JPH01247155A - Double-layer structural fine substance - Google Patents

Abstract

PURPOSE:To obtain a double-layer structural fine substance capable of being bonded and fixed to a substrate in a state capable of obtaining desired adhesiveness, by forming a titanium oxide layer to the surface of each of solid particles and providing a hot melt type adhesive resin layer to said surface. CONSTITUTION:In a pref. method for coating the surfaces of solid particles with an organotitanate compound, said organotitanate compound is dissolved in a solvent such as n-hexane, cyclohexane or benzene and said solid particles are immersed in the resulting solution and the solvent is evaporated under sufficient mixing. The organotitanate compound thus formed to the surfaces of the solid particles is reacted with moisture in air and hydrolyzed to form a titanium oxide layer. In coating the surface of the obtained titanium oxide layer with a hot melt type adhesive resin, the hot melt type adhesive is dissolved in a solvent and the resulting solution is applied to the surfaces of the solid particles each having the titanium oxide layer formed thereto and the solvent is evaporated. After coating, it is pref. to post-crosslink the resin by the irradiation with radioactive rays or heating.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a multi-layer structure fine material in which a pot-melt adhesive resin layer is provided on the surface of solid particles, and more specifically, to a gap for liquid crystal display cells. materials, gap materials for electromink display cells, conductive or insulating spacers for electrode plates, or spacers for maintaining gaps between films, sheets, and blocks for uses other than those listed above, flat or concave surfaces for optical and other uses. The present invention relates to a multilayer structure fine material used for forming fine protrusions thereon.

(Prior Art) A case where a multilayer structure fine material is used as a gap material for a liquid crystal display cell will be described.

Generally, in liquid crystal display devices, it is necessary to maintain a constant gap between two transparent glass substrates or plastic substrates, so a gap material for liquid crystal display cells with a nearly constant diameter is placed between the two substrates at an appropriate distance. It is placed after.

As conventional gap materials, resin microspheres made of linear polymers without a crosslinked structure, resin microspheres with a crosslinked structure, glass microspheres, or short glass fibers have been proposed. However, since these were not fixed to the substrate, the following problems occurred.

(2) In the process of assembling a liquid crystal display cell, when air is blown or sucked onto the substrate, the gap material once placed on the substrate scatters and disappears.

■During the process of injecting liquid crystal into the same cell as above, the gap material moves, causing uneven placement of the gap material.

■The gap material moves due to electrical and hydrodynamic forces while driving the liquid crystal display cell.

Therefore, the gear knob material disposed between the liquid crystal display cells is required to be fixed to the substrate.

Conventionally, when resin microspheres made of linear polymers that do not have the above-mentioned crosslinked structure are used as gap materials, they melt when heated on a substrate and are unable to maintain their shape. , cannot be heated. It is also conceivable to coat the surface of solid particles such as resin microspheres, glass microspheres, or short glass fibers that have a crosslinked structure that does not easily melt by heating with a resin that has adhesive properties to the substrate.

(Problems to be Solved by the Invention) However, when solid particles are coated with an adhesive resin as described above, there is a drawback that the adhesive resin easily peels off from the surface of the solid particles. In addition, because the wettability between the surface of the solid particles and the adhesive resin is poor, it is necessary to coat a relatively large amount of the adhesive resin. There is also the drawback that the gap materials aggregate together. This tendency is particularly remarkable when a polyolefin resin is used as the adhesive resin.

The present invention solves the above-mentioned drawbacks, and its purpose is to:
For example, an object of the present invention is to provide a multilayer structure fine material that can be adhesively fixed to a substrate while providing desired adhesion to the substrate when used as a gap material for a liquid crystal display cell. Another object of the present invention is to provide a multilayer structure fine material in which the adhesive resin does not peel off from the surface of solid particles and does not aggregate.

(Means for Solving the Problems) In the multilayer structure fine particles of the present invention, a titanium oxide layer obtained by treating an organic titanate compound is formed on the surface of a solid particle, and the surface of the titanium oxide layer is It is characterized by being provided with a hot-melt adhesive resin layer, thereby achieving the above object.

As for the material and shape of the solid particles according to the present invention, those shown below can be used.

[Material]

polyethylene, polypropylene, polymethylpentene,
Linear or crosslinked polymers such as polyvinyl chloride, polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polysulfone, polyphenylene oxide, polyacetal; epoxy resin, phenolic resin, melamine Network structure of resin, unsaturated polyester resin, divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylic acid ester copolymer, diacryl phthalate polymer, triallyl isocyanurate polymer, benzoguanamine polymer, etc. resin with

Among the solid particles mentioned above, particularly preferred are resins having a network structure such as divinylbenzene copolymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylic acid ester copolymer, and diacryl phthalate polymer. be.

Inorganic materials include silicate glass, borosilicate glass,
Lead glass, soda lime glass, alumina, alumina silicate, etc. can be used. Among these, particularly preferred are silicate glass and borosilicate glass.

(Shape) Although the shape of the solid particles is not limited, for example,
A true spherical shape, an elliptical spherical shape, and a cylindrical shape having the following dimensions can be used.

In the case of true spherical solid particles, the diameter is between 0.1 μm and 1 μm.
000 μm, and a particularly preferred range is 1 μm to 100 μm.

In the case of elliptic spherical solid particles, the short axis is preferably in the range of 0.1 μm to 1000 μm, particularly preferably in the range of 1 μm to 100 μm. The ratio of major axis to minor axis is preferably in the range of 1 to 10, with a particularly preferred range of 1 to 5.

For cylindrical solid particles, the diameter is between 0.5 μm and 1 μm.
000 μm, and a particularly preferred range is 3 μm to 1008 m. The length to diameter ratio of the cylinder may range from 1 to 50, with a particularly preferred range from 1 to 1O.

[Method for Forming a Titanium Oxide Layer] A method for forming a titanium oxide layer on the surface of the solid particles as described above can be performed, for example, by the following method. After applying the organic titanate compound to the solid particle surface,
The organic chicknate compound is hydrolyzed to form a titanium oxide layer.

Here, as the organic titanate compound used, for example, tetraethoxytitanium Ti (OC2115)
a. Tetrapropoxy titanium TI (OC311?)
a, Tetrabutoxytitanium Ti (OC4119) a
, tetrapentoxytitanium Ti (OCsH+t)4, tetrahexoxytitanium Ti (OCJl+s)n, tetrakis(2-ethylhexoxy)titanium Ti [0CII
□CH(CzHs)CJ*] 4, Tetradodecyl alkoxy titanium Ti (OC+zHzs) 4, Tetrastearoxytitanium Ti (OC+Jas) 4, Dipropoxy
Bis(acetylacetonato)titanium (QC: +II
+)z [0C(C11i)CIICOCII:+]
t, dibutoxy bis(triethanolaminato) titanium Ti (OCnllJg [0CJJ(CJ40H)r
l t, dihydroxy bis(lactato)titanium Ti (
OH)z [0CR(Clh)COOH] z, titanium proboxyoctylene glycolate Ti [0C
11□CH(CtHs)CH(C311t)01134
Among the above, particularly preferred are tetrapropoxy titanium, tetrabutoxy titanium, tetrakis(2-ethylhexoxy) titanium, dipropoxy titanium, etc.
Bis(acetylacenato) titanium, dibutoxy bis(
triethanolaminato) titanium.

As a method for applying the above organic titanate compound to the surface of solid particles, the organic titanate compound is dissolved in i81FI of n-hexane, cyclohexane, benzene, toluene, trichlene, or freon-111, and the solid particles are dissolved in the solvent. A preferred method is to immerse the material in the material and evaporate the solvent while thoroughly mixing the material. After evaporating the solvent,
Although heating at 60°C to 100"C is preferable, this heating step may be omitted.

It is thought that the organic titanate compound formed on the surface of the solid particles through the above steps reacts with moisture in the air and is hydrolyzed to form, for example, a titanium oxide layer having the structure shown below. It will be done.

[About the amount of titanium oxide layer] The amount of the titanium oxide layer formed in the form of a thin film on the surface of the solid particle is the surface area In? of the solid particle in terms of titanium equivalent weight. It is preferable to set the amount in the range of 0.01 mg to 500 mg. A more preferable amount of titanium oxide layer is 0
．． 1mg to 1100rn. The amount of the titanium oxide layer is the titanium equivalent weight, and the surface area of the solid particles In? If the amount is less than 0.01 mg, adhesion between the solid particles and the hot-melt olefin resin will not be developed. On the other hand, if the amount of the titanium oxide layer is more than 100 mg per 1 rrf of surface area of the solid particles in terms of titanium weight, unfavorable results such as a decrease in electrical resistance will occur.

[Hot melt adhesive resin]

Solid particles having a titanium oxide layer formed on their surfaces are coated with a hot-melt adhesive resin shown below. Examples of the hot melt adhesive resin used in the present invention are shown below.

(1) Olefin adhesive resin polyethylene wax, polyethylene wax oxide, low density polyethylene, high density polyethylene, polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-
Carboxyl group-containing ethylene-vinyl acetate copolymers such as vinyl acetate-carbon oxide three-dimensional copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, and ethylene-vinyl acetate-acrylic acid three-dimensional copolymers. Coalescence, ethylene-vinyl acetate-vinyl alcohol three-dimensional copolymer, ethylene-oxide ion copolymer, sulfonated polyethylene, ethylene-propyne copolymer, polypropylene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated polybutadiene-styrene Block copolymers, hydrogenated polyisoprene-styrene block copolymers, and oxides thereof.

(2) Other adhesive resins polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polybutadiene, polyisoprene, polyamide, polyurethane, polyester, polyimide, acetalized polyvinyl alcohol, butyralized polyvinyl alcohol, butadiene-styrene random copolymer , butadiene-styrene block copolymer,
Isoprene-styrene block copolymers, etc.

Among the resins shown in (1) and (2) above, a preferable adhesive resin is the polyolefin shown in (1), and particularly preferable adhesive resins are polyethylene wax, its oxide, and ethylene-vinyl acetate. These are a polymer, its oxide, and a carboxyl group-containing ethylene vinyl acetate copolymer. These resins have relatively low melting points or softening temperatures, and therefore easily melt or soften at relatively low temperatures. Therefore, when the produced multilayer structure fine material is used as a gap material for a liquid crystal display cell, for example, desired adhesion to the substrate can be easily obtained. In addition, although the above resins have inferior adhesive properties compared to resins such as polyamide, they have low polarity, so when the multilayer structure fine particles are used as a gap material for liquid crystal display cells, they have the advantage of not interfering with the alignment of liquid crystals. have

The hot-melt adhesive resin must be softened or melted by heating at a temperature lower than the softening temperature or decomposition temperature of the solid particles. Desired softening or melting temperature range of adhesive resin is 85°C
to 200°C, with a particularly preferred temperature range of 90°C to 200°C.
°C to 170°C.

[Method for coating with hot melt adhesive resin] By dissolving the above hot melt adhesive resin in a solvent, applying the solution to the surface of the solid particles, and then evaporating the solvent,
This can be carried out by coating the surfaces of solid particles with a hot-melt adhesive resin. Note that, after coating the surface of the solid particles with the hot-melt adhesive resin, it is preferable to post-crosslink the resin by means such as radiation irradiation or heating, but this step may be omitted.

[Aspects of hot-melt adhesive resin layer] The thickness of the hot-melt adhesive resin layer formed on the surface of the solid particles is 0.
．． The thickness is preferably in the range of 0.01 μm to 100 pm.

(Example) Examples of the present invention will be described in detail below.

Average particle size of Senzen Kando divinylbenzene polymer: 10.10μ
0.15 g of tetrapropoxy titanium (manufactured by Nippon Soda ■, product side A-1) is 15 Ilj! A solution of the above in n-hexane was added and mixed well with a spatula, and then the n-hexane was evaporated. Next, this material was thoroughly ground in a mortar to eliminate any lumps.

On the other hand, as a hot-melt adhesive resin, polyethylene wax (manufactured by Sanyo Chemical Industries, trade name: Sunwax 15) is used.
1-P) 2.6g was added to 10cc of toluene, and 80
The resin microspheres treated with the above-mentioned organic titanate compound were added to this solution and dispersed until it became completely milky, and then heated at 90°C and 1300mmHg.
The mixture was dried by heating under reduced pressure.

In this way, resin microspheres coated with hot-melt resin are obtained in the form of a lump. Next, 20 grams of glycerin was added to this mass, the mass was sufficiently ground in a mortar, and the mass was further passed through three rolls to completely loosen the mass.

This was then washed on a glass filter with 142 ethanol and then ethanol/Freon 11
3 mixed solution (2:1 by volume) if. Next, the mixture was allowed to stand for 15 hours in this state, and the supernatant was decanted to remove fine pieces of polyethylene wax. This product was filtered again on a glass filter and then washed with Freon 113. This is 60°
By heating and drying at C with the gear open,
A multilayer structure fine material was obtained.

The particle size of this multilayer structure fine material is measured using Coulter Counter ZB.
As a result of measurement using a /C-1000 type particle size measuring device, the average particle size was 10.42 μm and the standard deviation was 0.43 μm. The results revealed that polyethylene wax was formed on the surface of the resin microspheres with an average thickness of 0.16 μm. Furthermore, as a result of observing the surface of the multilayer microscopic object using a scanning electron microscope, it was found that the surface of the resin microsphere was uniformly coated with polyethylene wax without any gaps.

A spray solution in which the multilayer structure fine particles were suspended in Freon 113 was sprayed onto a glass plate from a nozzle.

On the glass plate, each multilayer structure fine material showed good single particle dispersibility without agglomeration.

After leaving this glass plate in a heating furnace at 110'C for 10 minutes, we observed the bonded area between the glass plate and the multilayer structure fine particles using a 200x magnifying glass, and found that the polyethylene wax layer melted and the polyethylene wax It was confirmed that the layer was sufficiently interposed between the glass plate and the resin microspheres, and that the resin microspheres were adhered to the glass plate.

Implementation group 1: Made of silicate glass, particle size is 7.30μ, standard deviation is 0.
．． Tetrabutoxytitanium (manufactured by Nippon Soda, trade name B-1) was added to 10 g of inorganic microspheres with a particle size distribution of 32 μm.
) Add a solution of 0.35 g dissolved in 15 d of n-hexane, mix well with a spatula, and then evaporate the n-hexane. 6 Next, thoroughly crush this in a mortar to remove any lumps. did.

On the other hand, as a hot-melt adhesive resin, carboxyl group-containing ethylene-vinyl acetate copolymer (Takeda Pharmaceutical Co., Ltd.
2.9 g of Duramin C-2280 (manufactured by Co., Ltd., trade name: Duramin C-2280) was used. Except for the above, a fine multilayer structure was obtained by the same operation as in Example 1.

It was found that the particle size of this multilayer structure fine material was 7.58 μm, the standard deviation was 0.43 μm, and the average thickness of the carboxy group-containing ethylene-vinyl acetate copolymer layer was 0.14 μm. . In addition, by spraying in the same manner as in Example 1, good single particle dispersion of the multilayer structure fine particles was obtained on the glass plate. Place this glass plate in a heating furnace at 120″C for 10 minutes.
It was confirmed that good adhesion was achieved between the microspheres and the glass plate by allowing the microspheres to stand for a minute.

In Example 1, the solid particles were made of borosilicate glass, had an average diameter of 9.05 μm, and an average length of 15.1 μm.
Using short glass fibers, add a solution of 0.3 g of tetrakis(2-ethylhexoxy) titanium (trade name: TOT, manufactured by Nippon Soda) in 15 d of n-hexane to 10 g of the short glass fibers, and After mixing well, n-hexane was evaporated. Next, this material was thoroughly ground in a mortar to eliminate any lumps.

On the other hand, 2.5 g of polyethylene wax oxide (trade name: Sunwax E-300, manufactured by Sanyo Chemical Industries, Ltd.) was used as a hot-melt adhesive resin.

Except for the above, a fine multilayer structure was obtained by the same operation as in Example 1. As a result of scanning electron microscope observation, the diameter of this multilayer structure fine material was 9.31 μm. From this result, it was found that a hot melt type adhesive resin layer was formed on the short glass fibers with an average thickness of 0.13 μm.

(Effects of the Invention) As described above, according to the present invention, since the hot-melt adhesive resin layer is provided on the surface of the solid particles, the hot-melt adhesive resin layer can be applied while maintaining a predetermined interval by the solid particles. By heating and melting the layers, this multilayer structure fine material can be adhered to the substrate. Therefore, when the multilayer structure fine material of the present invention is used, for example, as a gap material for a liquid crystal display cell, the gap material will not scatter or move from the substrate surface, and the gap between two transparent substrates will be closed. It is possible to reliably maintain the temperature almost constant and improve quality.

Moreover, a titanium oxide layer with good adhesive properties, which is presumed to be derived from the rough surface structure, is provided on the surface of the solid particles, and a hot-melt adhesive resin layer is provided on the surface of the titanium oxide layer. This adhesive resin has good adhesion and can be formed into a thin film. Therefore, it is not necessary to use a resin that has excellent adhesion to solid particles as the adhesive resin, and a resin with poor polarity such as a polyolefin resin can also be used, and the resulting multilayer structure fine material can be used as a liquid crystal. When used as a gap material for display cells,
Problems such as the adhesive resin interfering with the alignment of liquid crystals do not occur. Furthermore, it becomes possible to use a resin with a low melting point or a low softening temperature, which not only improves productivity but also improves the adhesion of the gap material to the substrate. Moreover, since the adhesive resin has good wettability with respect to the titanium oxide layer, it is sufficient to coat only a monomolecular layer of the adhesive resin, and there is no fear that fine particles in the multilayer structure will aggregate together.

Applicant Hiroshi Onishi, Patent Attorney, Sekisui Fine Chemical Co., Ltd.

Claims (1)

[Claims] 1. A titanium oxide layer obtained by treating an organic titanate compound is formed on the surface of the solid particles, and a hot-melt adhesive resin layer is provided on the surface of the titanium oxide layer. Multi-layered fine particles.