as said solvent whose boiling point is less than 150 degreeC and surface tension is less than 28 mN / m, Ethanol, 2-propanol (IPA), t-butanol etc. are used suitably.
The solvent having a boiling point of 150 ° C. or higher and a surface tension of 30 mN / m or higher is not particularly limited, but propylene glycol, diethylene glycol monomethyl ether, ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerin. Etc. are preferably used.

The blending amount of the solvent having a boiling point of less than 150 ° C. and a surface tension of less than 28 mN / m in the mixed solvent (1) is not particularly limited, but the preferred lower limit is 2% by weight and the preferred upper limit is 40% by weight (more preferred lower limit is 5% by weight, more preferred upper limit is 20% by weight), the preferred lower limit of the amount of the solvent having a boiling point of 150 ° C. or higher and a surface tension of 30 mN / m or higher is 30% by weight, and the preferred upper limit is 96% by weight (more preferred) The lower limit is 40% by weight, and the more preferred upper limit is 90% by weight. The preferred lower limit of the amount of water is 0% by weight, the preferred upper limit is 60% by weight (the more preferred lower limit is 5% by weight, and the more preferred upper limit is 40% by weight). %).
In the mixed solvent (1), the ratio of the solvent having a boiling point of less than 150 ° C. and a surface tension of less than 28 mN / m and water is determined by adding a solvent having a boiling point of 150 ° C. or more and a surface tension of 30 mN / m or more. The excluded amount, that is, the preferred lower limit is 4% by weight and the preferred upper limit is 70% by weight (more preferred lower limit is 6% by weight, more preferred upper limit is 55% by weight).

If the solvent having a boiling point of less than 150 ° C. and a surface tension of less than 28 mN / m is less than 2% by weight, the surface tension of the spacer particle dispersion of the present invention becomes too high, and the spacer particle dispersion is applied to the head of the inkjet apparatus. When introduced, bubbles may remain in the ink chamber, which may cause a problem that nozzles that do not discharge are generated. Further, when the amount of water and a solvent having a boiling point of less than 150 ° C. and a surface tension of less than 28 mN / m is less than 4% by weight, the viscosity of the spacer particle dispersion of the present invention is too high, and is discharged from the inkjet head. When the amount exceeds 70% by weight, the viscosity of the spacer particle dispersion of the present invention becomes too low, and the discharge stability, particularly in the high frequency driving state, may occur. There may be a problem that the stability is lowered, or the spacer particle dispersion may be dried at the tip of the nozzle of the ink jet apparatus.

In addition, when the SUS filter of the ink jet device is particularly highly hydrophilic, or before introducing the spacer particle dispersion of the present invention, a solvent that has a low surface tension such as 2-propanol and can wet the liquid contact part well. When the SUS filter can be replaced with the spacer particle dispersion liquid so that the bubbles are not entrained after the bubbles are sufficiently removed by filling with the above, the mixed solvent has a boiling point of less than 150 ° C. and a surface tension of 28 mN / There is no particular necessity to add a solvent of less than m.
In this case, the preferable lower limit of the amount of the solvent having the boiling point of 150 ° C. or higher and the surface tension of 30 mN / m or higher is 30% by weight, and the preferable upper limit is 96% by weight (the more preferable lower limit is 45% by weight, and the more preferable upper limit is 94 %) And a preferred lower limit of the amount of water mixed is 4% by weight, and a preferred upper limit is 70% by weight (more preferred lower limit is 6% by weight, more preferred upper limit is 55% by weight). Is mentioned.
When the blending amount of water in the mixed solvent (2) in such a combination is less than 4% by weight, the viscosity of the spacer particle dispersion of the present invention is too high and it is difficult to eject from the inkjet head (the driving voltage is high). Problems may occur. When the blending amount of water in the mixed solvent (2) exceeds 70% by weight, there is a problem that the viscosity of the spacer particle dispersion of the present invention becomes too low and the discharge stability, particularly the stability in a high frequency driving state is lowered. May occur. Even in this case, there is no problem in adding a solvent having a surface tension of less than 150 mN / m at less than 150 ° C. However, when adding a solvent having a surface tension of less than 150 ° C. and a surface tension of less than 28 mN / m in an amount of 2% by weight or more, the mixed solvent (1) composed of the combinations described above is preferable due to the limitation on the viscosity and the like that affect the discharge performance.

The spacer particle dispersion of the present invention improves the dispersibility of the spacer particles within the range that does not impair the purpose of the present invention, controls the physical properties such as surface tension and viscosity, improves the discharge accuracy, Various surfactants, viscosity modifiers, and the like may be contained for the purpose of improving the mobility of these.

Although it does not specifically limit as pH of the spacer particle dispersion liquid of this invention, A preferable minimum is 7 and a preferable upper limit is 13. If the pH of the spacer particle dispersion of the present invention is less than 7, the effect of inhibiting the adhesion of the spacer particles to the SUS filter becomes insufficient, and the filter may be clogged. When the pH of the spacer particle dispersion of the present invention exceeds 13, the alignment film on the portion where the spacer particle dispersion of the present invention has landed is contaminated, or the base resistance used in the head and flow path of the inkjet device The weak member may be deteriorated. The more preferred lower limit of the pH of the spacer particle dispersion of the present invention is 8, and the more preferred upper limit is 12.
In general, the pH of the ink of the present invention before adding the cationic compound is often around 5. When a small amount of a cationic compound is added, the pH rises. Although it cannot be generally stated depending on the surface state of the spacer, the solvent composition, the type of the cationic compound, etc., the pH becomes around 7 when 0.1 mmol / kg of the cationic compound is added. When 1.0 to 10 mmol / kg of the cationic compound is added, the amount is about 8. When 10 to 200 mmol / kg is added, the amount is about 9.

The residual amount of the cationic compound is not particularly limited, but a preferable upper limit is 1% by weight. If the residual amount of the cationic compound exceeds 1% by weight, the alignment film may become abnormal, and when the liquid crystal cell is assembled, alignment failure may occur and display failure may occur. A more preferable upper limit of the residual amount of the cationic compound is 0.1% by weight.

The spacer particle dispersion of the present invention preferably has a small content of non-volatile components excluding the spacer particles. Specifically, the spacer particle dispersion has a particle size of less than 1 μm with respect to the entire spacer particle dispersion of the present invention. The upper limit with preferable content of a component is 0.001 weight%. When the content of the nonvolatile component exceeds 0.001% by weight, the liquid crystal and the alignment film are contaminated, and the display quality such as contrast of the liquid crystal display device may be deteriorated.
The non-volatile component is not particularly limited, for example, dust in the atmosphere, impurities contained in the solvent used to disperse the spacer particles, pulverized spacer particles, ionic compounds such as metal ions, etc. Examples thereof include solids and non-spherical fine particles having no shape retention in the spacer particle dispersion.

The method for reducing the non-volatile components in the spacer particle dispersion of the present invention is not particularly limited. For example, the spacer particle dispersion of the present invention is first filtered with a filter having a filtration diameter larger than the particle diameter of the spacer particles. After removing large dust, the spacer particle dispersion of the present invention was centrifuged to precipitate the spacer particles, and then the supernatant was discarded. Further, the filtered spacer particles were filtered through a filter having a filtration diameter of 1 μm and added with a solvent. A method of dispersing spacer particles, a method of filtering spacer particles with a filter having a filtration diameter smaller than the particle diameter of the spacer particles, and dispersing the filtered spacer particles in a solvent filtered with a filter having a filtration diameter of 1 μm And a method using an ion-adsorptive solid such as a layered silicate. These methods may be repeated.

The difference between the specific gravity of the spacer particles in the spacer particle dispersion of the present invention and the specific gravity of the liquid portion excluding the spacer particles is not particularly limited, but a preferable upper limit is 0.5. When the difference in specific gravity between the liquid particles excluding the spacer particles and the spacer particles exceeds 0.5, the spacer particles settle during storage of the spacer particle dispersion of the present invention and the dispersed spacer particle of the present invention is dispersed. The number of spacer particles in the liquid may become uneven.

The difference between the solubility parameter value of the spacer particle surface in the spacer particle dispersion of the present invention and the solubility parameter value of the liquid part excluding the spacer particles is not particularly limited, but a preferred upper limit is 5.0. When the difference in solubility parameter value between the liquid particles excluding the spacer particles and the spacer particles exceeds 5.0, the dispersibility of the spacer particles in the spacer particle dispersion of the present invention is inferior, and the dispersed spacer particles of the present invention are dispersed. The number of spacer particles in the liquid may become uneven.

Although it does not specifically limit as surface tension in 23 degreeC of the spacer particle dispersion liquid of this invention, A preferable minimum is 25 mN / m and a preferable upper limit is 50 mN / m. If the surface tension is outside this range, it may be difficult to stably discharge the spacer particle dispersion of the present invention using an inkjet apparatus.
Further, the value obtained by subtracting the surface tension value of the substrate from the surface tension value of the spacer particle dispersion is not particularly limited, but a preferable lower limit is −2 mN / m and a preferable upper limit is 40 mN / m. When the value obtained by subtracting the surface tension value of the substrate from the surface tension value of the spacer particle dispersion liquid is less than −2 mN / m, the landing diameter when the spacer particle dispersion liquid of the present invention lands on the substrate is very large. May become large. If the value obtained by subtracting the surface tension value of the substrate from the surface tension value of the spacer particle dispersion exceeds 40 mN / m, the landed spacer particle dispersion easily moves, and the spacer particles cannot be arranged accurately. Sometimes.
In the present specification, the surface tension is a value measured by a Wilhelmy method using a platinum plate.

In the spacer particle dispersion of the present invention, for example, it is preferable to mix the above-described low boiling point low surface tension solvent and high boiling point high surface tension solvent so as to satisfy the above-mentioned requirements for surface tension. By selecting such a combination, the surface tension increases as the landed droplets of the spacer particle dispersion liquid of the present invention dry, so that the force that reduces the diameter of the droplets as the droplets dry is obtained. It can limit the range in which the final spacer particles are disposed.

The receding contact angle (θr) with respect to the substrate in the spacer particle dispersion of the present invention is not particularly limited, but is preferably 5 degrees or more. When the receding contact angle is 5 degrees or more, when the droplet of the spacer particle dispersion liquid of the present invention that has landed on the substrate is dried, it shrinks toward the center and one droplet in the droplet. The spacer particles contained above can be gathered near the center of the droplet. When the receding contact angle is less than 5 degrees, the droplet dries around the center (landing center) where the droplet landed on the substrate, the droplet diameter is reduced, and the spacer particle is centered. It may be difficult to get together.
In this specification, the receding contact angle refers to the process in which the droplet of the spacer particle dispersion liquid of the present invention placed on the substrate is first placed on the substrate after it is placed on the substrate and dried. The contact angle shown when it starts to become smaller than the landing diameter when it is applied (when the droplet starts to shrink), or the contact angle shown when 80 to 95% by weight of the volatile components of the droplet volatilizes. .

The receding contact angle tends to be smaller than the so-called contact angle (the initial contact angle when a droplet is placed on a substrate, which is usually called the contact angle in most cases). This is the contact angle of the droplet with respect to the substrate on the substrate surface that is not in contact with the solvent constituting the spacer particle dispersion of the present invention, whereas the receding contact angle is that of the present invention. This is considered to be due to the contact angle of the droplet with respect to the substrate on the substrate surface after contacting the solvent constituting the spacer particle dispersion. That is, when the receding contact angle is significantly lower than the initial contact angle, it indicates that the alignment film is damaged by those solvents, and it is preferable to use these solvents against alignment film contamination. It is thought that it shows that there is not.

The initial contact angle θ between the spacer particle dispersion of the present invention and the substrate surface is not particularly limited, but a preferred lower limit is 10 degrees and a preferred upper limit is 110 degrees. When the initial contact angle θ is less than 10 degrees, the spacer particle dispersion liquid droplets of the present invention discharged onto the substrate may be wet and spread on the substrate, and the arrangement interval of the spacer particles may not be narrowed. When the initial contact angle θ exceeds 110 degrees, the liquid droplets easily move around on the substrate with a slight vibration, and as a result, the placement accuracy may deteriorate and the adhesion between the spacer particles and the substrate may deteriorate. .

The viscosity of the spacer particle dispersion of the present invention measured with an E-type viscometer or a B-type viscometer at the head temperature during ejection from an inkjet apparatus is not particularly limited, but a preferred lower limit is 0.5 mPa · s, a preferred upper limit. Is 15 mPa · s. When the viscosity at the head temperature during ejection is less than 0.5 mPa · s, it may be difficult to control the ejection amount when ejecting from the ink jet apparatus. When the viscosity at the head temperature at the time of ejection exceeds 15 mPa · s, the ink jet apparatus may not be able to eject. A more preferable lower limit of the viscosity at the head temperature at the time of ejection is 5 mPa · s, and a more preferable upper limit is 10 mPa · s.
When discharging the spacer particle dispersion liquid of the present invention, the head temperature of the ink jet apparatus is cooled by a Peltier element, a refrigerant, or the like, or heated by a heater, etc. The temperature may be adjusted between -5 ° C and 50 ° C.

The solubility of the alignment particles in the spacer particle dispersion of the present invention is not particularly limited, but the preferred upper limit is 5%. When the solubility of the spacer film in the alignment film exceeds 5%, the alignment film may be damaged or liquid crystal contamination may occur.
The alignment film solvent solubility can be measured, for example, by the following method. That is, the spacer particle dispersion of the present invention corresponding to 100 mg in solid content was dried at 90 ° C. for 5 hours in a vacuum and further dried at 150 ° C. for 5 hours in a vacuum, and then dried at 220 ° C. Bake for 1 hour. After measuring the weight (Wa) of the cured product, it was placed in 10 g of N-methyl-2-pyrrolidone and allowed to stand for 5 hours while shaking, the solid content was filtered off, dried in vacuum at 150 ° C. for 5 hours and dried. The solidified weight (Wb) is measured.
In addition, the alignment film solvent solubility can be obtained by the following formula.
Alignment film solvent solubility = (Wa−Wb) / Wa

As described above, the spacer particle dispersion of the present invention containing spacer particles having a negative charge has been invented. For example, when a cationic functional group (such as amine) is introduced on the surface of the spacer particles, the spacer particles Charge (zeta potential) is positive. On the other hand, when the surface of the SUS filter of the ink jet apparatus is coated (water repellent treatment) with, for example, an epoxy compound or fluorine, the charge of the SUS filter is negative. Even in such a case, the spacer particles adhere to the filter of the ink jet apparatus by electrostatic interaction.
When the surface charge of the spacer particles is positive, the spacer particle dispersion of the present invention preferably contains one or more anionic compounds in place of the cationic compound in the solvent described above. By using a spacer particle dispersion containing an anionic compound in such a solvent, the spacer particles can be prevented from adhering to the SUS filter.
This is because, by adding an anionic compound, particularly an acidic compound, to the spacer particle dispersion of the present invention, an acid is added as a counter anion to the cationic functional group on the surface of the spacer particle. This is thought to be because the electrostatic interaction with is weakened. Further, the anionic compound has an effect of forming a complex with a cationic functional group on the surface of the spacer particle, improving hydrophilicity and weakening hydrophobic interaction.

The acidic compound is not particularly limited, and examples thereof include organic acids such as malonic acid, acetic acid, and oxalic acid, and inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid, and also include carboxylic acid, phosphoric acid, sulfonic acid, and the like. Examples include derivatives having functional groups. The acidic compound may be a polymer. Further, it may be a general surfactant such as a modified polyvinyl alcohol acid.

The spacer particle dispersion liquid of the present invention is a method in which droplets of the spacer particle dispersion liquid are ejected by using an ink jet apparatus to land on a predetermined position on the substrate and then dried to dry the spacer particles on the substrate. Can be placed in position.
That is, a method of manufacturing a liquid crystal display device having a pixel region and a non-pixel region, wherein the spacer particle dispersion of the present invention is applied to the non-pixel region of the first substrate or the second substrate using an inkjet device. A step of arranging at a specific position, a step of drying the spacer particle dispersion, and a step of superposing the first substrate and the second substrate so as to face each other through the liquid crystal and the spacer particles. A method for manufacturing a liquid crystal display device is also one aspect of the present invention.

In the method for producing a liquid crystal display device of the present invention, the ink jet device used for discharging the spacer particle dispersion onto the substrate is not particularly limited. For example, a piezo method for discharging liquid by vibration of a piezo element, or a rapid Examples thereof include an inkjet apparatus using a conventionally known ejection method such as a thermal method in which liquid is ejected by utilizing expansion of the liquid by heating. Among these, a piezo method having a small thermal influence on the discharged spacer particle dispersion is preferable.

It does not specifically limit as a board | substrate provided with the manufacturing method of the liquid crystal display device of this invention, What is normally used as a panel substrate of a liquid crystal display device, such as glass and resin, can be used. Of the pair of substrates, a substrate in which a color filter is provided in a pixel region can be used as one substrate. In this case, the pixel region is defined by a black matrix such as a resin in which a metal such as chrome or carbon black that hardly transmits light is dispersed. This black matrix constitutes a non-pixel region.

The substrate is preferably subjected to a water repellent treatment in advance so that the contact angle with the spacer particle dispersion of the present invention is 20 degrees or more.

In the method for manufacturing a liquid crystal display device of the present invention, the location where the spacer particle dispersion of the present invention is discharged and landed is a position corresponding to a non-pixel region.
The position corresponding to the non-pixel area is the position of the substrate on the non-pixel area (the above-described black matrix for a color filter substrate) or the other substrate (a TFT array substrate for a TFT liquid crystal panel). It means any one of the areas corresponding to the non-pixel areas when overlapped with the substrate having the non-pixel areas (in the case of a TFT array substrate, a wiring portion or the like).
The position corresponding to the non-pixel region may include a portion having a periphery and a step. The step here means an unintentional unevenness (level difference from the surroundings) caused by wiring provided on the substrate, an unevenness intentionally provided to collect spacer particles, and is below the uneven surface. Any structure is acceptable. Therefore, the step here refers to a step between a concave portion or a convex portion and a flat portion (reference surface) in the surface uneven shape.

Although it does not specifically limit as a space | interval of the spacer particle | grains in a board | substrate with which the said spacer particle | grains are arrange | positioned, A preferable upper limit is 0.2 micrometer. If the distance between the spacer particles and the substrate exceeds 0.2 μm, the cell gap may not be realized accurately.
The variation (standard deviation) between the uppermost portion of the spacer particles (the place farthest from the substrate) and the substrate in the substrate on which the spacer particles are disposed is not particularly limited, but is preferably 10% or less. If the variation (standard deviation) between the top of the spacer particles and the substrate exceeds 10%, the cell gap may not be realized accurately.

The stress (10% deformation stress) when displaced 10% in the substrate direction from the uppermost portion of the spacer particles (the place farthest from the substrate) in the substrate on which the spacer particles are arranged is not particularly limited, but the preferred lower limit is The upper limit is preferably 0.2 mN and 10 mN.
The 10% deformation stress can be measured by the following method. That is, at 10 positions, the stress when 10% is displaced with a 100 μm stylus using a micro hardness meter (for example, manufactured by Shimadzu Corporation) is measured. For each placement position, the stress is measured, a value obtained by dividing the stress by the number of spacer particles present at the placement position is determined, and the average value is defined as 10% deformation stress.

The recovery rate of the spacer particles in the substrate on which the spacer particles are arranged is not particularly limited, but a preferable lower limit is 40%.
The recovery rate can be measured by the following method. That is, at 10 arrangement positions, for each arrangement, a weight obtained by multiplying 9.8 (mN) by the number of spacer particles present at the arrangement position is applied for 1 second, and the top of the substrate and the spacer particles (from the substrate) The change in distance to the farthest point) is measured before and after weighting. The average value at the ten arrangement positions of the value obtained by dividing the weighted distance by the distance before weighting is taken as the recovery rate.

In the substrate on which the spacer particles are arranged, it is preferable that 80% or more of the spacer particles exist in a region on the substrate corresponding to the light shielding region of the liquid crystal display device.

In the substrate on which the spacer particles are arranged, before and after a vibration test by a method according to JIS C 0040 (shock excitation (acceleration 50G (9 msec))) and sine wave excitation for 5 minutes (0.1 KHz30G, 1 KHz30G). The change rate of the abundance ratio of the spacer particles is preferably within ± 20%.

As described above, after obtaining the substrate on which the spacer particles are arranged by arranging the spacer particles on the substrate, the other substrate is opposed to the substrate on which the spacer particles are arranged through the spacer particles by a conventional method. After being superposed in such a manner, the liquid crystal is filled in the gap between the formed substrates by heat-compression bonding, and a liquid crystal display device is manufactured (vacuum injection method). Also, a peripheral sealing agent is applied to one substrate, liquid crystal is dropped within a range surrounded by the other substrate, the other substrate is bonded, the sealing agent is cured, and a liquid crystal display device is manufactured (liquid crystal dropping method).

In the method for producing a liquid crystal display device of the present invention, since the spacer particle dispersion of the present invention described above is used, the SUS filter of the ink jet device is not clogged, and the arrangement of the spacer particles is continuously stabilized. The liquid crystal display measure which can be performed and is excellent in display quality can be manufactured.
A liquid crystal display device produced by the method for producing a liquid crystal display device of the present invention is also one aspect of the present invention.

The spacer particle dispersion of the present invention contains spacer particles, a cationic compound, and a solvent as described above, but the components other than the spacer particles (hereinafter also referred to as the dispersion solvent according to the present invention), That is, a dispersion solvent containing a cationic compound, a solvent, and the like is an inkjet device for cleaning an inkjet device used when a spacer particle dispersion liquid containing spacer particles having a charge on the surface is discharged onto a substrate. It can also be used as a cleaning solution.

Conventionally, when spacer particles adhere to a liquid contact portion of an ink jet device, a method of cleaning the ink jet device using a dispersion solvent or the like used for the spacer particle dispersion as a cleaning liquid to remove the spacer particles has been used. However, the conventional cleaning liquid cannot efficiently remove the spacer particles.

By using a dispersion solvent used in the spacer particle dispersion of the present invention, that is, a dispersion solvent containing a cationic compound and a solvent, as a cleaning liquid for cleaning the inkjet apparatus, a flow path, head, or head in the inkjet apparatus is used. By neutralizing the surface charge of the spacer particles adhering to the SUS filter, the spacer particles can be removed easily and efficiently.

When the surface charge of the spacer particles is positive, the dispersion solvent according to the present invention preferably contains one or more anionic compounds instead of the cationic compounds. When the dispersion solvent according to the present invention contains an anionic compound instead of a cationic compound, the spacer particles adhering to the liquid contact portion of the inkjet device can be easily and efficiently removed when the inkjet device is washed. be able to.
This is because by adding an anionic compound, particularly an acidic compound, to the dispersion solvent according to the present invention, an acid is added as a counter anion to the cationic functional group on the surface of the spacer particles adhering to the liquid contact portion of the ink jet device. This is considered to be because the electrostatic interaction between the spacer particles and the liquid contact portion of the ink jet apparatus can be weakened. Further, the anionic compound has an effect of forming a complex with a cationic functional group on the surface of the spacer particle, improving hydrophilicity and weakening hydrophobic interaction.

When the dispersion solvent according to the present invention is used as a cleaning liquid, as a method for cleaning an ink jet apparatus, for example, after the cleaning liquid using the dispersion solvent according to the present invention is filled in the ink jet apparatus, the dispersion solvent according to the present invention is used. Examples thereof include a method of discharging the used cleaning liquid, a method of discharging from a head of an ink jet apparatus by suction or a pump, and the like.

ADVANTAGE OF THE INVENTION According to this invention, the spacer particle dispersion which can arrange | position the spacer particle | grain on the board | substrate by an inkjet apparatus stably continuously and can obtain the liquid crystal display device excellent in display quality can be provided. . Moreover, the manufacturing method of the liquid crystal display device using this spacer particle dispersion liquid, and a liquid crystal display device can be provided.

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

(Examples 1-19, Comparative Examples 1-3)
(Preparation of spacer particles 1)
In a separable flask, 15 parts by weight of divinylbenzene, 3 parts by weight of butyl acrylate, 2 parts by weight of 2-hydroxyethyl methacrylate, and 1.3 parts by weight of benzoyl peroxide as a polymerization initiator were added and stirred and mixed uniformly. . Next, 20 parts by weight of a 3% by weight aqueous solution of polyvinyl alcohol (trade name “Kuraray Poval GL-03”, manufactured by Kuraray Co., Ltd.) and 0.5 parts by weight of sodium dodecyl sulfate were added, mixed uniformly, and then ion exchanged. 140 parts by weight of water was added. Next, under a nitrogen gas stream, this aqueous solution was stirred and polymerized at 80 ° C. for 15 hours to obtain fine particles. After the obtained fine particles were sufficiently washed with hot water and acetone, classification operation was performed, and acetone was volatilized to obtain spacer particles 1 according to Example 1. The average particle diameter of the obtained spacer particles 1 was 4 μm, and the CV value was 3.0%. The zeta potential of the obtained spacer particles 1 was measured using a laser / rotating prism type zeta potential measuring device (manufactured by Nippon Luft). The results are shown in Tables 1-3.

(Preparation of spacer particles 2)
In a separable flask, 15 parts by weight of divinylbenzene, 5 parts by weight of isooctyl acrylate, and 1.3 parts by weight of benzoyl peroxide as a polymerization initiator were added and stirred and mixed uniformly. Next, 20 parts by weight of a 5% by weight aqueous solution of polyacrylic acid having a weight average molecular weight of 250,000 was added, and after stirring and mixing uniformly, 140 parts by weight of ion-exchanged water was added. Next, under a nitrogen gas stream, this aqueous solution was stirred and polymerized at 80 ° C. for 15 hours to obtain fine particles. After the fine particles obtained were sufficiently washed with hot water and acetone, classification operation was performed, and acetone was volatilized to obtain spacer particles 2 according to Example 2 and Comparative Example 1. The average particle diameter of the obtained spacer particles 2 was 4 μm, and the CV value was 2.8%. The zeta potential of the obtained spacer particles 2 was measured using a laser / rotating prism type zeta potential measuring device (manufactured by Nippon Luft). The results are shown in Tables 1-3.

(Preparation of spacer particles 3)
5 parts by weight of fine particles having an average particle size of 4.0 μm (trade name “Micropearl EX004”, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by weight of dimethyl sulfoxide (DMSO) were mixed with each material in the ratios shown in Tables 1 to 3. The raw material monomer was introduced into 100 parts by weight of the raw material monomer and dispersed uniformly by a sonicator. Thereafter, nitrogen gas was introduced into the reaction system and stirring was continued at 30 ° C. for 2 hours. Next, 20 parts by weight of a 0.1 mol / L ceric ammonium nitrate solution prepared with a 1N nitric acid aqueous solution is added, and the reaction is continued at 40 ° C. for 5 hours to form a coating layer having a thickness of 30 nm on the surface of the spacer particles. did. Thereafter, the spacer particles and the reaction solution were separated by filtration using a 1 μm membrane filter. The spacer particles were sufficiently washed with ethanol and acetone, and dried under reduced pressure in a vacuum drier to obtain spacer particles 3 according to Examples 3 to 19 and Comparative Examples 2 and 3. The zeta potential of the obtained spacer particles 3 was measured using a laser / rotating prism type zeta potential measuring device (manufactured by Nippon Luft). The results are shown in Tables 1-3.

(Preparation of spacer particle dispersion)
The required amount that gives a predetermined particle concentration (1.5% by weight) from the obtained spacer particles is slowly added to a mixed solvent of 75% by weight of ethylene glycol, 15% by weight of isopropyl alcohol, and 10% by weight of water, Dispersion was performed by thorough stirring while using a sonicator. The cationic compound shown to Tables 1-3 was added there so that it might become the density | concentration shown to Tables 1-3. Then, the aggregate was removed by filtering with a 20 μm mesh stainless steel mesh to obtain spacer particle dispersions according to Examples 1 to 19 and Comparative Examples 1 to 3. The pH of the obtained dispersion was measured with a pH meter (“Canister LAB pH meter F-21”, manufactured by Horiba, Ltd.). The results are shown in Tables 1-3.

(Evaluation of residual amount of cationic compound)
The spacer particle dispersions according to Examples 1 to 19 and Comparative Examples 1 to 3 were discharged onto a 0.7 mm thick glass substrate by an inkjet head (appropriate amount of liquid 40 Ng / droplet, discharge pitch 133 μm × 133 μm), and the substrate was It was dried on a hot plate at 180 ° C. for 10 minutes. The dried glass substrate was sealed in a gas chromatography ampoule and cured at 180 ° C. for 20 minutes to vaporize the residue. The vaporized residue was quantified by gas chromatography, and the residual amount of the cationic compound was quantified.
The residual amount (% by weight) was calculated by (the amount of the cation compound determined by gas chromatography) / (the amount of the cation compound in the ink ejected on the substrate). The results are shown in Tables 1-3.

(Circulation evaluation)
Take 1 kg of spacer particle dispersions according to Examples 1 to 19 and Comparative Examples 1 to 3 in a container that can be sealed, and use a tube with a 10 mm diameter SUS filter (270/2000 mesh, opening 10 μm) installed in the middle. Used and circulated at a flow rate of 150 mL per hour. Circulation was continued for 3 hours, and the degree of clogging of the filter was confirmed. The degree of filter clogging was determined according to the following criteria. The results are shown in Tables 1-3.
A: After 3 hours, there is no solid matter on the filter, and the circulation of the spacer particle dispersion does not stop.
◯: Solid matter that can be visually recognized is present on the filter after 3 hours, but the circulation of the spacer particle dispersion does not stop.
Δ: Circulation of the spacer particle dispersion is stopped between 1 hour and less than 3 hours.
X: The circulation of the spacer particle dispersion stops in less than 1 hour.

(Preparation of spacer particles 4)
5 parts by weight of fine particles having an average particle size of 4.0 μm (trade name “Micropearl EX004”, manufactured by Sekisui Chemical Co., Ltd.), 20 parts by weight of dimethyl sulfoxide (DMSO), 20 parts by weight of hydroxymethyl methacrylate, and lauryl acrylate 8 It was put in a weight part and dispersed uniformly by a sonicator. Thereafter, nitrogen gas was introduced into the reaction system, and stirring was continued at 30 ° C. for 2 hours. Next, 10 parts by weight of a 0.1 mol / L ceric ammonium nitrate solution prepared with a 1N aqueous nitric acid solution was added to the reaction system, and after 5 hours of reaction, the reaction solution was taken out and a 3 μm membrane filter was used. The particles and the reaction solution were separated by filtration. Next, the obtained particles were sufficiently washed with ethanol and acetone, and then dried under reduced pressure with a vacuum drier to obtain surface-modified spacer particles 4.
The zeta potential of the obtained spacer particles 4 was measured using a laser / rotating prism type zeta potential measuring device (manufactured by Nippon Luft). The results are shown in Table 4.

(Preparation of spacer particles 5)
5 parts by weight of fine particles having an average particle size of 4.0 μm (trade name “Micropearl EX004” manufactured by Sekisui Chemical Co., Ltd.), 20 parts by weight of DMSO, 10 parts by weight of hydroxymethyl methacrylate, 16 parts by weight of methacrylic acid, and lauryl acrylate Charged into 2 parts by weight. Thereafter, the surface-modified spacer particles 5 were produced in the same manner as the spacer particles 4.
The zeta potential of the obtained spacer particles 5 was measured using a laser / rotating prism type zeta potential measuring device (manufactured by Nippon Luft). The results are shown in Table 4.

(Preparation of spacer particle dispersion 1)
60 parts by weight of ethylene glycol, 20 parts by weight of isopropyl alcohol and 20 parts by weight of ion-exchanged water were uniformly stirred and mixed to prepare a dispersion solvent. The surface tension of the obtained dispersion solvent at 20 ° C. was 32.0 mN / m. The produced spacer particles 4 were slowly added to 0.5 part by weight and 100 parts by weight of the dispersion solvent, and stirred and mixed uniformly with a sonicator to prepare spacer particle dispersion 1.

(Preparation of spacer particle dispersion 2)
A spacer particle dispersion 2 was prepared in the same manner as the spacer particle dispersion 1, except that the spacer particles 4 were replaced with the spacer particles 5.

(Preparation of cleaning solution 1)
Cleaning solution 1 was prepared by dissolving 0.5 part by weight of diethylamine in 100 parts by weight of isopropanol.
In addition, the viscosity at 20 ° C. of the obtained cleaning liquid 1 measured with a rotary viscometer is 2.4 mPa · s, and the surface tension at 20 ° C. measured by the Wilhelmy method using a platinum plate is 22.8 mN / s. m.

(Preparation of cleaning solution 2)
Cleaning solution 2 was prepared by dissolving 0.5 parts by weight of diethanolamine in 50 parts by weight of isopropanol and 50 parts by weight of water.
In addition, the viscosity at 20 ° C. of the obtained cleaning liquid 2 measured with a rotary viscometer is 3.9 mPa · s, and the surface tension at 20 ° C. measured by the Wilhelmy method using a platinum plate is 26.8 mN / s. m.

(Preparation of cleaning solution 3)
Cleaning solution 3 was prepared by dissolving 0.5 parts by weight of N-methylisopropylamine in 50 parts by weight of ethylene glycol, 30 parts by weight of isopropanol, and 20 parts by weight of water.
The cleaning liquid 3 obtained had a viscosity at 20 ° C. measured with a rotary viscometer of 6.5 mPa · s, and the surface tension at 20 ° C. measured by the Wilhelmy method using a platinum plate was 31.6 mN / s. m.

(Preparation of cleaning solution 4)
Cleaning solution 4 was prepared by dissolving 0.5 parts by weight of triethanolamine in 100 parts by weight of isopropanol.
In addition, the viscosity at 20 ° C. of the obtained cleaning liquid 4 measured with a rotary viscometer is 2.4 mPa · s, and the surface tension at 20 ° C. measured by the Wilhelmy method using a platinum plate is 22.7 mN / s. m.

(Preparation of cleaning solution 5)
Cleaning solution 5 was prepared by dissolving 0.5 parts by weight of trimethylamine in 50 parts by weight of isopropanol and 50 parts by weight of water.
In addition, the viscosity at 20 ° C. of the obtained cleaning liquid 5 measured with a rotary viscometer is 3.9 mPa · s, and the surface tension at 20 ° C. measured by the Wilhelmy method using a platinum plate is 26.7 mN / s. m.

(Preparation of cleaning solution 6)
A cleaning solution 6 was prepared by dissolving 0.5 parts by weight of triethylamine in 50 parts by weight of ethylene glycol, 30 parts by weight of isopropanol, and 20 parts by weight of water.
In addition, the viscosity at 20 ° C. measured with a rotary viscometer of the obtained cleaning liquid 6 is 6.5 mPa · s, and the surface tension at 20 ° C. measured by the Wilhelmy method using a platinum plate is 31.5 mN / s. m.

(Preparation of SUS plate 1 with spacer particles attached)
In the prepared spacer particle dispersion 1 (5% solids), a SUS plate (SUS304) was immersed for 1 hour as an alternative to the wetted part of the ink jet device, and the SUS plate 1 with the spacer particles 4 attached to the surface was produced. .

(Preparation of SUS plate 2 with spacer particles attached)
In the prepared spacer particle dispersion 2 (solid content 5%), a SUS plate (SUS304) was immersed for 1 hour as an alternative to the liquid contact part of the ink jet device, and the SUS plate 2 with the spacer particles 5 attached to the surface was produced. .

(Reference Example 1)
The 200 mL beaker was filled with the cleaning liquid 1, the SUS plate 1 was immersed, and lightly shaken for cleaning.

(Reference Example 2)
A 200 mL beaker was filled with the cleaning liquid 1, the SUS plate 2 was immersed, and lightly shaken for cleaning.

(Reference Example 3)
The 200 mL beaker was filled with the cleaning liquid 2, the SUS plate 1 was immersed, and lightly shaken for cleaning.

(Reference Example 4)
The 200 mL beaker was filled with the cleaning liquid 2, the SUS plate 2 was immersed, and lightly shaken for cleaning.

(Reference Example 5)
A 200 mL beaker was filled with the cleaning solution 3, the SUS plate 1 was immersed, and lightly shaken for cleaning.

(Reference Example 6)
The 200 mL beaker was filled with the cleaning solution 3, the SUS plate 2 was immersed, and lightly shaken for cleaning.

(Reference Example 7)
A 200 mL beaker was filled with the cleaning solution 4, the SUS plate 1 was immersed, and lightly shaken for cleaning.

(Reference Example 8)
The 200 mL beaker was filled with the cleaning solution 4, the SUS plate 2 was immersed, and lightly shaken for cleaning.

(Reference Example 9)
A 200 mL beaker was filled with the cleaning solution 5, the SUS plate 1 was immersed, and lightly shaken for cleaning.

(Reference Example 10)
The 200 mL beaker was filled with the cleaning solution 5, the SUS plate 2 was immersed, and lightly shaken for cleaning.

(Reference Example 11)
The 200 mL beaker was filled with the cleaning liquid 6, the SUS plate 1 was immersed, and lightly shaken for cleaning.

(Reference Example 12)
The 200 mL beaker was filled with the cleaning liquid 6, the SUS plate 2 was immersed, and lightly shaken for cleaning.

(Reference Example 13)
A cleaning liquid 7 comprising only isopropanol was prepared.
The 200 mL beaker was filled with the cleaning solution 7, the SUS plate 1 was immersed, and lightly shaken for cleaning.

(Reference Example 14)
The 200 mL beaker was filled with the cleaning solution 7, the SUS plate 2 was immersed, and lightly shaken for cleaning.

(Cleaning evaluation)
The surface of the SUS board after washing performed in Reference Examples 1 to 14 was observed with an optical microscope and evaluated according to the following criteria. The results are shown in Table 4.
◎: Spacer particle adhesion on the SUS plate is less than 0 to 10 in one field of view (400 times) ○: Spacer particle adhesion on the SUS plate is less than 10 to several tens in one field of view (400 times) Δ : Adhesion of spacer particles on SUS plate within several tens to less than hundreds within one field of view (400 times) Δ ×: Adhesion of spacer particles on SUS plate within one field of view (400 times) ×: Spacer particles adhere to the SUS plate in one field of view (400 times)

ADVANTAGE OF THE INVENTION According to this invention, the spacer particle dispersion liquid which can arrange | position the spacer particle | grain on the board | substrate by an inkjet apparatus stably continuously, and can obtain the liquid crystal display device excellent in display quality is provided. it can. Moreover, the manufacturing method of the liquid crystal display device using this spacer particle dispersion liquid, and a liquid crystal display device can be provided.

Claims (5)

A spacer particle dispersion for disposing spacer particles at an arbitrary position on a substrate using an inkjet device,
A spacer particle dispersion, comprising spacer particles having a negative charge on the surface, a cationic compound, and a solvent. The spacer particle dispersion according to claim 1, wherein the cationic compound is an amine derivative. The spacer particle dispersion according to claim 1 or 2, wherein the solvent contains at least one selected from the group consisting of water, isopropanol, ethylene glycol, propylene glycol, and glycerin. The spacer particle dispersion according to claim 1, wherein the pH is 7 or more and the concentration of the cationic compound is 0.1 mmol / kg to 10 mol / kg. A method of manufacturing a liquid crystal display device having a pixel region and a non-pixel region,
Disposing the spacer particle dispersion according to claim 1, 2, 3, or 4 at a specific position corresponding to a non-pixel region of the first substrate or the second substrate using an ink jet device, the spacer particle dispersion A method of manufacturing a liquid crystal display device comprising: a step of drying a liquid; and a step of superposing the first substrate and the second substrate so as to face each other with liquid crystal and spacer particles interposed therebetween.