JP2007156320A - Method for manufacturing strongly sticking liquid crystal spacer, strongly sticking liquid crystal spacer, spacer dispersion liquid, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a strongly sticking liquid crystal spacer for obtaining a liquid crystal display device revealing excellent display quality by possessing an adhesive layer with a sufficient thickness on the surface of base substance particles, accurately arranging an ink jet system at an arbitrary position being a target on a substrate, hardly brittle-breaking the adhesive layer between a glass substrate and the spacer due to vibration, impact or the like, and eliminating light void or the like caused by the strongly sticking liquid crystal spacer. <P>SOLUTION: The method for manufacturing the strongly sticking liquid crystal spacer has: a process for preparing core shell particles forming a shell layer comprising a swelling resin on the surface of non-swelling base substance particles; a process for swelling the shell layer by absorbing a polymerization monomer being a raw material of the adhesive resin in the shell layer of the core shell particles; and a process for forming the adhesive layer comprising the adhesive resin on the surface of the base substance particles by polymerizing the polymerization monomer absorbed to the shell layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention has an adhesive layer having a sufficient thickness on the surface of the base particle, and can be accurately placed at a desired position on the substrate by an ink jet method, and between the glass substrate and the spacer by vibration or impact. Adhesive layer does not break brittlely, and there is no light leakage due to the adhesive liquid crystal spacer, and a liquid crystal display device that exhibits excellent display quality can be obtained. The present invention relates to a conductive liquid crystal spacer, a spacer dispersion liquid, and a liquid crystal display device.

Liquid crystal display devices are currently widely used in personal computers, portable electronic devices, and the like. FIG. 1 is a cross-sectional view illustrating an example of a liquid crystal display device. As shown in FIG. 1, in general, a liquid crystal display device has two transparent substrates in which a transparent electrode 3, an alignment film 8, a color filter 4, a black matrix 5 and the like are arranged on the inner side and a polarizing plate 2 is arranged on the outer side. 1 is arranged so as to face each other with a sealant 9 disposed around them, and the liquid crystal 6 is sealed in the formed gap. In this liquid crystal display device, the spacer 7 is used for the purpose of regulating the distance between the two transparent substrates 1 and maintaining an appropriate thickness (cell gap) of the liquid crystal layer.

In the conventional method for manufacturing a liquid crystal display device, spacers are distributed randomly and uniformly on the substrate on which the pixel electrodes are formed. Therefore, the spacers are also provided on the pixel electrodes, that is, the display portion (pixel region) of the liquid crystal display device. Will be placed. The spacer is generally made of synthetic resin, glass or the like. When the spacer is arranged on the pixel electrode, the phenomenon that the polarization is disturbed and the polarization is lost, the so-called depolarization phenomenon occurs. May cause a problem of light leakage. In addition, the alignment of the liquid crystal on the spacer surface may cause a problem that light leakage occurs and the display quality deteriorates due to a decrease in contrast and color tone. Further, in the TFT liquid crystal display device, the TFT element is disposed on the substrate. However, if the spacer is disposed on the TFT element, the TFT element may be damaged when pressure is applied to the substrate. Sometimes caused problems.

In order to suppress the occurrence of such problems due to the random and uniform distribution of the spacers, it has been studied to dispose the spacers only under the light shielding layer (the portion defining the pixel region, hereinafter also referred to as the black matrix). As a method of arranging the spacer only at a specific position as described above, for example, after aligning the opening of the mask having the opening with the position to be arranged, the spacer is arranged only at the position corresponding to the opening. A color liquid crystal panel is disclosed (for example, see Patent Document 1). In addition, a liquid crystal display device in which a spacer is electrostatically attracted to a photosensitive member and then transferred to a transparent substrate and a manufacturing method thereof are disclosed (for example, see Patent Document 2).
However, these methods have a problem that the alignment film on the substrate is easily damaged because the mask or the photosensitive member is in direct contact with the substrate, resulting in a deterioration in display quality.

In addition, a method for manufacturing a liquid crystal display device is disclosed in which spacers are arranged at specific positions by electrostatic repulsion by applying spacers charged by applying a voltage to pixel electrodes on a substrate (for example, (See Patent Document 3).
However, since this method requires electrodes according to the pattern to be arranged, it is impossible to completely arrange the spacers at arbitrary positions, and there is a problem that the types of applicable liquid crystal display devices are restricted. there were.

On the other hand, in a liquid crystal display element in which a spacer and a liquid crystal are interposed in a gap portion between translucent electrode substrates on which transparent electrodes are deposited on opposite surfaces, the spacers are dispersedly arranged on the electrode substrate using an inkjet device. That is, a manufacturing method of a liquid crystal display device in which spacers are arranged by an ink jet printing method is disclosed (for example, see Patent Document 4).
This method can be said to be an effective method because it does not directly contact the substrate itself as in the above-described method, and the spacer can be arranged in an arbitrary pattern at an arbitrary position.

However, since the spacer dispersion liquid ejected by the ink jet printing method includes spacers having a size of about 1 to 10 μm, the nozzle diameter of the head of the ink jet apparatus must be increased in order to eject straightly. As a result, the spacer dispersion liquid droplets discharged onto the substrate become large, and even if the spacer dispersion liquid is discharged to aim at the light shielding area on the substrate, the spacer dispersion liquid droplets are removed from the light shielding area. There was a problem of protruding into the pixel area.
In order to solve such a problem, there is known a method of drying and reducing the droplets of the spacer dispersion liquid around the landing point on the light shielding region, and collecting the spacers on the landing point accordingly.

On the other hand, since the conventional spacer has low adhesion to the substrate, as described above, the spacer dispersion liquid is dried and reduced around the landing point, and the spacer is collected at the landing point. However, the spacer moves when the liquid crystal is injected, and light leakage occurs in the liquid crystal display device to be manufactured, resulting in a problem that the display quality deteriorates due to a decrease in contrast and color tone.

As a method for improving the adhesion of the spacer to the substrate, for example, by reacting an isocyanate compound having a polymerizable vinyl group with particles having active hydrogen on the surface in an organic solvent, polymerization is performed on the particle surface. After the introduction of the polymerizable vinyl group and washing, the adhesive vinyl layer is formed by graft polymerization of a polymerizable vinyl monomer starting from the polymerizable vinyl group introduced onto the particle surface in an organic solvent. An adhesive spacer is disclosed (see, for example, Patent Document 5).

However, since such an adhesive spacer forms a large amount of non-grafted polymer by combining ordinary solution polymerization when performing graft polymerization, the conversion rate of the added polymerizable monomer to graft polymerization is increased. However, it was extremely difficult to form an adhesive layer of substantially 100 nm or more. In addition, because of the nature of graft polymerization, it is difficult to add a polymerizable monomer having two or more polymerizable vinyl groups and introduce crosslinking into the graft chain. There is also a problem that the adhesive layer between the glass substrate and the spacer is brittlely broken due to an impact or the like, the spacer arranged at a predetermined position moves, light is lost, the contrast and color tone are lowered, and the display quality is deteriorated. It was.
Japanese Patent Laid-Open No. 4-198919 JP-A-6-258647 JP-A-10-339878 JP-A-57-58124 Japanese Patent Application Laid-Open No. 07-300587

In view of the above-described situation, the present invention has an adhesive layer with a sufficient thickness on the surface of base material particles, and can be accurately placed at a desired position on the substrate by an inkjet method, and can be vibrated by vibration or impact. Method for producing a liquid crystal display device capable of obtaining a liquid crystal display device that exhibits excellent display quality without causing brittle fracture of the adhesive layer between the spacer and the spacer, without light leakage due to the liquid crystal spacer An object of the present invention is to provide a strongly adherent liquid crystal spacer, a spacer dispersion liquid, and a liquid crystal display device.

The present invention includes a step of preparing a core-shell particle in which a shell layer made of a swellable resin is formed on the surface of a non-swellable substrate particle, and a polymerizable material that is a raw material for an adhesive resin in the shell layer of the core-shell particle. A step of causing the shell layer to swell by absorbing a monomer, and polymerizing the polymerizable monomer absorbed in the shell layer to form an adhesive layer made of an adhesive resin on the surface of the base particle A process for producing a strongly adherent liquid crystal spacer.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have determined that a strongly adherent liquid crystal spacer in which an adhesive layer is formed on the surface of the base particle by a predetermined method has an adhesive layer with a sufficient thickness on the surface of the base particle. Excellent adhesion to the substrate, and can be accurately placed at the desired position on the substrate by the inkjet method, and the adhesive layer between the glass substrate and the spacer does not brittlely break due to vibration or impact, etc. The inventors have found that a liquid crystal display device that exhibits excellent display quality without light leakage due to spacers can be obtained, and the present invention has been completed.

The method for producing a firmly adherent liquid crystal spacer of the present invention includes a step of preparing core-shell particles in which a shell layer made of a swellable resin is formed on the surface of non-swellable substrate particles.
The non-swellable base particles are sandwiched between two substrates when the liquid crystal display device is manufactured using the firmly adherent liquid crystal spacer manufactured according to the present invention, and the interval between the two substrates is regulated. However, it plays a role of maintaining an appropriate cell gap.
In the present specification, “non-swelling” means a property that does not absorb a polymerizable monomer as a raw material of an adhesive resin described later and does not swell by the polymerizable monomer. means.

The material constituting the base particle is not particularly limited as long as it is a non-swelling material, and for example, conventionally known organic and / or inorganic materials can be used.

When the base particles are made of an organic material, the base particles are preferably cross-linked resin particles (hereinafter also referred to as cross-linked resin particles).

Examples of the organic material used as the base particles include olefins such as ethylene, propylene, butylene, isoprene, and methylpentene, and derivatives thereof; styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, and divinylbenzene. Styrene derivatives such as chloromethylstyrene; vinyl halides such as vinyl fluoride and vinyl chloride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl stearate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether Unsaturated nitriles such as (meth) acrylonitrile; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate Glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, cyclohexyl (meth) acrylate, di ( (Meth) acrylic such as polyethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acid ester derivatives; unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and maleic anhydride; polymers using polymerizable monomers such as acrylamides and acrylamides such as N-isopropylacrylamide, polyamides, (unsaturated) Poly Examples thereof include esters, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyether ether ketone, polyether sulfone, epoxy resin, phenol resin, melamine resin, and benzoguanamine resin. The said organic material may be used independently and may use 2 or more types together.

The method for obtaining the crosslinked resin particles is not particularly limited, and examples thereof include conventionally known polymerization methods such as suspension polymerization method, emulsion polymerization method, seed polymerization method, and dispersion polymerization method.

When the said base particle consists of inorganic materials, it does not specifically limit as this inorganic material, For example, a metal, a metal oxide, a silica etc. are mentioned.

In the method for producing a firmly adherent liquid crystal spacer according to the present invention, the substrate particles may be composed of only the organic material or only the inorganic material, and have a composite structure of the organic material and the inorganic material. It may be. Among them, the organic material is that the adherent liquid crystal spacer produced has an appropriate hardness that does not damage the alignment film formed on the substrate of the liquid crystal display device, and can easily follow the thickness change due to thermal expansion and contraction. It is preferable that it consists only of.

The average particle size of the substrate particles is not particularly limited because it varies depending on the liquid crystal display device to be produced, but the preferred lower limit is 0.5 μm. If it is less than 0.5 μm, the cell gap of the liquid crystal display device produced by using the firmly adherent liquid crystal spacer obtained by the present invention becomes too narrow, and it may not be possible to obtain a liquid crystal display device excellent in display quality. . A more preferred lower limit is 1 μm.
The upper limit of the average particle diameter of the substrate particles is not particularly limited, but the preferable upper limit is 20 μm, and the more preferable upper limit is 10 μm.
The average particle size of the substrate particles can be obtained by statistically processing the particle size measured using an optical microscope, an electron microscope, a coulter counter, or the like.

Moreover, it is preferable that the variation coefficient of the average particle diameter of the substrate particles is 10% or less. If it exceeds 10%, it becomes difficult to arbitrarily control the distance between the two substrates facing each other when manufacturing a liquid crystal display device. The coefficient of variation is a numerical value obtained by dividing the standard deviation obtained from the particle size distribution by the average particle size.

In addition, since the base particle is used as a spacer (gap material) that regulates the distance between two substrates, it preferably has a certain strength, and the diameter of the base particle is displaced by 10%. The preferable lower limit of the compression modulus (10% K value) is 2000 MPa, and the preferable upper limit is 15000 MPa. If the pressure is less than 2000 MPa, the substrate particles may be deformed due to the press pressure when assembling the liquid crystal display device, making it difficult to produce an appropriate gap. If the pressure exceeds 15000 MPa, the strong adhesion obtained by the present invention may be obtained. When the conductive liquid crystal spacer is incorporated in the liquid crystal display device, the alignment film on the substrate may be damaged to cause display abnormality.
The above 10% K value is obtained by using a micro-compression tester (for example, “PCT-200” manufactured by Shimadzu Corporation), and using a smooth indenter end face made of a diamond cylinder having a diameter of 50 μm and a compression speed of 2.6 mN / The compression displacement (mm) when the substrate particles are compressed under the condition of second and maximum test load of 10 g can be measured and determined by the following formula.
K value (N / mm ² ) = (3/2 ^1/2 ) · F · S ⁻³ / ² · R ^−1/2
F: Load value (N) at 10% compression deformation of the base particle
S: Compression displacement (mm) in 10% compression deformation of substrate particles
R: radius of base particle (mm)

In order to obtain base particles having a 10% K value satisfying the above conditions, the base particles are preferably made of a resin obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group. It is more preferable to contain at least 20% by weight of a polyfunctional monomer as a constituent component.

The base particles preferably have a lower recovery rate of 20%. If it is less than 20%, the strongly adherent liquid crystal spacers obtained by the present invention may not be restored even if they are deformed, so that the opposing substrates of the liquid crystal display device may not be fixed. A more preferred lower limit is 40%. In addition, the said recovery rate means the recovery rate after applying a 9.8 mN load to base material particle | grains.

Furthermore, the base particles are preferably uniform in size, and specifically, the CV value of the particle diameter of the base particles is preferably 10% or less. If it exceeds 10%, when a liquid crystal display device is produced using the firmly adherent liquid crystal spacer obtained by the present invention, the cell gap may become non-uniform and the quality of the display screen may be deteriorated.

In this step, a shell layer made of a swellable resin is formed on the surface of the non-swellable substrate particles to prepare core-shell particles.
In the present specification, the “swellable resin” means a property of absorbing a polymerizable monomer as a raw material of an adhesive resin described later and swelling with the polymerizable monomer.

The resin that constitutes the shell layer is not particularly limited as long as it can absorb a polymerizable monomer that is a raw material of the adhesive resin described later, and the organic material that constitutes the base particle described above is used. Is possible. The resin constituting the shell is preferably non-crosslinked because it absorbs the polymerizable monomer and easily swells.

The method for forming the shell layer on the surface of the base particle is not particularly limited. For example, (1) a method for depositing the resin constituting the shell layer on the surface of the base particle, (2) the base particle and the shell A method in which the raw material monomer of the layer is dispersed in a medium, and the shell layer is formed on the surface of the substrate particles by dispersion polymerization, emulsion polymerization, suspension polymerization, soap-free precipitation polymerization, or the like. A method of introducing a reactive functional group and graft-reacting a resin having a functional group capable of being chemically bonded to the reactive functional group, and (4) introducing a polymerizable functional group onto the surface of the substrate particle, Examples thereof include a method of graft polymerization of the raw material monomer for the shell layer starting from the group.

As a specific method of the above (1), for example, there is a method in which base particles are dispersed in a polystyrene solution obtained by dissolving polystyrene in ethanol, and polystyrene is precipitated on the surface of the base particles by adding water. Can be mentioned.

As a specific method of the above (2), for example, after dissolving a styrene monomer, a polymerization initiator and polyvinyl pyrrolidone in methanol, the base particles are dispersed, and the styrene monomer is polymerized by heating to form base particles. Examples thereof include a method of forming a shell layer on the surface.

As a specific method of the above (3), for example, an epoxy group is introduced into the surface of the base particle by coexisting glycidyl methacrylate at the time of manufacturing the base particle, and a hydroxyl group and a reactive functional group (for example, Examples thereof include a method of forming a shell layer by reacting a polymer having a hydroxyl group, a carboxyl group, an amino group, etc. (for example, low saponified polyvinyl alcohol) in a solution such as methyl ethyl ketone.

As a specific method of the above (4), for example, after introducing a hydroxyl group on the surface by coexisting polyvinyl alcohol during the production of the base particles, it is dispersed in methyl acrylate and dimethylformamide, and redox initiation such as cerium nitrate is started. A method of adding an agent to form a shell layer of polymethacrylic acid, or reacting 2-methacryloyloxyethyl isocyanate with the base particles having a hydroxyl group to introduce a methacryl group, and then dispersing in toluene or the like, Examples include a method in which methyl methacrylate and a radical initiator (for example, AIBN) are added, and methyl methacrylate is polymerized by heating to form a polymethyl methacrylate shell layer.

Since the thickness of the shell layer is reflected in the thickness of the adhesive layer formed on the surface of the base material particles through the steps described later, the particle diameter of the base material particles, the desired adhesion liquid crystal spacer It is determined appropriately in consideration of the size and the like. Since it becomes difficult to absorb the polymerizable monomer, the preferred lower limit is 10 nm.

The method for producing a firmly adherent liquid crystal spacer according to the present invention includes a step of causing the shell layer of the core-shell particles to absorb a polymerizable monomer that is a raw material for the adhesive resin to swell the shell layer.

In this step, the polymerizable monomer that is absorbed and swollen in the shell layer of the core-shell particles is not particularly limited as long as it is a monomer that can be polymerized by radical polymerization, polycondensation, polyaddition reaction, etc. For example, olefins such as ethylene, propylene, butylene, methylpentene, butadiene, isoprene and derivatives thereof; styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, divinylbenzene, chloromethylstyrene; Vinyl fluoride; vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated nitriles such as acrylonitrile; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, stearyl (meth) acrylate , Ethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, cyclohexyl (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylol Methane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate; glycerol di (meth) acrylate, polyethylene glycol (Meth) acrylate derivatives such as di (meth) acrylate and polypropylene glycol di (meth) acrylate; acrylic Acrylamides such as amide, isopropylacrylamide, propylene diacrylamide; silane-containing monomers such as γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane; dicarboxylic acids such as phthalic acid; diamine Epoxies; diallyl phthalate; benzoguanamine; triallyl (iso) cyanurate, triallyl trimellitate, diallyl ether, diallyl phthalate, benzoguanamine, triallyl isocyanate and the like. The said polymerizable monomer may be used independently and may use 2 or more types together.

In addition, since the adhesive layer to be formed has a cross-linked structure, the adhesive layer existing between the substrate and the base particle is less likely to be brittlely broken due to vibration or impact. It is preferable to use 0.5 to 50% by weight of the polymerizable monomer. If the amount is 0.5% by weight or less, sufficient strength cannot be obtained in the adhesive layer of the strong adherence liquid crystal spacer to be manufactured, and if it exceeds 50% by weight, the adhesive layer of the strong adherence liquid crystal spacer to be produced becomes too stiff. Adhesive strength may be reduced.

In the method for producing a strongly adherent liquid crystal spacer of the present invention, it is preferable that the shell layer of the core-shell particle and the polymerizable monomer absorbed in the shell layer have good compatibility.

The method for causing the shell layer to absorb and swell the polymerizable monomer that is the raw material of the adhesive resin is not particularly limited. For example, (1) the polymerizable monomer that is the raw material of the adhesive resin and the core shell After mixing the particles, a method of adding a solvent incompatible with the polymerizable monomer that is the raw material of the adhesive resin, (2) the polymerizable monomer that is the raw material of the adhesive resin is incompatible For example, a method of adding a polymerizable monomer, which is a raw material for the adhesive resin, after dispersing the core-shell particles in a solvent can be used.

The amount of the polymeric monomer to be added varies depending on the thickness of the adhesive layer of the target adherent liquid crystal spacer, and is not particularly limited. However, the preferred lower limit is 0.1 weight with respect to 1 part by weight of the shell layer. Parts, and the preferred upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the physical properties of the adhesive layer of the obtained firmly adherent liquid crystal spacer are governed by the physical properties of the shell layer, making it difficult to obtain the desired physical properties. When the amount exceeds 100 parts by weight, a polymerizable monomer that is not absorbed is generated, which may cause aggregation or foreign matter.

The method for producing a firmly adherent liquid crystal spacer according to the present invention comprises a step of polymerizing the polymerizable monomer absorbed in the shell layer to form an adhesive layer made of an adhesive resin on the surface of the substrate particles. Have.
The adhesive layer is obtained by sandwiching the base material particles between two substrates and then melting the base material particles when manufacturing a liquid crystal display device using the firmly adherent liquid crystal spacer manufactured according to the present invention. It plays the role of firmly bonding and fixing to two substrates.

The conditions for polymerizing the polymerizable monomer absorbed in the shell layer are not particularly limited, and are appropriately determined depending on the type of the polymerizable monomer absorbed in the shell layer, the thickness of the swollen shell layer, and the like. Selected. For example, when the polymerizable monomer is polymerized only by light or heat, the polymerizable monomer is absorbed by the shell layer and then polymerized by light irradiation or heating. When the polymerizable monomer is polymerized with a radical initiator, the radical initiator is absorbed into the shell layer simultaneously with the polymerizable monomer and polymerized by light irradiation or heating.

Although it does not specifically limit as a softening point of the contact bonding layer formed in the said base material particle surface, A preferable minimum is 40 degreeC and a preferable upper limit is 120 degreeC. When the temperature is lower than 40 ° C., the strongly adherent liquid crystal spacers produced during transportation or the like aggregate or when dispersed in an inkjet ink described later, aggregates are formed when the adherent liquid crystal spacers settle in the dispersion. May occur. When the temperature exceeds 120 ° C., the burden on the substrate increases due to heating when fixing the firmly adherent liquid crystal spacer manufactured according to the present invention between the two substrates.

Although it does not specifically limit as thickness of the contact bonding layer formed in the said base particle surface at this process, A preferable minimum is 50 nm and a preferable upper limit is 50% of the base particle diameter to be used. If the thickness is 50 nm or less, sufficient adhesion to the substrate may not be obtained, and if it exceeds 50% of the base particle diameter, the gap between the substrates may not be properly maintained.

When polymerizing the polymerizable monomer absorbed in the shell layer, it is preferable to use a dispersion stabilizer.
The dispersion stabilizer is not particularly limited, and examples thereof include water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyacrylic acid, polyacrylamide, and polyethylene oxide; nonionic surfactants, anionic properties Surfactants such as surfactants, cationic surfactants, and amphoteric surfactants are included. These dispersion stabilizers may be used alone or in combination of two or more. Of these, water-soluble polymers are preferred.

When a dispersion stabilizer composed of a water-soluble polymer is used together with the polymerizable monomer when forming the adhesive layer by polymerizing the polymerizable monomer, the polymerizable monomer is polymerized. An adhesive layer is formed on the surface of the substrate particles, and a hydrophilic layer is formed on the surface of the adhesive layer by the dispersion stabilizer made of the water-soluble polymer. As described above, when the hydrophilic layer is formed on the surface of the adhesive layer, when the adherent liquid crystal spacer manufactured according to the present invention is dispersed in the dispersion medium to form a spacer dispersion liquid, Can be prevented from attaching.

According to the method for producing a strongly adherent liquid crystal spacer of the present invention having the steps described above, it is possible to suitably produce a strongly adherent liquid crystal spacer having a structure in which an adhesive layer is formed on the surface of the substrate particles. In addition, the thickness of the adhesive layer of the manufactured strong adhesion liquid crystal spacer can be made sufficient.
That is, according to the adherent liquid crystal spacer manufactured by the method for producing an adherent liquid crystal spacer of the present invention, the adhesive layer having a sufficient thickness on the surface of the base material particles, and any desired target on the substrate by the inkjet method Liquid crystal that can be placed in a precise position and does not cause brittle fracture of the adhesive layer between the glass substrate and the spacer due to vibration, impact, etc. A display device can be suitably manufactured.
A firmly adherent liquid crystal spacer produced by the method for producing an adherent liquid crystal spacer of the present invention is also one aspect of the present invention.

Further, the firmly adherent liquid crystal spacer of the present invention can be dispersed in a dispersion medium so that the adhesive layer can be dispersed and disposed at any desired position on the substrate using an ink jet apparatus or the like without causing the adhesive layer to peel off. it can.
A spacer dispersion liquid comprising such a strongly adherent liquid crystal spacer of the present invention and a dispersion medium in which the adherent liquid crystal spacer is dispersed is also one aspect of the present invention.

The dispersion medium constituting the spacer dispersion liquid of the present invention is not particularly limited as long as the firmly adherent liquid crystal spacer of the present invention is dispersed in a medium in which spacer particles can be dispersed, but water and / or It is preferable to consist of a hydrophilic organic solvent.

In general, inkjet devices tend to be able to eject stably when the dispersion medium is water or a hydrophilic organic solvent. When the dispersion medium is a highly hydrophobic organic solvent, the member constituting the head is the dispersion medium. Or a part of the adhesive that adheres the member is dissolved in the dispersion medium. Therefore, when the arrangement of the firmly adherent liquid crystal spacer of the present invention is performed using an ink jet apparatus, the dispersion medium of the spacer dispersion liquid is preferably water or a hydrophilic organic solvent.

In addition, the spacer discharged from the nozzle of the ink jet apparatus is preferably a dispersion medium in which the spacer dispersion liquid is deposited on the substrate and then gathered on the substrate as it is inside the landing diameter. In order to gather the spacers near the center of the landing droplet in the drying process in this way, the boiling point of the medium, the drying temperature, the drying time, the surface tension of the medium, the contact angle of the medium with respect to the alignment film, the concentration of the spacer, etc. are appropriate. It is important to set the correct conditions.

It does not specifically limit as said water, For example, ion-exchange water, pure water, ground water, tap water, industrial water etc. are mentioned. These may be used alone or in combination of two or more.

The hydrophilic organic solvent is not particularly limited, and examples thereof include ethanol, n-propanol, 2-propanol, 1-butanol, 2-butanol, 1-methoxy-2-propanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol. Monoalcohols; ethylene glycol multimers such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol; propylene glycol multimers such as propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol; ethylene glycol multimers And lower polymers such as monomethyl ether, monoethyl ether, monoisopropyl ether, monopropyl ether, monobutyl ether Alkyl ethers; ethylene glycol multimers and propylene glycol multimers dimethyl ether, diethyl ether, diisopropyl ether, dipropyl ether and other lower dialkyl ethers; ethylene glycol multimers and propylene glycol multimers monoacetate, di Alkyl esters such as acetate; 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 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, etc. Diols; ethers of diols Conductor; acetate derivatives of diols; glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,5-pentanetriol, trimethylolpropane, trimethylolethane, pentaerythritol, etc. Polyhydric alcohols; ether derivatives of polyhydric alcohols; acetate derivatives of polyhydric alcohols, 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 Chromatography, bis -β- hydroxyethyl sulfone, bis -β- hydroxyethyl urea, N, N-diethylethanolamine, Abiechinoru, diacetone alcohol, urea, and the like. These hydrophilic organic solvents may be used independently and 2 or more types may be used together.
The water and the hydrophilic organic solvent may be used alone or in combination.

In the spacer dispersion liquid of the present invention, when the liquid crystal spacer of the present invention is arranged using an inkjet apparatus, the dispersion medium composed of water and / or a hydrophilic organic solvent has a lower surface tension at 20 ° C. It is preferably 25 mN / m and the upper limit is 45 mN / m. When the surface tension of the dispersion medium at 20 ° C. deviates from the above range, the dischargeability and discharge accuracy of the resulting spacer dispersion liquid may be insufficient.

The dispersion medium used in the present invention preferably contains a hydrophilic organic solvent having a boiling point of less than 100 ° C., more preferably a hydrophilic organic solvent having a boiling point of 70 ° C. or more and less than 100 ° C. That is. In addition, in this specification, a boiling point means the boiling point on 1 atmosphere conditions.

The hydrophilic organic solvent having a boiling point of less than 100 ° C. is not particularly limited, and examples thereof include lower monoalcohols such as ethanol, n-propanol, and 2-propanol, acetone, and the like. These may be used alone or in combination of two or more.

The hydrophilic organic solvent having a boiling point of less than 100 ° C. volatilizes at a relatively low temperature when the spacer dispersion liquid of the present invention is discharged onto the substrate and then dried. In particular, in the spacer dispersion liquid of the present invention, when the dispersion medium contacts the alignment film at a high temperature, the alignment film is contaminated and the display quality of the liquid crystal display device is impaired. Therefore, the drying temperature cannot be increased too much. Therefore, it is preferable to use a hydrophilic organic solvent having a boiling point of less than 100 ° C. However, if the hydrophilic organic solvent having a boiling point of less than 100 ° C. is likely to be volatilized at room temperature, aggregated particles are likely to be generated during the production or storage of the spacer dispersion liquid of the present invention, or the present invention near the nozzle of the inkjet device. Since the spacer dispersion liquid is easily dried and the ink jet discharge property is impaired, a hydrophilic organic solvent that easily volatilizes at room temperature is not preferable.

The hydrophilic organic solvent having a boiling point of less than 100 ° C. is not particularly limited, but the upper limit of the surface tension at 20 ° C. is preferably 25 mN / m.
In general, an ink jet apparatus exhibits good ejection accuracy when the surface tension of a spacer dispersion liquid to be ejected is 20 to 50 mN / m at 20 ° C. On the other hand, the higher the surface tension of the spacer dispersion liquid droplets discharged onto the substrate, the more suitable for moving the adherent liquid crystal spacer of the present invention during the drying process.
When the surface tension at 20 ° C. of the hydrophilic organic solvent having a boiling point of less than 100 ° C. is 25 mN / m or less, the surface tension of the spacer dispersion liquid of the present invention is relatively low at the time of discharge. It becomes possible to obtain accuracy, and after being ejected onto the substrate, it volatilizes prior to other medium components in the spacer dispersion liquid of the present invention, and the surface tension of the spacer dispersion liquid of the present invention becomes high, The movement of the firmly adherent liquid crystal spacer of the present invention during the drying process is facilitated.

The content of the hydrophilic organic solvent having a boiling point of less than 100 ° C. in the dispersion medium used in the present invention is such that the lower limit of the surface tension of the dispersion medium at 20 ° C. is 25 mN / m and the upper limit is not deviated from the range of 45 mN / m. If it is, it will not specifically limit, However, A preferable minimum is 10 weight% and a preferable upper limit is 80 weight%. When the amount is less than 10% by weight, the above effect due to the inclusion of a hydrophilic organic solvent having a boiling point of less than 100 ° C. may not be sufficiently obtained. When the amount exceeds 80% by weight, the spacer dispersion of the present invention is produced. In some cases, it becomes easy to dry at the time of storage or storage, and aggregated particles are generated, or the spacer dispersion liquid of the present invention near the nozzle of the ink jet apparatus is excessively dried, thereby impairing the discharge property and the discharge accuracy.

Further, the dispersion medium used in the present invention preferably contains a hydrophilic organic solvent having a boiling point of 150 ° C. or higher, more preferably a hydrophilic organic solvent having a boiling point of 150 to 200 ° C. That is.

The hydrophilic organic solvent having a boiling point of 150 ° C. or higher is not particularly limited, and examples thereof include lower alcohols such as ethylene glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,2-butanediol, and glycerin, ethers, and the like. . This may be used alone or in combination of two or more.

The hydrophilic organic solvent having a boiling point of 150 ° C. or higher suppresses the generation of aggregated particles by drying during production or storage of the spacer dispersion of the present invention, or the liquid crystal spacer of the present invention using an inkjet device. When arranging, it can suppress that the spacer dispersion liquid of this invention dries excessively in the vicinity of a nozzle, and discharge property and discharge accuracy are impaired.

The hydrophilic organic solvent having a boiling point of 150 ° C. or higher is not particularly limited, but the lower limit of the surface tension at 20 ° C. is preferably 30 mN / m. When the lower limit of the surface tension at 20 ° C. of the hydrophilic organic solvent having a boiling point of 150 ° C. or higher was 30 mN / m, the hydrophilic organic solvent having a lower boiling point was volatilized from the spacer dispersion liquid of the present invention discharged onto the substrate. Later, since the surface tension of the spacer dispersion of the present invention is kept high, it is easy to move the liquid crystal spacer of the present invention during the drying process.

The content of the hydrophilic organic solvent having a boiling point of 150 ° C. or higher in the dispersion medium used in the present invention is such that the lower limit of the surface tension of the dispersion medium at 20 ° C. is 25 mN / m and the upper limit is not deviated from the range of 45 mN / m. If it is, it will not specifically limit, However, A preferable minimum is 10 weight% and a preferable upper limit is 80 weight%. When the amount is less than 10% by weight, the above effect due to the inclusion of a hydrophilic organic solvent having a boiling point of 150 ° C. or higher may not be sufficiently obtained. When the amount exceeds 80% by weight, the spacer dispersion of the present invention is dried In some cases, the time is remarkably increased, the productivity is lowered, and the alignment film is contaminated to deteriorate the display quality of the liquid crystal display device.

Although it does not specifically limit as solid content concentration of the firm adhesion liquid crystal spacer of this invention in the spacer dispersion liquid of this invention, A preferable minimum is 0.01 weight% and a preferable upper limit is 20 weight%. When the amount is less than 0.01% by weight, an effective amount of the strongly adherent liquid crystal spacer may not be contained in the discharged droplets of the spacer dispersion liquid of the present invention. When the liquid crystal spacer of the present invention is used to arrange the nozzle, the nozzle of the ink jet device is likely to be clogged, or the content of the liquid crystal spacer of the liquid dispersion of the discharged spacer dispersion liquid of the present invention is high. If it becomes excessive, it may be difficult to move the liquid crystal spacer of the present invention during the drying process. A more preferred lower limit is 0.1% by weight, and a more preferred upper limit is 10% by weight.

In the spacer dispersion liquid of the present invention, it is preferable that the adherent liquid crystal spacer of the present invention is dispersed in a single particle form in the dispersion medium. When the strongly adherent liquid crystal spacer of the present invention is not dispersed in a single particle form in a dispersion medium and is in an aggregated state, when the strongly adherent liquid crystal spacer of the present invention is arranged using an inkjet device, In some cases, the discharge accuracy may decrease, or the nozzles of the ink jet apparatus may be blocked.

In addition, the spacer dispersion of the present invention can be applied, for example, to an adhesiveness imparting agent, a viscosity adjusting agent, a pH adjusting agent, a surfactant, or an antifoaming agent as long as the object of the present invention is not impaired One type or two or more types of various additives such as antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, and colorants may be added.

The method for discharging the above-described spacer dispersion liquid of the present invention to a desired arbitrary position on the substrate is appropriately determined depending on the ink jet apparatus to be used.
When the liquid crystal spacer of the present invention is arranged using an ink jet device, the ink jet device is not particularly limited. For example, a piezo method in which liquid is ejected from a nozzle by vibration of a piezo element, liquid by rapid heating A thermal method in which liquid is ejected from the nozzle using the expansion of the nozzle, a bubble jet (registered trademark) method in which liquid is ejected from the nozzle by rapid heating of the heat generating element, and the like may be used.

Although it does not specifically limit as a nozzle diameter of the said inkjet apparatus, A preferable minimum is 20 micrometers and a preferable upper limit is 100 micrometers. When it is less than 20 μm, when the adherent liquid crystal spacer of the present invention having a particle diameter of 2 to 10 μm is discharged, the difference from the particle diameter is too small and the discharge accuracy is lowered or the nozzle is clogged and cannot be discharged. It may become. If it exceeds 100 μm, the diameter of the ejected liquid droplets becomes large and the diameter of the liquid droplets ejected on the substrate also increases, so that the placement accuracy of the firmly adherent liquid crystal spacer of the present invention may be rough.

The diameter of the droplets ejected from the nozzle is not particularly limited, but a preferred lower limit is 10 μm and a preferred upper limit is 80 μm.
The method for controlling the diameter of the droplets ejected from the nozzle within the above preferable range is not particularly limited, and examples thereof include a method for optimizing the nozzle diameter and a method for optimizing the electric signal for controlling the ink jet apparatus. Any method may be adopted. In particular, when using a piezo ink jet apparatus, the latter method is preferably employed.

Further, the diameter of the droplets ejected on the substrate is not particularly limited, but a preferable lower limit is 30 μm and a preferable upper limit is 150 μm. In order to make it less than 30 μm, it is necessary to make the nozzle diameter very small, and there is a possibility that the possibility of nozzle clogging by the firmly adherent liquid crystal spacer of the present invention is increased, or the accuracy of nozzle processing must be improved. is there. If it exceeds 150 μm, the placement accuracy of the firmly adherent liquid crystal spacer of the present invention may become rough.

The substrate to which the spacer dispersion liquid of the present invention is discharged is not particularly limited, and examples thereof include those generally used as a panel substrate of a liquid crystal display device such as a glass plate and a resin plate.

By using such a spacer dispersion liquid of the present invention, it is possible to dispose the strongly adherent liquid crystal spacer of the present invention at any desired position, and to accurately control the cell gap of the liquid crystal display device to be manufactured. In addition, the liquid crystal display according to the present invention can be firmly fixed to the above-mentioned substrate, there is no light leakage due to the liquid crystal spacer of the present invention, and the liquid crystal display exhibits excellent display quality. A device can be obtained.
A liquid crystal display device using such a spacer dispersion of the present invention is also one aspect of the present invention.

The method for producing a firmly adherent liquid crystal spacer according to the present invention includes a step of preparing core-shell particles in which a shell layer made of a swellable resin is formed on the surface of non-swellable substrate particles, and a shell layer of the core-shell particles, A step of swelling the shell layer by absorbing a polymerizable monomer as a raw material of the adhesive resin; and polymerizing the polymerizable monomer absorbed in the shell layer to form a surface on the surface of the substrate particle The adhesive layer of the adhesive liquid crystal spacer to be manufactured has a sufficient thickness and has excellent adhesion to the surface of the substrate particles. It can be.
Therefore, according to the present invention, the adhesive layer having a sufficient thickness on the surface of the substrate particles can be accurately placed at a desired position on the substrate by the ink jet method, and the glass substrate and the spacer can be arranged by vibration or impact. Since the adhesive layer between the layers does not brittlely break, there is no light leakage caused by the strong adhesive liquid crystal spacer, and a method for manufacturing a strong adhesive liquid crystal spacer that can provide a liquid crystal display device that exhibits excellent display quality, An adhesive liquid crystal spacer, a spacer dispersion liquid, and a liquid crystal display device can be suitably 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.

Example 1
(1) Preparation of substrate particles 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 mixed with stirring uniformly. did.
Next, 20 parts by weight of a 3% by weight aqueous solution of polyvinyl alcohol (GOHSENOL GL-03, manufactured by Nippon Synthetic Chemical Co., Ltd.) and 0.5 parts by weight of sodium dodecyl sulfate were added and stirred and mixed uniformly. Department was put in.
Next, a polymerization reaction was carried out at 80 ° C. for 15 hours while stirring the aqueous solution under a nitrogen gas stream to obtain fine particles. After the obtained fine particles were sufficiently washed with hot water and acetone, classification operation was carried out to volatilize acetone to produce base particles. The average particle diameter of the obtained base material particles was 5 μm, and the CV value was 3.0%.

(2) Formation of core-shell particles 50 parts by weight of the obtained base particles were put into a mixed monomer composed of 200 parts by weight of N, N-dimethylformamide, 120 parts by weight of isobutyl methacrylate and 80 parts by weight of methyl methacrylate, and a sonicator. Then, the mixture was stirred and mixed uniformly.
Next, the reaction system was replaced with nitrogen gas, and stirring was continued at 30 ° C. for 2 hours.
Next, 10 parts by weight of 0.1 mol / L ceric ammonium nitrate aqueous solution prepared with 1N nitric acid aqueous solution was added to the reaction system, and after 5 hours of polymerization reaction, the reaction solution was taken out and a 3 μm membrane filter was attached. The particles and the reaction solution were separated by filtration. The obtained particles were sufficiently washed with THF and methanol to obtain core-shell particles (1). The average particle diameter of the obtained core-shell particles (1) was 5.06 μm (CV value is 3.0%), and a shell layer having a thickness of 0.03 μm was formed on the surface of the base particles.

(3) Formation of adhesive layer In a separable flask, 200 parts by weight of ion-exchanged water, 40 parts by weight of a 5% aqueous solution of polyvinyl alcohol (GOHSENOL GL-03, manufactured by Nippon Synthetic Chemical), and 50 parts by weight of core-shell particles (1) are weighed. And stirred at 200 rpm to obtain a core-shell particle dispersion (1).
Separately, 160 parts by weight of ion exchange water, 5 parts by weight of methyl methacrylate, 5 parts by weight of 2-ethylhexyl methacrylate, 0.5 parts by weight of ethylene glycol dimethacrylate, 1.5 parts by weight of benzoyl peroxide, and sodium dodecyl sulfonate 1.2 parts by weight were uniformly emulsified with a homogenizer to obtain a polymerizable monomer emulsion.
The obtained polymerizable monomer emulsion is added to the obtained core-shell particle dispersion (1), stirred at 100 rpm, and the polymerizable monomer is absorbed into the graft layer under a nitrogen stream at room temperature for 24 hours. Polymerizable droplets were obtained.
Next, after the stirring speed was set to 200 rpm, 50 parts by weight of 5% polyvinyl alcohol (GOHSENOL GH-20, manufactured by Nippon Synthetic Chemical) was added and heated to 90 ° C. to polymerize the polymerizable droplets and adhere. A strongly adherent liquid crystal spacer (1) having a layer was obtained.
The obtained firmly adherent liquid crystal spacer (1) had an average particle diameter of 5.2 μm (CV value is 3.0%), and the thickness of the adhesive layer was 0.1 μm. In addition, in the process of manufacturing the strong adhesion liquid crystal spacer (1), the coalescence of the base material particles did not occur.

(4) Preparation of spacer dispersion liquid 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 medium. The resulting dispersion medium had a surface tension at 20 ° C. of 35 mN / m.
0.5 parts by weight of the firmly adhered liquid crystal spacer (1) produced was slowly added to 100 parts by weight of the dispersion medium, and the mixture was uniformly stirred and mixed with a sonicator to prepare a spacer dispersion liquid (1).

(Example 2)
In the step of forming the adhesive layer, Example 1 and Example 1 were prepared except that a polymerizable monomer emulsion was prepared using 15 parts by weight of methyl methacrylate, 15 parts by weight of 2-ethylhexyl methacrylate, and 4 parts by weight of ethylene glycol dimethacrylate. In the same manner, a strongly adherent liquid crystal spacer (2) and a spacer dispersion liquid (2) were prepared. The average particle size of the firmly adherent liquid crystal spacer (2) was 5.6 μm (CV value was 3.5%), and the thickness of the adhesive layer was 300 nm.

(Comparative Example 1)
In a separable flask, 1000 parts by weight of methyl ethyl ketone, 150 parts by weight of methacryloyl isocyanate, and 50 parts by weight of substrate particles prepared in the same manner as in Example 1 are weighed, mixed and stirred uniformly, and reacted at room temperature for 30 minutes. As a result, particles having a polymerizable vinyl group on the surface were obtained.
Next, after washing with methyl ethyl ketone, 500 parts by weight of methyl ethyl ketone, 50 parts by weight of methyl methacrylate, 50 parts by weight of 2-ethylhexyl methacrylate, 10 parts by weight of hydroxyethyl methacrylate, and 5 parts by weight of benzoyl peroxide were added. A graft polymerization reaction was carried out at 4 ° C. for 4 hours to obtain a liquid crystal spacer (3) having an adhesive layer.
The average particle diameter of the obtained liquid crystal spacer (3) having an adhesive layer was 5.16 μm (CV value is 3.0%), and the thickness of the adhesive layer was 0.08 μm.
Thereafter, a spacer dispersion liquid (3) was prepared in the same manner as in Example 1.

(Manufacture of liquid crystal display devices)
A spacer dispersion liquid prepared using an ink jet apparatus was discharged onto a substrate, and an adherent liquid crystal spacer was arranged.
A predetermined TFT array substrate was placed on a stage heated to 45 ° C. with an attached heater.
The prepared spacer dispersion liquid is filtered through a stainless mesh (mesh opening 10 μm) to remove aggregates, and then the color filter substrate of the TFT array substrate is mounted on an inkjet apparatus in which a nozzle with a diameter of 50 μm is mounted on the tip of a piezo head. Aiming at the position corresponding to the black matrix, every other vertical line, droplets of spacer dispersion liquid are ejected on the vertical lines at intervals of 110 μm, and the liquid crystal spacers are firmly attached at a pitch of 110 μm × 150 μm Arranged. The distance between the nozzle (head surface) and the substrate during ejection was 0.5 mm, and a double pulse method was used. The dispersion density of the firmly adhered liquid crystal spacers thus arranged was 180 pieces / mm ² .
After confirming that the spacer dispersion liquid discharged onto the substrate on the stage was completely dried by visual observation, the remaining dispersion medium was further removed, and the adherent liquid crystal spacer was fixed to the substrate at 150 ° C. It was transferred to a heated hot plate, heated and left for 15 minutes.

The peripheral part of the TFT array substrate on which the liquid crystal spacer is disposed and the color filter glass substrate are bonded together via a sealant, and the sealant is cured by heating at 150 ° C. for 1 hour to firmly adhere the cell gap. An empty cell having a particle size of the base particle of the conductive liquid crystal spacer was prepared, and then the liquid cell (trade name “ZLI-4720-000”, manufactured by Merck & Co., Inc.) was filled into the empty cell by a vacuum method. The injection port was sealed with a liquid crystal display device.

(Evaluation)
(Fixability)
Measures the number of liquid crystal spacers in the range of 1.0 mm ² before and after applying air with an air gun to the TFT array substrate on which the liquid crystal spacers were spread and heat-treated before being bonded to the color filter glass substrate. The ratio of the number of remaining particles was calculated and obtained as a percentage. The air blowing conditions used here were air blowing pressure of 5.0 and 15.0 kgf / cm ² , nozzle diameter of 2 mm, vertical distance of 5 mm, and time of 15 seconds. The results are shown in Table 1.

(Display quality)
A predetermined voltage was applied to the liquid crystal display device, and the presence or absence of display defects such as light leakage caused by the firmly adherent liquid crystal spacer was observed with an electron microscope, and the display image quality was evaluated according to the following criteria.
◯: Almost no adherent liquid crystal spacers were observed in the display area, and there was no light leakage due to the adherent liquid crystal spacers, and the image quality was good.
Δ: Some strongly adherent liquid crystal spacers were observed in the display area, and light leakage due to the adherent liquid crystal spacers was observed.
X: Many strongly adherent liquid crystal spacers were recognized in the display area, and light leakage due to the adherent liquid crystal spacers was observed.

According to the present invention, the surface of the base material particle has a sufficiently cross-linked adhesive layer, and can be accurately placed at a desired position on the substrate by an inkjet method, and can be vibrated or shocked. An adhesive layer between the spacer and the spacer is not brittlely broken, and there is no light leakage caused by the strong adhesive liquid crystal spacer, and a liquid crystal display device that exhibits excellent display quality can be obtained. It is possible to provide a manufacturing method, a firmly adherent liquid crystal spacer, a spacer dispersion liquid, and a liquid crystal display device.

It is sectional drawing which shows an example of a liquid crystal display device typically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Polarizing plate 3 Transparent electrode 4 Color filter 5 Black matrix 6 Liquid crystal 7 Spacer 8 Alignment film 9 Sealing material

Claims (6)

A step of preparing a core-shell particle in which a shell layer made of a swellable resin is formed on the surface of a non-swellable substrate particle; and a polymerizable monomer as a raw material for the adhesive resin on the shell layer of the core-shell particle A step of swelling the shell layer by absorbing, and a step of polymerizing the polymerizable monomer absorbed in the shell layer to form an adhesive layer made of an adhesive resin on the surface of the base particle. A method for producing a firmly adherent liquid crystal spacer, comprising: The method for producing a firmly adherent liquid crystal spacer according to claim 1, wherein the softening point of the adhesive layer is in the range of 40 to 120 ° C. A strongly adherent liquid crystal spacer produced by the method for producing an adherent liquid crystal spacer according to claim 1. A spacer dispersion liquid comprising: the adherent liquid crystal spacer according to claim 3; and a dispersion medium in which the adherent liquid crystal spacer is dispersed. 5. The dispersion medium has a surface tension of 25 to 45 mN / m at 20 [deg.] C., and the firmly adherent liquid crystal spacer according to claim 3 is dispersed in a single particle form in the dispersion medium. The spacer dispersion described. 6. A liquid crystal display device comprising the spacer dispersion liquid according to claim 4 disposed at an arbitrary position on a substrate by an ink jet method.

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