JPH11326915A - Adhesive resin particle for spacer of liquid crystal element and spacer composition of liquid crystal element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystal element of stable characteristics which surely adheres two opposite substrates to each other and prevents the unequal presence of spacers. SOLUTION: The resin particles consist of (meth)acrylic adhesive resin particles formed by copolymerization of 10 to 60 pts.wt. glycidyl (meth)acrylate and/or 1 to 10 pts.wt. alkoxysilane compd. with a (meth)acrylic adhesive resin. The spacer compsn. consists of the spacers and 10 to 10000 pts.wt. adhesive resin particles per 100 pts.wt. spacer component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive resin particle which is compounded with a spacer in a liquid crystal element to adhere and fix an opposing substrate and a spacer composition containing the adhesive resin particle. More specifically, the present invention forms a gap capable of filling the liquid crystal between the opposing substrates by heating and pressing the opposing substrates without risk of contaminating the liquid crystal,
The present invention relates to adhesive resin particles which are less likely to deteriorate the liquid crystal display function due to such an adhesive component and are particularly suitable for producing a large liquid crystal element, and a spacer composition for the adhesive resin particle liquid crystal element.

[0002]

2. Description of the Related Art There is known a liquid crystal device in which liquid crystal is injected into a gap in which a pair of flat electrode substrates face each other in parallel.

Heretofore, in such a liquid crystal element, spacer particles have been used in order to keep a gap between substrates for filling liquid crystal constant. As a liquid crystal element using such spacer particles, silica particles or divinylbenzene resin particles are used, and such spacer particles have no adhesiveness to a substrate,
Such spacer particles may move in the gap filled with the liquid crystal when manufacturing the liquid crystal element or operating the liquid crystal element such as applying a voltage to the liquid crystal element. If the area of the liquid crystal display part is small, even if the spacer particles are unevenly distributed to some extent, it is unlikely to cause a serious problem, but recently, with the enlargement of the liquid crystal display screen, the deterioration of the liquid crystal performance due to such uneven distribution of the spacer particles will occur. Is in question.

[0004] Under such circumstances, it has been proposed to mix spacers and adhesive resin particles and bond the opposing substrates to each other with the adhesive resin particles. For example, JP-A-62-2
258426 discloses that the withstand voltage against friction against iron powder is A
μC / g spacer particles and friction withstand voltage BμC
A powder adhesive is disclosed in which spacer particles and spherical polymer particles are blended so that the adhesive particles having a specific weight of 0.1 g / g have the following specific relationship.

[0005]

(Equation 1)

The present invention aims to prevent spacer particles from being unevenly distributed by electrostatically adsorbing spacer particles around polymer particles.

Further, as the adhesive resin particles used for such a liquid crystal element, epoxy adhesive resin particles, polyolefin resin particles, ionomer resin particles, polyester resin particles, acrylic resin particles and the like are used. However, in such resin particles, a liquid crystal compound filled with a low molecular weight additive such as a curing agent may be adversely affected.

For example, Japanese Patent Application Laid-Open No. 3-47877 discloses a spherical particle adhesive whose main component is at least an epoxy resin, a latent curing agent inside the spherical particles, and which is partially cured with a water-soluble curing agent. Particle size 0.3 to 5
A 00 μm epoxy-based particulate adhesive is disclosed.
It is desirable that such adhesive resin particles have good adhesiveness to the opposing substrate and be immobilized after adhering the substrate so as not to adversely affect the liquid crystal.

However, for example, when resin particles such as those described in the above-mentioned publications, particularly epoxy resins, are used, a latent curing agent is compounded inside the spherical particle adhesive, so that the latent particles are hardened during curing. A part of the curing agent may remain without reacting. Such a residual curing agent has high reactivity and may react with the filled liquid crystal compound,
Such reactions may change the characteristics of the liquid crystal compound.

As described above, it is necessary that the adhesive used for the liquid crystal element does not have a reactive group remaining before the liquid crystal compound is filled. Insufficient chemical stability.

In addition to the method of using adhesive particles as particles different from the spacer particles as described above, a method of imparting adhesiveness to the spacer itself to prevent the movement of the spacer particles is known. For example, JP-A-6-1726
No. 59 describes that a coating layer made of a resin composition containing a vinyl polymer and a polyvalent carboxylic acid compound is formed on the surface of core fine particles, and the substrate is adhered by the coating layer. ing.

By forming the coating layer as described above,
The spacer particles adhere to the substrate, but the core of the spacer particles is formed of an organic material or an inorganic material. Therefore, the spacer particles on which the coating layer is formed have a particle shape during thermocompression bonding. Does not have such elasticity that it can be deformed. Therefore, such spacer particles and the substrate are point-bonded, and there is a problem that the adhesion stability of the spacer particles to the substrate is insufficient.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and does not contain a curing agent, so that the display function of the liquid crystal may be deteriorated. Another object of the present invention is to provide an adhesive resin particle for a spacer of a liquid crystal element and a spacer composition for a liquid crystal element which can be used particularly for a large liquid crystal element because the substrate has excellent adhesive strength.

[0014]

SUMMARY OF THE INVENTION The present invention relates to a (meth) acrylic adhesive resin comprising 10 to 60 parts by weight of glycidyl (meth) acrylate and / or 0.1 to 10 parts of an alkoxysilane compound.
Part by weight is the adhesive resin particles for spacers of the liquid crystal element, which are composed of copolymerized (meth) acrylic adhesive resin particles.

The spacer composition for a liquid crystal device of the present invention is a spacer composition for a liquid crystal device comprising a spacer and 10 to 10,000 parts by weight of adhesive resin particles per 100 parts by weight of the spacer component. (Meth) acrylic adhesive in which adhesive resin particles are copolymerized with 10 to 60 parts by weight of glycidyl (meth) acrylate and / or 0.1 to 10 parts by weight of an alkoxysilane compound on a (meth) acrylic adhesive resin It is characterized by being resin particles.

The distance between the substrates of the liquid crystal element secured by the spacer is in the range of 1 to 10 μm, and the average particle diameter of the (meth) acrylic adhesive resin particles is secured by the spacer. It is preferably in the range of 101 to 200% with respect to the distance,
Further, the (meth) acrylic adhesive resin preferably has a glass transition temperature of 20 ° C. or higher.

Such adhesive resin particles have heat cross-linking properties and exhibit very good adhesion to the surface of the liquid crystal element which comes into contact with the liquid crystal, usually to the alignment film formed of polyimide. Most of the polymer becomes a giant gel due to crosslinking between the polymers due to the heat crosslinking reaction, and does not adversely affect the liquid crystal thus formed. Further, the adhesive resin particles have elasticity,
By heat-press bonding, it is heated and cross-linked while being crushed. Accordingly, since the alignment film and the adhesive resin particles are not point-adhesive but are surface-adhered, good adhesiveness is maintained for a long time without change over time.

[0018]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the adhesive resin particles for a spacer of a liquid crystal device and the spacer composition of a liquid crystal device according to the present invention will be described in order.

The adhesive resin particles for a spacer of a liquid crystal element according to the present invention are obtained by adding 10 to 60 parts by weight of glycidyl (meth) acrylate to a (meth) acrylic adhesive resin.
Alternatively, 0.1 to 10 parts by weight of an alkoxysilane compound is composed of copolymerized (meth) acrylic adhesive resin particles.

An acrylic adhesive resin is used for the adhesive resin particles for a spacer of the liquid crystal element according to the present invention as described below. As the (meth) acrylic adhesive resin used in the present invention, a resin obtained by (co) polymerizing a (meth) acrylic compound represented by the following formula (A) is generally used.

CH ₂ = CRCOOR '(A) In the above formula (A), R is hydrogen or a methyl group, and R' is a monovalent group containing no hydrogen.

More specifically, such (meth) acrylic compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, methoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) And (meth) acrylate compounds such as acrylate and isobornyl (meth) acrylate.

As the (meth) acrylic adhesive resin used in the present invention, a (co) polymer using at least one of the above (meth) acrylic compounds is used. It may be a copolymer of at least one (meth) acrylic compound and the following compounds.

Examples of the compound copolymerizable with the (meth) acrylic compound include a styrene compound, a vinyl compound and a compound having two or more functions. Here, examples of the styrene compound include alkylstyrenes such as styrene, methylstyrene, dimethylstyrene, trimethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene. Styrene, iodide styrene; styrene compounds such as nitrostyrene, acetylstyrene and methoxystyrene.

Examples of the vinyl compound include vinylpyridine, vinylpyrrolidone, vinylcarbazole,
Vinyl acetate and acrylonitrile; conjugated diene compounds such as butadiene, isoprene and chloroprene; and vinylidene halides such as vinyl chloride and vinyl bromide.

Examples of the compound having two or more functions include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and trimethylol. Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trihydroxymethylmethane triacrylate, 1,1,1-trihydroxymethylethane triacrylate, 1,1,1
-Trihydroxymethylpropane triacrylate, divinylbenzene and trivinylbenzene.

Further, methyl (meth) acrylic acid, α-ethyl (meth) acrylic acid, crotonic acid, α-methyl crotonic acid, α-ethyl crotonic acid, and the like, as long as the properties of the adhesive resin particles of the present invention are not impaired. Isocrotonic acid, tiglic acid and ungeric acid; addition-polymerizable unsaturated aliphatic carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid and hydromuconic acid may be copolymerized.

The adhesive resin particles for a spacer of a liquid crystal element according to the present invention are obtained by adding glycidyl (meth) acrylate and / or
Alternatively, it is composed of methacrylic resin particles obtained by copolymerizing the following alkoxysilane compound.

The glycidyl (meth) acrylate used here is the compound shown below.

[0030]

Embedded image

However, in the above formula (1), R ⁰ is a hydrogen atom or a methyl group. Glycidyl methacrylate is particularly preferred in the present invention.

In the present invention, an epoxy compound such as glycidoxymethyl (meth) acrylate or glycidoxyethyl (meth) acrylate is used together with glycidyl methacrylate as long as the adhesiveness of the adhesive resin particles does not change. be able to.

Further, in the present invention, the following alkoxysilanes can be used together with the glycidyl (meth) acrylate or in place of the glycidyl (meth) acrylate.

As the alkoxysilane compound used in the present invention, silane compounds represented by the following formulas (2) and (3) are used. _{^{SiR 1 k R 2 m R 3}} 4 _{over k} over m ··· (2) However, in the above formula (2), k is 1 to 3, m
Is 0-2, and k + m is 1-3.

R ¹ is a vinyl-containing group, and R ² is one selected from an alkyl group, an aryl group, an epoxy-containing group, an amine-containing group, a halogen group and an isocyanuric group.
Is a valence group.

When k is 2 or 3, R ¹
May be the same or different, and R ³ is an alkoxy group such as an alkyloxy group, an alkenyloxy group or an aryloxy group.

Examples of R ¹ include a vinyl group and a (meth) acryl-containing group. Here, examples of the (meth) acryl-containing group include a (meth) acrylate group,
(Meth) acryloxyethyl group, (meth) acryloxypropyl group, (meth) acryloxymethoxypropyl group, (meth) acryloxyethoxypropyl group, (meth) acryloxypropoxypropyl group and the like.

Examples of R ² include a hydrogen atom and carbon number 1
To 20 alkyl groups, aryl groups, epoxy groups, amine-containing groups, halogen atoms, and isocyanuric groups.

Here, examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of aryl groups include
Examples include a phenyl group which may have a substituent and a phenoxy group which may have a substituent.

Examples of the epoxy group include a glycidyl group,
Glycidyl (meth) acrylate group, glycidylethyl group, glycidylpropyl group and the like can be mentioned.
Examples of the amine-containing group include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminomethylaminopropyl group, and an aminoethylaminopropyl group.

As an example of a halogen atom, F
, Cl, Br and I. In the formula (2), examples of R ³ include an alkyloxy group having a hydrocarbon group having 1 to 20 carbon atoms, and an alkyloxy group having 1 to 20 carbon atoms.
And an alkenyloxy group and an aryloxy group having a hydrocarbon group.

Here, examples of the alkyloxy group having a hydrocarbon group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group and a butoxy group.

Examples of the alkenyloxy group having a hydrocarbon group having 1 to 20 carbon atoms include a propenyloxy group. Examples of the aryloxy group include a phenoxy group and a benzyloxy group.

As the alkoxysilane compound used in the present invention, a silane compound represented by the following formula (3) can be used. ^{_{R 4 (SiOR 5 2) x}} R 6 ··· (3) However, in the above formula (3), R ⁴ are the same groups as the groups represented by R ¹ in the formula (2), R ⁵ Is the above formula (2)
Is the same group as the group represented by R ^{1 to} R ³ , R ⁶ is the same group as the group represented by R ³ in the formula (2), and x is an integer of 2 or more. .

Examples of the compound represented by the above formula (2) or (3) include trialkyloxyvinylsilane having a hydrocarbon group having 1 to 20 carbon atoms, and alkyl having a hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include a dialkyloxyvinylsilane having a group, a monoalkyloxyvinylsilane having a hydrocarbon group having 1 to 20 carbon atoms, a vinyl compound, and a (meth) acryloxy compound.

Here, specific examples of the trialkyloxyvinylsilane having a hydrocarbon group having 1 to 20 carbon atoms include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyltributoxysilane and vinyltributoxysilane. Such as tripentoxysilane; (meth)
Acrylate trimethoxysilane, (meth) acrylate triethoxysilane, (meth) acrylate tripropoxysilane, (meth) acrylate tributoxysilane,
(Meth) acrylate tripentoxysilane, etc .; (Meth)
(Acryloxyethyltrimethoxysilane, (meth) acryloxyethyltriethoxysilane, (meth) acryloxyethyltripropoxysilane, (meth) acryloxyethyltributoxysilane, (meth) acryloxyethyltripentoxysilane, etc .; (Meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropyltripropoxysilane, (meth) acryloxypropyltributoxysilane, (meth) acryloxypropyltripentoxysilane, etc. ; (Meth) acryloxymethoxypropyltrimethoxysilane, (meth) acryloxymethoxypropyltriethoxysilane, (meth) acryloxymethoxypropyltripropoxysilane, (meth) acryloxymethoxypropyltributoxysila , (Meth) acryloxy-methoxypropyl tri pent silane etc .; (meth) acryloxy ethoxy propyl trimethoxy silane, (meth)
Acryloxyethoxypropyltriethoxysilane,
(Meth) acryloxyethoxypropyltripropoxysilane, (meth) acryloxyethoxypropyltributoxysilane, (meth) acryloxyethoxypropyltripentoxysilane, etc .; (meth) acryloxypropoxypropyltrimethoxysilane, (meth) acrylic Roxypropoxypropyltriethoxysilane, (meth) acryloxypropoxypropyltripropoxysilane, (meth) acryloxypropoxypropyltributoxysilane, (meth) acryloxypropoxypropyltripentoxysilane and the like can be mentioned.

Examples of the dialkyloxyvinylsilane having a hydrocarbon group having 1 to 20 carbon atoms include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropoxysilane, vinylmethyldibutoxysilane, and vinylmethyldipentoxysilane. Silane, etc .; vinyl dimethoxy silane, vinyl diethoxy silane, vinyl dipropoxy silane, vinyl dibutoxy silane, vinyl dipentoxy silane, etc .; (meth) acrylate methyl dimethoxy silane, (meth) acrylate methyl diethoxy silane, (meth) acrylate Methyl dipropoxy silane, (meth) acrylate methyl dibutoxy silane, (meth) acrylate methyl dipentoxy silane, etc .; (meth) acrylate dimethoxy silane, (meth) acrylate diethoxy silane, (meth) acrylate Acrylate dipropoxysilane, (meth) acrylate dibutoxysilane, (meth)
Acrylate dipentoxysilane, etc .; (meth) acrylate dimethoxysilane chloride, (meth) acrylate diethoxysilane chloride, (meth) acrylate dipropoxysilane chloride, (meth) acrylate dibutoxysilane chloride, (meth) acrylate dipentoxysilane Chlorides and the like; (meth) acryloxyethyldimethoxysilane, (meth) acryloxyethyldiethoxysilane, (meth) acryloxyethyldipropoxysilane, (meth) acryloxyethyldibutoxysilane,
(Meth) acryloxyethyldipentoxysilane and the like;
(Meth) acryloxyethyldimethoxymethylsilane,
(Meth) acryloxyethyldiethoxymethylsilane,
(Meth) acryloxyethyldipropoxymethylsilane,
(Meth) acryloxyethyldibutoxymethylsilane,
(Meth) acryloxyethyldipentoxymethylsilane, etc .; (meth) acryloxyethyldimethoxysilane chloride, (meth) acryloxyethyldiethoxysilane chloride, (meth) acryloxyethyldipropoxysilane chloride, (meth) acryloxy Ethyldibutoxysilane chloride, (meth) acryloxyethyldipentoxysilane chloride, etc .; (meth) acryloxypropyldimethoxysilane, (meth) acryloxypropyldiethoxysilane, (meth) acryloxypropyldipropoxysilane, (meth) ) Acryloxypropyl dibutoxy silane,
(Meth) acryloxypropyldipentoxysilane and the like;
(Meth) acryloxymethoxypropyl dimethoxysilane, (meth) acryloxymethoxypropyldiethoxysilane, (meth) acryloxymethoxypropyldipropoxysilane, (meth) acryloxymethoxypropyldibutoxysilane, (meth) acryloxymethoxypropyl Dipentoxysilane and the like; (meth) acryloxyethoxypropyldimethoxysilane, (meth) acryloxyethoxypropyldiethoxysilane, (meth) acryloxyethoxypropyldipropoxysilane, (meth) acryloxyethoxypropyldibutoxysilane, ( (Meth) acryloxyethoxypropyldipentoxysilane, etc .; (meth) acryloxypropoxypropyldimethoxysilane, (meth) acryloxypropoxypropyldiethoxysilane, (meth) acryloxypropoxyp Pildipropoxysilane, (meth) acryloxypropoxypropyldibutoxysilane, (meth) acryloxypropoxypropyldipentoxysilane, etc .; vinylmethoxymethylsilane, vinylethoxymethylsilane, vinylpropoxysilane, vinylbutoxymethylsilane, vinyl pen Toximethylsilane and the like can be mentioned.

Examples of the monoalkyloxyvinylsilane having a hydrocarbon group having 1 to 20 carbon atoms include vinyl methoxymethyl silane chloride, vinyl ethoxymethyl silane chloride, vinyl propoxy silane chloride, vinyl butoxymethyl silane chloride, vinyl pen Methoxymethylsilane chloride, etc .; vinylmethoxydimethylsilane, vinylethoxydimethylsilane, vinylpropoxydimethylsilane, vinylbutoxydimethylsilane, vinylpentoxydimethylsilane, etc .; (meth) acrylate methoxymethylsilane, (meth) acrylateethoxymethylsilane, ( (Meth) acrylate propoxymethylsilane, (meth) acrylatebutoxymethylsilane, (meth) acrylatepentoxymethylsilane, etc .; (meth) acrylate Methoxymethyl silane chloride, (meth) acrylate ethoxymethyl silane chloride, (meth) acrylate propoxymethyl silane chloride, (meth) acrylate butoxymethyl silane chloride, (meth) acrylate pentoxymethyl silane chloride, etc .; (meth) acrylate methoxy dimethyl silane , (Meth) acrylate ethoxydimethylsilane,
(Meth) acrylatepropoxydimethylsilane, (meth) acrylatebutoxydimethylsilane, (meth) acrylatepentoxydimethylsilane, etc .; (meth) acryloxyethylmethoxymethylsilane, (meth) acryloxyethylethoxymethylsilane, (meth) acryl Roxyethylpropoxymethylsilane, (meth) acryloxyethylbutoxymethylsilane, (meth) acryloxyethylpentoxymethylsilane, etc .; (meth) acryloxyethylmethoxymethylsilane chloride, (meth) acryloxyethylethoxymethylsilane chloride, (Meth) acryloxyethylpropoxymethylsilane chloride,
(Meth) acryloxyethylbutoxymethylsilane chloride, (meth) acryloxyethylpentoxymethylsilane chloride, etc .; (meth) acryloxypropylmethoxymethylsilane, (meth) acryloxypropylethoxymethylsilane, (meth) acryloxypropyl Propoxymethylsilane, (meth) acryloxypropylbutoxymethylsilane, (meth) acryloxypropylpentoxymethylsilane, etc .; (meth) acryloxypropylmethoxymethylsilane chloride, (meth) acryloxypropylethoxymethylsilane chloride, (meth) ) Acryloxypropylpropoxymethylsilane chloride, (meth) acryloxypropylbutoxymethylsilane chloride,
(Meth) acryloxypropylpentoxymethylsilane chloride, etc .; (meth) acryloxypropylmethoxydimethylsilane, (meth) acryloxypropylethoxydimethylsilane, (meth) acryloxypropylpropoxydimethylsilane, (meth) acryloxypropylbutoxy Dimethylsilane, (meth) acryloxypropylpentoxydimethylsilane, etc .; (meth) acryloxymethoxypropylmethoxymethylsilane, (meth) acryloxymethoxypropylethoxymethylsilane, (meth) acryloxymethoxypropylpropoxymethylsilane, (meta) ) Acryloxymethoxypropylbutoxymethylsilane,
(Meth) acryloxymethoxypropylpentoxymethylsilane, etc .; (meth) acryloxymethoxypropylmethoxymethylsilane chloride, (meth) acryloxymethoxypropylethoxymethylsilane chloride, (meth)
Acryloxymethoxypropylpropoxymethylsilane chloride, (meth) acryloxymethoxypropylbutoxymethylsilane chloride, (meth) acryloxymethoxypropylpentoxymethylsilane chloride, and the like;
(Meth) acryloxymethoxypropylmethoxydimethylsilane, (meth) acryloxymethoxypropylethoxydimethylsilane, (meth) acryloxymethoxypropylpropoxydimethylsilane, (meth) acryloxymethoxypropylbutoxydimethylsilane, (meth) acryloxymethoxy Propylpentoxydimethylsilane and the like;
(Meth) acryloxyethoxypropylmethoxymethylsilane, (meth) acryloxyethoxypropylethoxymethylsilane, (meth) acryloxyethoxypropylpropoxymethylsilane, (meth) acryloxyethoxypropylbutoxymethylsilane, (meth) acryloxyethoxy Propylpentoxymethylsilane, etc .; (meth) acryloxyethoxypropylmethoxymethylsilane chloride, (meth) acryloxyethoxypropylethoxymethylsilane chloride, (meth) acryloxyethoxypropylpropoxymethylsilane chloride, (meth) acryloxyethoxypropyl Butoxymethylsilane chloride, (meth) acryloxyethoxypropylpentoxymethylsilane chloride, etc .; (meth) acryloxyethoxypropyl methoxydimethyl Silane, (meth) acryloxyethoxypropylethoxydimethylsilane, (meth) acryloxyethoxypropylpropoxydimethylsilane, (meth) acryloxyethoxypropylbutoxydimethylsilane, (meth) acryloxyethoxypropylpentoxydimethylsilane, etc .; ) Acryloxypropoxypropylmethoxymethylsilane, (meth) acryloxypropoxypropylethoxymethylsilane, (meth) acryloxypropoxypropylpropoxymethylsilane, (meth) acryloxypropoxypropylbutoxymethylsilane, (meth) acryloxypropoxypropyl pen (Meth) acryloxypropoxypropyl methoxymethyl silane chloride, (meth)
Acryloxypropoxypropylethoxymethylsilane chloride, (meth) acryloxypropoxypropylpropoxymethylsilane chloride, (meth) acryloxypropoxypropylbutoxymethylsilane chloride,
(Meth) acryloxypropoxypropylpentoxymethylsilane chloride, etc .; (meth) acryloxypropoxypropylmethoxydimethylsilane, (meth) acryloxypropoxypropylethoxydimethylsilane, (meth) acryloxypropoxypropylpropoxydimethylsilane, (meth) Acryloxypropoxypropylbutoxydimethylsilane, (meth) acryloxypropoxypropylpentoxydimethylsilane and the like can be mentioned.

Examples of the vinyl compound used as the compound represented by the above formula (3) include vinyldimethylsilyloxytrimethoxysilane, vinyldimethylsilyloxytriethoxysilane, vinyldimethylsilyloxytripropoxysilane, vinyl Dimethylsilyloxytributoxysilane and the like can be mentioned.

Further, examples of the (meth) acryloxy compound include (meth) acryloxydimethylsilyloxytrimethoxysilane, (meth) acryloxydimethylsilyloxytriethoxysilane, and (meth) acryloxydimethylsilyloxytripropoxysilane. , (Meta)
Acryloxydimethylsilyloxytributoxysilane, (meth) acryloxypropyldimethylsilyloxytrimethoxysilane, (meth) acryloxypropyldimethylsilyloxytriethoxysilane, (meth) acryloxypropyldimethylsilyloxytripropoxysilane, ) Acryloxypropyldimethylsilyloxytributoxysilane and the like.

The adhesive resin particles for a spacer of a liquid crystal element according to the present invention are made of a (meth) ataacryl-based adhesive obtained by copolymerizing the above-mentioned glycidyl methacrylate and / or the above-mentioned alkoxysilane compound with an acrylic adhesive resin. Consists of resin particles.

The (meth) acrylic adhesive resin particles as described above can be produced by various production methods, and are preferably produced by soap-free emulsion polymerization, dispersion polymerization, and seed polymerization, and particularly preferably by seed polymerization. Polymerization is preferred.

The polymerization initiator used here is preferably a radical polymerization initiator. Examples of such radical polymerization initiators include organic peroxides, azo-based initiators and other radical polymerization initiators, for example, inorganic peroxides such as potassium thiosulfate and hydrogen peroxide.

Examples of the organic peroxide used here include cumene hydroperoxide (CHP), ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide (BPO), lauryl peroxide (LPO), Dimethyl bis (tertiary butylperoxy) hexane, dimethylbis (tertiary butylperoxy) hexyne-3, bis (tertiary butylperoxyisopropyl) benzene, bis (tertiary butylperoxy) trimethylcyclohexane, butyl-bis ( Tertiary butyl peroxy) valerate, dibenzoyl peroxide, paramenthane hydroperoxide and tertiary butyl peroxybenzoate can be mentioned. 2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile,
Examples thereof include 2,2'-azobis-2,4-dimethylvaleronitrile and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile.

To disperse these components in an aqueous medium, an emulsifier or a dispersant is used. As the emulsifier or dispersant used here, it is preferable to use a polymer dispersant and / or a surfactant having an HLB value of 8 to 18. Examples of such dispersing agents or surfactants include proteins (eg, gelatin, etc.); lecithin; water-soluble gums such as gum arabic and gum tragacanth; sodium alginate; cellulose derivatives such as carboxymethylcellulose and ethoxycellulose; A polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether,
Polyethylene glycol fatty acid esters, polyvinyl alcohol, etc .; sorbitan fatty acid esters such as sorbitan oleate, sorbitan stearate, sorbitan palmitate; cetyl alcohol; sodium alkylbenzene sulfonate;

These dispersants or surfactants can be used alone or in combination. Such (meth) acrylic adhesive resin particles used in the present invention contain a (meth) acrylate compound,
0-100 parts by weight, preferably 40-100 parts by weight, glycidyl (meth) acrylate is usually 10-60 parts by weight, preferably 20-50 parts by weight, and the styrene compound is usually 0-80 parts by weight; Preferably 0 to 60 parts by weight, bifunctional or more functional compound is usually 0 to 20 parts by weight, preferably 0 to 15 parts by weight, vinyl compound, usually 0 to 50 parts by weight, preferably 0 to 50 parts by weight. 30 parts by weight of the addition-polymerizable unsaturated aliphatic carboxylic acid is (co) polymerized usually in an amount of 0 to 20 parts by weight, preferably 0 to 15 parts by weight.

The (meth) acrylic adhesive resin particles used in the present invention contain a (meth) acrylate compound in an amount of usually 20 to 100 parts by weight, preferably 40 to 100 parts by weight, The silane is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, and the styrene compound is usually 0 to 80 parts by weight, preferably 0 to 10 parts by weight.
60 parts by weight, bifunctional or more compound is usually 0 to 20 parts by weight, preferably 0 to 15 parts by weight, vinyl compound, usually 0 to 50 parts by weight, preferably 0 to 30 parts by weight, The addition-polymerizable unsaturated aliphatic carboxylic acid is usually 0 to
It is (co) polymerized in an amount of 20 parts by weight, preferably 0 to 15 parts by weight.

When both glycidyl (meth) acrylate and alkoxysilane compound are used, the (meth) acrylic adhesive resin particles contain the (meth) acrylate compound usually in an amount of 20 to 100 parts by weight, preferably 40 parts by weight. -100 parts by weight, glycidyl (meth) acrylate is usually 10 to 60 parts by weight, preferably 20 to 50 parts by weight, alkoxysilane is usually 0.1 to 10 parts by weight,
Preferably 1 to 5 parts by weight, a styrene compound is usually 0 to 80 parts by weight, preferably 0 to 60 parts by weight, a bifunctional or more compound is usually 0 to 20 parts by weight, preferably 0 to 0 parts by weight.
15 parts by weight of a vinyl compound, usually 0 to 50 parts by weight
The addition-polymerizable unsaturated aliphatic carboxylic acid is (co) polymerized in an amount of usually 0 to 20 parts by weight, preferably 0 to 15 parts by weight, preferably 0 to 30 parts by weight.

The glass transition temperature of such (meth) acrylic adhesive resin particles is usually in the range of 20 to 150 ° C., and more preferably in the range of 40 to 120 ° C. The glass transition temperature Tg is determined by the Fox (FOX) equation (a) [Bulletin of American Physics Society 1.3, p.
age 123 (1956)].

[0060]

(Equation 2)

Here, Tg is the absolute temperature, W is the weight fraction, and Tg ₁ to _m are the glass transition temperatures (absolute temperatures) of the homopolymer of each component.

The (meth) acrylic adhesive resin particles having such a glass transition temperature have good adhesive strength to a polyimide alignment film by heat and pressure bonding, and have a (meth) acrylic adhesive resin particle. The difference between the coefficient of thermal expansion of the substrate and the coefficient of thermal expansion of the adherend is reduced, and peeling of the liquid crystal element due to such difference in the coefficient of thermal expansion is less likely to occur.

The average particle diameter of the (meth) acrylic adhesive resin particles is usually 1 to 20 μm, preferably 3 to 1 μm.
It is in the range of 5 μm. The particle diameter of the acrylic adhesive resin particles is preferably as uniform as possible, and the CV value indicating the dispersion of the particles is usually in the range of 15% or less, preferably 10% or less.

Since the (meth) acrylic adhesive resin particles are used together with the spacer particles, when the average particle diameter of the spacer particles used is 100%, the (meth) acrylic adhesive resin particles are used. The average particle diameter of the particles is usually 101 to 200%, preferably 130 to 17%.
It has a particle size in the range of 0%.

The (meth) acrylic adhesive resin particles of the present invention have elasticity, and adhere to the substrate while being crushed into a cross-sectional elliptical shape up to the particle diameter of the spacer by the pressure at the time of heat compression bonding. Accordingly, when the (meth) acrylic adhesive particles come into contact with the substrate while being crushed into an elliptical cross section, the substrate comes into surface contact with the particles. That is, if the particle diameter of the spacer particles is the same as the particle diameter of the (meth) acrylic adhesive resin particles, or if the particle diameter of the (meth) acrylic adhesive resin particles is small, the distance between the substrates is determined by the hard spacer particles. Because of the regulation, the substrate and the adhesive resin particles come into point contact. For this reason, it is difficult to develop a strong adhesive force between the substrate and the adhesive resin particles. On the other hand, by using particles having elasticity like the (meth) acrylic adhesive resin particles used in the present invention and larger than the spacer particles, the (meth) acrylic resin particles can be used at the time of thermocompression bonding. The adhesive resin particles are held between the substrates and deform to the particle diameter of the spacer particles. As the particles deform in this way,
The contact between the particles and the substrate changes from a point contact to a surface contact, and by increasing the contact area, the adhesion strength between the particles and the substrate is reduced and a high adhesive force can be maintained for a long period of time.

Such (meth) acrylic adhesive resin particles can be produced by polymerizing the above monomer components using a reaction initiator. In particular, in the present invention, the monomer component, a reaction initiator, an emulsifier,
The polymerization is preferably carried out by emulsification or dispersion in an aqueous medium such as water using a stirring means such as a homogenizer.
The reaction temperature at this time is usually 40 to 150 ° C, preferably 60 to 120 ° C, and the reaction time is usually 1 to 24.
Hours, preferably 2 to 12 hours.

The above reaction is preferably performed in the presence of seed particles. The seed particles used here are particles having an average particle diameter usually in the range of 0.3 to 20 μm, and particles having a CV value of usually 10% or less, preferably 5% or less. By dispersing and polymerizing the monomer component in an aqueous medium in the presence of the particles, the monomer component reacts while being incorporated into the seed particles, and the seed particles grow.

The seed particles used here include:
(Meth) acrylic (co) polymer particles are preferred, and the (meth) acrylic (co) polymer particles are polymerized by finely dispersing the (meth) acrylic monomer in an aqueous medium. It can be manufactured by the following.

Such a seed particle is composed of the monomer component 1
It is usually used in an amount of 1 to 100 parts by weight, preferably 3 to 50 parts by weight, based on 00 parts by weight. The reaction product thus obtained can be used together with a reaction solvent,
Further, the particles are separated from an aqueous medium which is a reaction solvent, and purified if necessary before use.

Further, the particles separated in this way can be used after being dried, or can be used by re-dispersing them in another dispersion medium. Next, the spacer composition of the liquid crystal device according to the present invention will be described.

The spacer composition of the liquid crystal device of the present invention comprises:
It consists of a spacer and the (meth) acrylic adhesive resin particles. The spacer particles used in the present invention are selected from the group consisting of organic polymer particles, inorganic particles, and composite particles.

Among such spacer particles, examples of the organic polymer particles include polyethylene particles, polypropylene particles, polymethylpentene particles, polyvinyl chloride particles, polytetrafluoride particles, polydivinylbenzene particles, polystyrene crosslinked particles, and polystyrene particles. Vinyl polymer particles such as isoprene crosslinked particles, polymethyl methacrylate crosslinked particles, polyacryl crosslinked particles; polyethylene terephthalate particles, polybutylene terephthalate particles, polyamide particles, polyimide particles,
Polysulfone particles, polyphenylene oxide particles,
Organic polymer particles such as polyacetal particles and benzoguanamine-formaldehyde polymer particles; condensed particles of organic silane compounds such as tetraalkoxysilane and trialkoxysilane; and the like.

The inorganic particles include inorganic oxide particles, inorganic carbide particles, and inorganic nitride particles. More specifically, examples thereof include silica particles, alumina particles, glass particles, and condensed particles of a tetraalkoxysilane and a metal alkoxide.

The average diameter of such spacer particles is as follows:
Usually 0.1 to 100 μm, preferably 0.5 to 20 μm
m, more preferably 1 to 10 μm. The spacer preferably used in the present invention is a spherical organic polymer particles and spherical inorganic particles, even if these spacers are spherical, fibrous, cylindrical, oval spherical and other non-spherical. It may have a shape.

The spacer composition of the liquid crystal device of the present invention comprises:
It is obtained by mixing such a spacer and the (meth) acrylic adhesive resin particles as described above. In the spacer composition of the liquid crystal device according to the present invention, the above-mentioned (meth) acrylic adhesive resin particles are usually used in an amount of 10 to 1 with respect to 100 parts by weight of the spacer.
0000 parts by weight, preferably 50 to 5000 parts by weight, more preferably 100 to 1000 parts by weight.

The (meth) acrylic adhesive resin particles and the spacer are uniformly dispersed in a medium that does not dissolve or swell these components, and can be applied as a spacer composition. Here, an organic solvent can be used as the medium, but since the (meth) acrylic adhesive resin particles of the present invention are produced by polymerizing a monomer component in an aqueous medium, such an aqueous medium is used. Spacer particles may be dispersed therein to form a spacer composition.

The spacer composition of the liquid crystal device of the present invention comprises:
For example, it is preferably used for a liquid crystal element as shown in FIG. FIG. 1 shows an example of a liquid crystal element structure. In the liquid crystal element as exemplified in FIG. 1, a pair of substrates in which alignment films C, C are formed on transparent substrates A, A on which conductive films B, B are formed, are arranged such that the alignment films face each other. The substrate is arranged substantially in parallel with. Between a pair of substrates arranged in this way, (meta)
The acrylic adhesive resin particles 1 are substantially uniformly dispersed to form a constant gap between a pair of substrates. The gap for filling the liquid crystal formed between the substrates substantially coincides with the particle diameter of the spacer particles 2 and is usually 0.5 to 20 μm.

In FIG. 1, the gap regulated by the spacer particles contains (meth) acrylic adhesive resin particles crushed into an elliptical cross section, and the (meth) acrylic adhesive resin particles form an alignment film. Are shown bonded to each other.

Then, by thermocompression bonding, a glycidyl group in the component unit derived from glycidyl (meth) acrylate present in the (meth) acrylic adhesive resin particles or a component in the component unit derived from alkoxysilane The alkoxy group is macrogelled by heating due to self-crosslinking. Therefore, the (meth) acrylic adhesive resin particles after thermocompression bonding are stable to liquid crystals because there is almost no low molecular weight polymer. For this reason, even if the liquid crystal is filled in the gap formed by using the spacer composition of the present invention, the liquid crystal is not affected by the (meth) acrylic adhesive resin particles.

The (meth) acrylic adhesive resin particles (particles which have been deformed into an elliptical shape) after being heat-pressed in this manner are crosslinked by heating and no longer have elasticity. The deformed (meth) acrylic adhesive resin particles themselves also function as spacers. Further, the (meth) acrylic adhesive resin particles are developed into spacers by the heat and pressure bonding as described above, so that the movement of the spacer particles formulated from the beginning is prevented by the newly formed spacers. Therefore, the movement of the spacer particles in the liquid crystal can be effectively prevented.

As described above, by using the spacer composition of the present invention, the spacer is not unevenly distributed. Therefore, by using the spacer composition of the present invention, a large-sized liquid crystal device having high stability is manufactured. be able to.

[0082]

As described above, the adhesive resin particles for a spacer according to the present invention are obtained by adding 10 to 60 parts by weight of glycidyl (meth) acrylate and / or alkoxysilane compound 1 to 10 in (meth) acrylic adhesive resin. Since the parts by weight are composed of copolymerized (meth) acrylic adhesive resin particles, the adhesiveness is excellent, and particularly, the adhesiveness to the alignment film constituting the liquid crystal element is excellent. In addition, since the adhesive resin particles for a spacer according to the present invention do not contain a curing agent, there is no possibility that the liquid crystal display function is deteriorated, and the adhesive force with the substrate is excellent. Further, the spacer composition of the liquid crystal element according to the present invention is composed of the above-mentioned adhesive resin particles for spacer and spacer particles, and thus is particularly suitable for producing a large-sized liquid crystal element.

[0083]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not construed as being limited to the following Examples.

[Measurement Conditions of Physical Properties] Measurement of Average Particle Size and CV Value of Particle Size The particle size of 200 particles is measured with a scanning electron microscope to determine the average particle size and CV value.

[0086] 0.1 g of the adhesion test particles was mixed with water-isopropyl alcohol (IP
A) Dispersed in 20 g of a mixed solution (mixing volume ratio = 1: 1) over 5 minutes under ultrasonic irradiation. This dispersion was sprayed on a polyimide alignment film of a glass substrate with a polyimide alignment film (40 mm × 45 mm), and dried at 60 ° C. for 1 hour. This substrate was heated at 150 ° C. for 1 hour at 50 g / cm ² ,
100 g / cm ² , 200 g / cm ² , 400 g / cm ²
A sample substrate was prepared by heating and bonding under the following pressure. Using this prepared sample substrate, the adhesive strength was measured by a tensile tester.

[0086]

Example 1 In a mixture of 25 g of methyl methacrylate, 30 g of isobutyl methacrylate and 40 g of glycidyl methacrylate, benzoyl peroxide (BP) was added.
O) A solution obtained by dissolving 1 g was emulsified and finely dispersed in 160 g of water.

The emulsified dispersion A thus prepared was added to
PMMA particles as seed particles (average particle size 2.9 μm,
15 g of an aqueous dispersion was charged in an amount of 30% by weight (CV value: 3%), heated to 40 ° C., and stirred for 1 hour.

To the dispersion thus prepared, 40 g of a 5% by weight aqueous solution of polyvinyl alcohol (manufactured by Kuraray; PVA-420) was added. After the addition, the dispersion was heated to 75 ° C. and maintained at this temperature for 3 hours to obtain uniform spherical particles having an average particle diameter of 8 μm and a CV value of 7%.

The obtained particles were washed three times with 200 ml of ion-exchanged water, dried at 50 ° C. for 72 hours, crushed and classified,
70 g of uniform spherical powder particles having an average particle diameter of 8 μm and a CV value of 4.0% were obtained. An adhesion test was performed using the obtained particles.

Table 1 shows the results.

[0091]

EXAMPLE 2 In Example 1, 65 g of isobutyl methacrylate was used instead of 28 g of methyl methacrylate, and γ was used instead of 40 g of glycidyl methacrylate.
-70 g of uniform spherical powder particles having an average particle diameter of 8 µm and a CV value of 4.2% were obtained in the same manner as in Example 1 except that emulsified fine dispersion liquid B was prepared using 2 g of methacryloxypropyltrimethoxysilane. Was. An adhesion test was performed using the obtained particles.

Table 1 shows the results.

[0093]

Example 3 An emulsified dispersion C was prepared in the same manner as in Example 1 except that 25 g of methyl methacrylate, 30 g of isobutyl methacrylate and 40 g of glycidyl methacrylate were used instead of 23 g of methyl methacrylate, 30 g of isobutyl methacrylate, 40 g of glycidyl methacrylate and 2 g of methacrylic acid. Except for the above, 70 g of uniform spherical powder particles having an average particle diameter of 8 μm and a CV value of 4.5% were obtained in the same manner as in Example 1. Using the obtained particles, the above-mentioned adhesion test was performed.

Table 1 shows the results.

[0095]

Example 4 In Example 1, an emulsified dispersion was prepared using 20 g of methyl methacrylate, 30 g of isobutyl methacrylate, 40 g of glycidyl methacrylate and 5 g of 2-hydroxyethyl methacrylate instead of 25 g of methyl methacrylate, 30 g of isobutyl methacrylate and 40 g of glycidyl methacrylate. Except for preparing D, the procedure of Example 1 was repeated to obtain 70 g of uniform true spherical powder particles having an average particle size of 8 μm and a CV value of 4.1%. Using the obtained particles, the above-mentioned adhesion test was performed.

The results are shown in Table 1.

[0097]

Comparative Example 1 Composition ratio of isobutyl methacrylate (i) to methyl methacrylate (ii) (weight ratio (i) / (i
i)) is 90/10 seed polymerized particles (average particle size 8 μm)
m, CV value 4.5%), and the above-mentioned adhesion test was performed.

Table 1 shows the results.

[0099]

Comparative Example 2 The composition ratio (weight ratio (i) / (ii) / (iii)) of isobutyl methacrylate (i), methyl methacrylate (ii) and ethylene glycol dimethacrylate (EGDMA) (iii) was 90/5 / The adhesion test described above was conducted using 5 seed polymer particles (average particle size: 8 μm, CV value: 4.2%).

Table 1 shows the results.

[0101]

Example 5 The above-mentioned adhesion test was carried out using 100 mg of the particles of Example 1 and 10 mg of 5 μm silica particles as spacer particles.

Table 1 shows the results.

[0103]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a schematic diagram schematically illustrating an example of a liquid crystal element structure.

[Explanation of symbols]

 1 ... Adhesive resin particles for spacer 2 ... Spacer particles A ... Transparent substrate B ... Transparent conductive film C ... Alignment film

Claims (6)

[Claims] 1. A method according to claim 1, wherein 10 to 60 parts by weight of glycidyl (meth) acrylate and / or
Alternatively, adhesive resin particles for a spacer of a liquid crystal element, comprising (meth) acrylic adhesive resin particles copolymerized with 0.1 to 10 parts by weight of an alkoxysilane compound. 2. The adhesive resin particles for a spacer of a liquid crystal element according to claim 1, wherein the (meth) acrylic adhesive resin particles have an average particle diameter in a range of 1 to 20 μm. 3. The adhesive resin particles for a spacer of a liquid crystal element according to claim 1, wherein the (meth) acrylic adhesive resin particles have a glass transition temperature of 20 ° C. or higher. 4. A spacer composition for a liquid crystal device comprising a spacer and 10 to 10000 parts by weight of adhesive resin particles per 100 parts by weight of the spacer component, wherein the adhesive resin particles are of a (meth) acrylic type. To the adhesive resin, 10 to 60 parts by weight of glycidyl (meth) acrylate and / or
Alternatively, a spacer composition for a liquid crystal device, comprising (meth) acrylic adhesive resin particles obtained by copolymerizing 0.1 to 10 parts by weight of an alkoxysilane compound. 5. A liquid crystal element in which a distance between substrates of the liquid crystal element secured by the spacer is in a range of 1 to 10 μm, and an average particle diameter of the (meth) acrylic adhesive resin particles is secured by the spacer. The spacer composition for a liquid crystal device according to claim 4, wherein the distance is in the range of 101 to 200% with respect to the distance between the substrates. 6. The spacer composition for a liquid crystal device according to claim 4, wherein the (meth) acrylic adhesive resin particles have a glass transition temperature of 20 ° C. or higher.