JP2000212442A - Elastic fine particles coated with polyorganosiloxane, method for producing the same, and liquid crystal display device - Google Patents
Elastic fine particles coated with polyorganosiloxane, method for producing the same, and liquid crystal display deviceInfo
- Publication number
- JP2000212442A JP2000212442A JP11012439A JP1243999A JP2000212442A JP 2000212442 A JP2000212442 A JP 2000212442A JP 11012439 A JP11012439 A JP 11012439A JP 1243999 A JP1243999 A JP 1243999A JP 2000212442 A JP2000212442 A JP 2000212442A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- polyorganosiloxane
- fine particles
- liquid crystal
- coating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010419 fine particle Substances 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 114
- 239000002245 particle Substances 0.000 claims abstract description 211
- 239000007771 core particle Substances 0.000 claims abstract description 79
- 239000011247 coating layer Substances 0.000 claims abstract description 62
- 125000006850 spacer group Chemical group 0.000 claims abstract description 55
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 35
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000007906 compression Methods 0.000 claims abstract description 26
- 230000006835 compression Effects 0.000 claims abstract description 25
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 55
- 210000002858 crystal cell Anatomy 0.000 claims description 52
- 239000010410 layer Substances 0.000 claims description 50
- 239000006185 dispersion Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- 230000002209 hydrophobic effect Effects 0.000 claims description 22
- 150000002430 hydrocarbons Chemical group 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 238000007789 sealing Methods 0.000 description 27
- 239000010408 film Substances 0.000 description 22
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 22
- 239000011347 resin Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 239000000758 substrate Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 230000001681 protective effect Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 125000000962 organic group Chemical group 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- -1 polysiloxane Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- CYGLRHJCEUFWFD-UHFFFAOYSA-N octyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCCCCCC)=CC=CC2=C1 CYGLRHJCEUFWFD-UHFFFAOYSA-N 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- PFJFNQUFMTYCHB-UHFFFAOYSA-N C[SiH2]N[SiH3] Chemical compound C[SiH2]N[SiH3] PFJFNQUFMTYCHB-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- VLFKGWCMFMCFRM-UHFFFAOYSA-N [diacetyloxy(phenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 VLFKGWCMFMCFRM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- OLTVTFUBQOLTND-UHFFFAOYSA-N tris(2-methoxyethoxy)-methylsilane Chemical compound COCCO[Si](C)(OCCOC)OCCOC OLTVTFUBQOLTND-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
(57)【要約】
【課題】圧縮弾性率、弾性復元率の粒子間のばらつきが
小さく、さらに製造バッチ毎のばらつきも小さいスペー
サー用粒子を提供する。
【解決手段】核粒子と核粒子表面のポリオルガノシロキ
サン被覆層とからなる積層微粒子であって、該ポリオル
ガノシロキサン被覆層が、下記式（１）で表される有機
珪素化合物の２種以上の混合物の加水分解物・縮重合物
からなり、かつ、該混合物が、有機珪素化合物の直接ケ
イ素原子に結合した炭化水素基（Ｒ1−Ｓｉ基）の分解
温度が互いに異なる２種以上の有機珪素化合物の混合物
であることを特徴とするポリオルガノシロキサン被覆弾
性微粒子。
Ｒ1 nＳi(ＯＲ2)4-n （１）
（式中、Ｒ1は置換または非置換の炭化水素基から選ば
れる炭素数１〜１０の炭化水素基を示し、Ｒ2は水素原
子、炭素数１〜５のアルキル基、炭素数２〜５のアシル
基を示し、ｎは１〜３の整数である）(57) Abstract: The present invention provides spacer particles having a small variation in compression elastic modulus and elastic recovery ratio among particles, and a small variation among manufacturing batches. Kind Code: A1 Abstract: Laminated fine particles comprising core particles and a polyorganosiloxane coating layer on the surface of the core particles, wherein the polyorganosiloxane coating layer comprises two or more kinds of organosilicon compounds represented by the following formula (1). A mixture of a hydrolyzate and a polycondensate, wherein the mixture is composed of two or more kinds of organic silicons having different decomposition temperatures of hydrocarbon groups (R 1 -Si groups) directly bonded to silicon atoms of the organic silicon compound. Polyorganosiloxane-coated elastic fine particles, which are a mixture of compounds. R 1 n Si (OR 2 ) 4-n (1) (wherein, R 1 represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, R 2 represents a hydrogen atom, Represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and n is an integer of 1 to 3)
Description
【０００１】[0001]
【発明の技術分野】本発明は、ポリオルガノシロキサン
被覆弾性微粒子、その製造方法および該ポリオルガノシ
ロキサン被覆弾性微粒子を液晶セルの電極間であって面
内および／または液晶層の周縁部に設けたシール部にス
ペーサーとして介在させた液晶表示装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyorganosiloxane-coated elastic fine particles, a method for producing the same, and the polyorganosiloxane-coated elastic fine particles provided between electrodes of a liquid crystal cell and in a plane and / or at a peripheral portion of a liquid crystal layer. The present invention relates to a liquid crystal display device in which a seal is interposed as a spacer.
【０００２】さらに詳しくは、粒子の弾性率が高精度に
制御されたスペーサー粒子であって、該粒子を面内用ス
ペーサーとして用いた場合、電極面上に保護膜が形成さ
れている場合には保護膜を傷つけることなく、高精度に
均一に電極間距離を調整することが可能であり、シール
用スペーサーとして用いた場合、シール用樹脂に均一に
分散し、電極を傷つけることが少なくなり、高精度に均
一に基板間距離、電極間距離を調整することが可能なポ
リオルガノシロキサン被覆弾性微粒子、その製造方法お
よび該ポリオルガノシロキサン被覆弾性微粒子を液晶セ
ルの面内用スペーサー、シール用スペーサーとして介在
させた液晶表示装置に関する。More specifically, when spacer particles are particles whose elastic modulus is controlled with high precision, when the particles are used as an in-plane spacer, or when a protective film is formed on an electrode surface, It is possible to adjust the distance between electrodes with high precision and uniformity without damaging the protective film.When used as a spacer for sealing, it is evenly dispersed in the resin for sealing and reduces damage to the electrodes. Polyorganosiloxane-coated elastic fine particles capable of accurately and uniformly adjusting the distance between substrates and the distance between electrodes, a method for producing the same, and the polyorganosiloxane-coated elastic fine particles interposed as in-plane spacers and sealing spacers of a liquid crystal cell. And a liquid crystal display device.
【０００３】[0003]
【発明の技術的背景】液晶表示装置では、液晶表示装置
用液晶セルに備えられた一対の電極間にスペーサーが介
設され、かつ液晶物質が封入されて液晶層を形成してい
る。この液晶層は、厚さが均一でないと、液晶セルに表
示された画像に色むらや点灯時のコントラストの低下を
引き起こすことがある。このため、液晶層には、厚さが
均一であることが望まれている。また高速で表示画像を
切り替える場合、視野角の広い画像を表示する場合に
も、液晶セル内部の液晶層の厚さが均一であること望ま
れている。2. Description of the Related Art In a liquid crystal display device, a spacer is provided between a pair of electrodes provided in a liquid crystal cell for a liquid crystal display device, and a liquid crystal material is sealed to form a liquid crystal layer. If the thickness of the liquid crystal layer is not uniform, the image displayed on the liquid crystal cell may cause color unevenness or decrease in contrast at the time of lighting. Therefore, it is desired that the liquid crystal layer has a uniform thickness. In addition, it is desired that the thickness of the liquid crystal layer inside the liquid crystal cell be uniform even when switching the display image at a high speed or displaying an image with a wide viewing angle.
【０００４】また、液晶層の周縁部に位置するシール部
についても、基板間距離が不均一であると、これに起因
して画像表示ムラやコントラストの低下などの問題を引
き起こすことがあり、シール部の厚さも均一であること
が要求されている。[0004] In addition, if the distance between the substrates is not uniform, the sealing portion located at the peripheral portion of the liquid crystal layer may cause problems such as uneven image display and reduced contrast. The thickness of the part is also required to be uniform.
【０００５】特に、ＳＴＮモードの大画面液晶表示装置
では、液晶セル内部の液晶層の厚さをより均一にして、
しかもシール部の面積を小さく保ち、表示部の面積を大
きく保ちながら電極間距離を一定に保つことが要求され
ている。In particular, in a large-screen STN mode liquid crystal display device, the thickness of a liquid crystal layer inside a liquid crystal cell is made more uniform,
In addition, it is required to keep the distance between the electrodes constant while keeping the area of the seal portion small and keeping the area of the display portion large.
【０００６】このようなシール部の基板間距離および液
晶セル内部の液晶層の厚さを均一にするため、従来よ
り、粒径の揃った球状粒子をシール部および液晶セルの
電極間に散在して介在させること、すなわちシール用ス
ペーサーおよび面内用スペーサーとして用いることが行
われている。このようなスペーサー粒子としてポリスチ
レンなどのような有機樹脂粒子、シリカ微粒子あるいは
有機樹脂で被覆したシリカ微粒子等が用いられている。In order to make the distance between the substrates of the seal portion and the thickness of the liquid crystal layer inside the liquid crystal cell uniform, spherical particles having a uniform particle size have been conventionally scattered between the seal portion and the electrodes of the liquid crystal cell. In other words, they are used as a sealing spacer and an in-plane spacer. As such spacer particles, organic resin particles such as polystyrene, silica fine particles, silica fine particles coated with an organic resin, and the like are used.
【０００７】しかしながら、ポリスチレンなどの有機樹
脂粒子は、柔らかすぎるため、面内用スペーサーとして
用いた液晶表示セルでは、液晶セル内部の液晶層に不均
一な圧力が負荷されると、この圧力のばらつきに応じて
スペーサーが変形し、液晶セル内部の液晶層の厚さを均
一に維持できないという問題があり、しかも有機樹脂粒
子を面内用スペーサーとして使用するには、散布個数を
多くする必要があるという問題点があった。さらには有
機樹脂粒子をシール用スペーサーとして用いると、粒子
の変形が大きくなり電極間距離を所望の厚さにすること
が困難となるという問題があった。However, since organic resin particles such as polystyrene are too soft, in a liquid crystal display cell used as an in-plane spacer, when a non-uniform pressure is applied to the liquid crystal layer inside the liquid crystal cell, this pressure variation will occur. The spacers are deformed in accordance with the conditions, and the thickness of the liquid crystal layer inside the liquid crystal cell cannot be maintained uniformly. In addition, in order to use the organic resin particles as the in-plane spacer, it is necessary to increase the number of sprayed particles. There was a problem. Further, when the organic resin particles are used as the sealing spacer, there is a problem that the deformation of the particles becomes large and it becomes difficult to make the distance between the electrodes a desired thickness.
【０００８】また、シリカ微粒子を液晶セルの面内用ス
ペーサーとして用いると、シリカ微粒子の粒度分布がシ
ャープでないと、シリカ微粒子の圧縮変形が小さいこと
に起因して、液晶セル内部の液晶層の厚さが不均一にな
るという問題点があった。さらに、液晶表示装置が低温
に曝された場合、液晶セル内部で液晶層の熱膨張係数と
スペーサーの熱膨張係数とが異なるため、液晶セルの電
極と液晶層との間に空隙が生じる、所謂、低温気泡が発
生するという問題点があった。Further, when the silica fine particles are used as an in-plane spacer of the liquid crystal cell, if the particle size distribution of the silica fine particles is not sharp, the compression deformation of the silica fine particles is small, and the thickness of the liquid crystal layer inside the liquid crystal cell is reduced. However, there is a problem that the non-uniformity is not uniform. Further, when the liquid crystal display device is exposed to a low temperature, since the thermal expansion coefficient of the liquid crystal layer and the thermal expansion coefficient of the spacer are different inside the liquid crystal cell, a gap is generated between the electrode of the liquid crystal cell and the liquid crystal layer. However, there is a problem that low-temperature bubbles are generated.
【０００９】また、シリカ微粒子をシール用スペーサー
として用いると、硬すぎるために電極を損傷したり、さ
らには断線することがあった。Further, when silica fine particles are used as a sealing spacer, the electrodes may be damaged or broken due to being too hard.
【００１０】上記のような問題点を解決するため、特開
平６−２５０１９３号公報では、加水分解可能なシリコ
ン化合物、例えばテトラエトキシシランなどを加水分解
してシリカ微粒子を調製し、このシリカ微粒子表面のシ
ラノール基を有機化合物でエステル化して調製したシリ
カ微粒子を液晶セルの電極間（面内）スペーサーとして
用いることが提案されている。In order to solve the above problems, JP-A-6-250193 discloses a method of preparing silica fine particles by hydrolyzing a hydrolyzable silicon compound, for example, tetraethoxysilane. It has been proposed to use silica fine particles prepared by esterifying the silanol group of the above with an organic compound as a spacer between electrodes (in-plane) of a liquid crystal cell.
【００１１】この方法で製造したシリカ微粒子は、適度
の硬さと機械的復元性とを有しているため、液晶セルの
電極間スペーサーとして好適であるといわれているもの
の、必ずしも液晶セルの電極間スペーサーとしては不充
分であった。Although the silica fine particles produced by this method have an appropriate hardness and mechanical resilience, they are said to be suitable as a spacer between electrodes of a liquid crystal cell. It was insufficient as a spacer.
【００１２】また、特開平７−１４０４７２号公報に
は、Ｒ'mＳｉ(ＯＲ2)4-m （式中のＲ’、Ｒ2は、それぞ
れ特定の有機基を表す。ｍは、０〜３の整数である。）
で表される有機珪素化合物を加水分解、縮重合して得ら
れた粒子を１００〜１０００℃の範囲で温度を変えて熱
処理することにより特定の圧縮弾性率を有する液晶セル
用スペーサー粒子が得られることが開示されている。こ
のスペーサー粒子の圧縮弾性率は、上記熱処理工程で粒
子内部に存在する有機基の一部を熱分解した後の残存有
機基量で制御されている。このような珪素化合物を用い
た弾性微粒子は、珪素化合物の加水分解により、Ｒ1基
は残留し、ＯＲ2基は加水分解によってアルコール（Ｒ2
ＯＨ）に転換すると共に、生成するＯＨ基は脱水反応を
ともなうポリシロキサン結合の生成によって弾性微粒子
を形成し、その後乾燥、加熱処理して得られる。この弾
性微粒子の、圧縮弾性率、弾性復元率は、加熱処理後の
残存する直接ケイ素原子に結合した炭化水素基（Ｒ
1基）に由来する炭素量に依存する。JP-A-7-140472 discloses R ′ m Si (OR 2 ) 4-m (wherein R ′ and R 2 each represent a specific organic group. It is an integer of 3.)
By subjecting the particles obtained by hydrolyzing and polycondensing the organosilicon compound represented by the formula to a heat treatment while changing the temperature in the range of 100 to 1000 ° C., spacer particles for a liquid crystal cell having a specific compression elastic modulus can be obtained. It is disclosed. The compression modulus of the spacer particles is controlled by the amount of residual organic groups after a part of the organic groups present inside the particles are thermally decomposed in the heat treatment step. Elastic fine particles using such silicon compound, by hydrolysis of a silicon compound, R 1 groups are remained, the alcohol (R 2 OR 2 groups by hydrolysis
OH), and the generated OH groups are formed by forming elastic fine particles by the formation of polysiloxane bonds accompanied by a dehydration reaction, followed by drying and heat treatment. The compression elastic modulus and elastic recovery rate of the elastic fine particles are determined by the hydrocarbon groups (R
1 ) depends on the carbon content.
【００１３】しかしながら、特開平７−１４０４７２号
公報に記載されたスペーサー粒子では、粒子径が異なる
と上記熱処理工程後に粒子内部に残存する有機基量が異
なることがあり、また加熱処理量、雰囲気、昇温速度、
保持温度、処理温度保持時間など加熱処理条件をバッチ
毎に同一にすることは困難であった。このため、弾性微
粒子中の残存有機基量の精密な制御は難しく、粒子毎、
バッチ毎の圧縮変形率が同一になるように制御すること
は非常に困難であり、液晶セル用スペーサー粒子の圧縮
弾性率を所望の値に調整できないという問題点があっ
た。However, in the spacer particles described in JP-A-7-140472, if the particle size is different, the amount of organic groups remaining inside the particles after the above heat treatment step may be different. Heating rate,
It has been difficult to make the heat treatment conditions such as the holding temperature and the processing temperature holding time the same for each batch. For this reason, it is difficult to precisely control the amount of residual organic groups in the elastic fine particles.
It is very difficult to control so that the compressive deformation rate of each batch becomes the same, and there is a problem that the compression elastic modulus of the spacer particles for a liquid crystal cell cannot be adjusted to a desired value.
【００１４】また、粒子の外側と内側とで残存有機基量
が異なることから粒子全体にわたって圧縮弾性率は一様
ではなく、さらに、上記熱処理工程で熱分解された粒子
内部の有機基部分にボイドが発生し、この結果、得られ
た液晶セル用スペーサー粒子の圧縮強度が低下するとい
った問題点があった。Further, since the amount of residual organic groups is different between the outside and inside of the particles, the compression elastic modulus is not uniform over the whole particles, and the organic groups inside the particles thermally decomposed in the heat treatment step have voids. This results in a problem that the compressive strength of the obtained spacer particles for a liquid crystal cell is reduced.
【００１５】このため、本発明者らは、特開昭６３−９
４２２４号において、無機絶縁物粒子の表面に合成樹脂
粉末を固着した粒子は、液晶層などの液晶表示装置中で
粒子が移動することがなく、凝集することが少ないので
微妙な厚さの変化にも対応でき、かつセルギャップを均
一にできることを提案している。For this reason, the present inventors have disclosed in
According to No. 4224, particles in which synthetic resin powder is fixed on the surface of inorganic insulating particles do not move in a liquid crystal display device such as a liquid crystal layer, and are less likely to aggregate, so that a fine change in thickness is caused. That the cell gap can be made uniform.
【００１６】また、本発明者らは、特開平９―５９３８
４号において、特定の有機珪素化合物を用いてオルガノ
ポリシロキサン微粒子を製造することによって、上記の
ような熱処理工程を経ずとも、オルガノポリシロキサン
微粒子内部の有機基量が制御され、高い弾性復元率を有
し、かつ、粒径の揃った微粒子を得ることが可能であ
り、この微粒子は液晶セルの電極間スペーサーとして好
適であることを提案している。The present inventors have also disclosed in Japanese Patent Application Laid-Open No. 9-5938.
In No. 4, by producing the organopolysiloxane fine particles using a specific organosilicon compound, the amount of organic groups inside the organopolysiloxane fine particles can be controlled without performing the above heat treatment step, and a high elastic recovery rate can be obtained. It has been proposed that fine particles having a uniform particle diameter can be obtained, and the fine particles are suitable as a spacer between electrodes of a liquid crystal cell.
【００１７】しかしながら、上記方法では、有機珪素化
合物の種類によっては完全に加水分解・縮重合しなかっ
たり、あるいは加水分解・重縮合が遅いために、得られ
る粒子の収率が低く、しかも収率がバッチによって変動
することがあり、粒子径の再現性が不十分であった。However, in the above-mentioned method, depending on the kind of the organosilicon compound, the hydrolysis / polycondensation is not completely performed, or the hydrolysis / polycondensation is slow, so that the yield of the obtained particles is low and the yield is low. May vary from batch to batch, and reproducibility of the particle size was insufficient.
【００１８】さらにまた、特開平４−３１３７２７号公
報および特開平５−８０３４３号公報には特定範囲の弾
性を有する球状粒子を液晶セルの電極間スペーサーとし
て用いることが提案されており、この球状粒子は、ビニ
ール系プラスチックビーズ、あるいは無機質と有機質と
のハイブリッド粒子であることが開示されている。Furthermore, JP-A-4-313727 and JP-A-5-80343 propose that spherical particles having a specific range of elasticity be used as spacers between electrodes of a liquid crystal cell. Are disclosed as vinyl-based plastic beads or hybrid particles of inorganic and organic substances.
【００１９】しかしながら、これらのような従来のスペ
ーサー粒子では、平均的には所望の圧縮弾性率、高い弾
性復元率を有しているものの、粒子間のばらつきが大き
く、スペーサーとしての機能を充分発現することができ
なかった。しかも、このような物性値の均一な粒子を得
るためには、製造規模を小さくしたり、製造条件を厳し
く管理したりする必要があった。さらに、製造規模を小
さくした場合でも、製造バッチ毎のばらつきが問題とな
ることがあった。However, these conventional spacer particles have a desired compression elastic modulus and a high elastic recovery rate on average, but have large variations among the particles and sufficiently exhibit a function as a spacer. I couldn't. Moreover, in order to obtain such particles having uniform physical property values, it was necessary to reduce the production scale and strictly control the production conditions. Further, even when the production scale is reduced, the variation between production batches may become a problem.
【００２０】[0020]
【発明の目的】本発明は、上記のような問題点を解決
し、圧縮弾性率、弾性復元率の粒子間のばらつきが小さ
く、さらに製造バッチ毎のばらつきも小さいスペーサー
用粒子を提供することを目的としている。An object of the present invention is to solve the above-mentioned problems and to provide spacer particles having a small variation in compression modulus and elastic recovery between particles and a small variation among production batches. The purpose is.
【００２１】具体的には、シール用スペーサーとして用
いた場合には、シール用樹脂に均一に分散し、電極部で
シールする場合には、電極と面接触するために電極が歪
むことも少なく、従って電極を損傷することが少なく、
電極基板間距離を高精度に均一に保つことが可能であ
り、面内用スペーサーとして用いた場合は、電極面上に
保護膜・配向膜が形成されている場合には保護膜・配向
膜と面接触するために保護膜・配向膜を損傷することも
なく液晶セル内部の液晶層の厚さを高精度に均一に維持
可能であり、しかも液晶表示セル内部に低温気泡が発生
することもなく、表示性能に優れた液晶表示装置を作製
可能なポリオルガノシロキサン被覆弾性微粒子、および
該ポリオルガノシロキサン被覆弾性微粒子を液晶セルの
シール用スペーサー、面内用スペーサーとして介在させ
た液晶表示装置を提供することを目的としている。Specifically, when it is used as a sealing spacer, it is uniformly dispersed in the sealing resin, and when it is sealed at the electrode portion, the electrode is hardly distorted due to surface contact with the electrode. Therefore, there is little damage to the electrodes,
It is possible to keep the distance between electrode substrates uniform with high precision.When used as an in-plane spacer, when a protective film / alignment film is formed on the electrode surface, the Due to the surface contact, the thickness of the liquid crystal layer inside the liquid crystal cell can be maintained uniformly with high precision without damaging the protective film and alignment film, and no low-temperature bubbles are generated inside the liquid crystal display cell. The present invention provides a polyorganosiloxane-coated elastic fine particle capable of producing a liquid crystal display device having excellent display performance, and a liquid crystal display device in which the polyorganosiloxane-coated elastic fine particle is interposed as a spacer for sealing a liquid crystal cell and an in-plane spacer. It is intended to be.
【００２２】[0022]
【発明の概要】本発明に係るポリオルガノシロキサン被
覆弾性微粒子は、核粒子と核粒子表面のポリオルガノシ
ロキサン被覆層とからなる積層微粒子であって、該ポリ
オルガノシロキサン被覆層が、下記式（１）で表される
有機珪素化合物の２種以上の混合物の加水分解物・縮重
合物からなり、かつ、該混合物が、珪素化合物の直接ケ
イ素原子に結合した炭化水素基（Ｒ1−Ｓｉ基）の分解
温度が互いに異なる珪素化合物の混合物であることを特
徴としている。SUMMARY OF THE INVENTION The polyorganosiloxane-coated elastic fine particles according to the present invention are laminated fine particles comprising core particles and a polyorganosiloxane coating layer on the surface of the core particles, wherein the polyorganosiloxane coating layer has the following formula (1) A) a hydrocarbon group (R 1 -Si group) comprising a hydrolyzate / polycondensate of a mixture of two or more of the organosilicon compounds represented by the formula ( 1 ), and the mixture being directly bonded to a silicon atom of the silicon compound. Is a mixture of silicon compounds having different decomposition temperatures from each other.
【００２３】 Ｒ1 nＳi(ＯＲ2)4-n （１） （式中、Ｒ1は置換または非置換の炭化水素基から選ば
れる炭素数１〜１０の炭化水素基を示し、Ｒ2は水素原
子、炭素数１〜５のアルキル基、炭素数２〜５のアシル
基を示し、ｎは１〜３の整数である） 前記ポリオルガノシロキサン被覆弾性微粒子は、(i)平
均粒子径が０.５〜３０μｍの範囲にあり、(ii)被覆層
の厚さが０.１〜１０μｍの範囲にあり、(iii)下記式
[I]で定義されるポリオルガノシロキサン被覆弾性微粒
子の１０％Ｋ値が１００〜６０００Kgf/mm2の範囲にあ
り、(iv)核粒子の１０％Ｋ値が５００〜６０００Kgf/mm
2の範囲にあり、(v)該核粒子およびポリオルガノシロキ
サン被覆弾性微粒子の粒子径変動係数が１０％以下であ
ることが好ましい。R 1 n Si (OR 2 ) 4-n (1) (wherein, R 1 represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, and R 2 represents A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acyl group having 2 to 5 carbon atoms, and n is an integer of 1 to 3) The polyorganosiloxane-coated elastic fine particles have (i) an average particle diameter of 0. (Ii) the thickness of the coating layer is in the range of 0.1 to 10 μm, and (iii) the following formula:
The 10% K value of the polyorganosiloxane-coated elastic fine particles defined in [I] is in the range of 100 to 6000 kgf / mm 2 , and (iv) the 10% K value of the core particles is 500 to 6000 kgf / mm 2
Is on the second range, (v) the particle size variation coefficient of the nucleic particles and polyorganosiloxane coated elastic fine particles is preferably 10% or less.
【００２４】 Ｋ＝(３／２1/2)・Ｆ・Ｓ-3/2・(Ｄ／２)-1/2 …[I] 式中、 Ｆ：微粒子の１０％圧縮変形時の荷重値（Kg
f） Ｓ：微粒子の１０％圧縮変形時の圧縮変位（mm） Ｄ：粒子直径（mm） を示
す。K = (3/2 1/2 ) ・FS -3 / 2 ・ (D / 2) -1/2 [I] In the formula, F: load value at the time of 10% compression deformation of the fine particles (Kg
f) S: Compressive displacement (mm) at the time of 10% compressive deformation of fine particles D: Particle diameter (mm)
【００２５】[0025]
【発明の具体的説明】以下、本発明について具体的に説
明する。DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically.
【００２６】ポリオルガノシロキサン被覆弾性微粒子 まず、本発明に係るポリオルガノシロキサン被覆弾性微
粒子について説明する。First, the polyorganosiloxane-coated elastic fine particles according to the present invention will be described.
【００２７】本発明に係るポリオルガノシロキサン被覆
弾性微粒子は、核粒子と核粒子表面のポリオルガノシロ
キサン被覆層とからなる積層微粒子である。The polyorganosiloxane-coated elastic fine particles according to the present invention are laminated fine particles comprising core particles and a polyorganosiloxane coating layer on the surface of the core particles.
【００２８】［核粒子］核粒子としては、従来公知の無
機酸化物粒子、有機樹脂粒子、有機無機複合酸化物粒子
（ポリオルガノシロキン粒子）、さらには従来公知の染
料、顔料を含む粒子を特に制限なく使用することができ
る。[Nucleus Particles] Examples of the core particles include conventionally known inorganic oxide particles, organic resin particles, organic-inorganic composite oxide particles (polyorganoshiroquine particles), and particles containing conventionally known dyes and pigments. It can be used without particular limitation.
【００２９】無機酸化物粒子としては、金属アルコキシ
ドを加水分解して得られるシリカ、アルミナ、ジルコニ
ア等の微粒子が挙げられる。このような核粒子を使用す
る場合、シール部用スペーサー、面内用スペーサーとし
て好適である。Examples of the inorganic oxide particles include fine particles of silica, alumina, zirconia, etc. obtained by hydrolyzing a metal alkoxide. When such a core particle is used, it is suitable as a spacer for a seal portion and a spacer for an in-plane.
【００３０】有機樹脂粒子としては、ジビニルベンゼン
重合体、ジビニルベンゼンースチレン共重合体、ジアル
キルフタレート重合体等の樹脂から形成された微粒子が
挙げられる。このような核粒子を使用する場合、面内用
スペーサーとして好適である。Examples of the organic resin particles include fine particles formed from a resin such as a divinylbenzene polymer, a divinylbenzene-styrene copolymer, and a dialkylphthalate polymer. When such a core particle is used, it is suitable as an in-plane spacer.
【００３１】有機無機複合酸化物粒子としては、上記し
た式（１）で表される有機珪素化合物を加水分解・縮重
合して得られる微粒子が挙げられる。Examples of the organic-inorganic composite oxide particles include fine particles obtained by hydrolyzing and polycondensing the organic silicon compound represented by the above formula (1).
【００３２】 Ｒ1 nＳi(ＯＲ2)4-n （１） （式中、Ｒ1は置換または非置換の炭化水素基から選ば
れる炭素数１〜１０の炭化水素基を示し、Ｒ2は水素原
子、炭素数１〜５のアルキル基、炭素数２〜５のアシル
基を示し、ｎは１〜３の整数である） このような有機無機複合酸化物粒子を核粒子として使用
する場合は、シール部用スペーサー、面内用スペーサー
として好適である。R 1 n Si (OR 2 ) 4-n (1) (wherein, R 1 represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, and R 2 represents A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and n is an integer of 1 to 3) When such organic-inorganic composite oxide particles are used as core particles, It is suitable as a spacer for a seal portion and an in-plane spacer.
【００３３】また、染料、顔料を含む前記各種粒子を核
粒子として用いた場合、スペーサー粒子の光の透過を抑
制することができるため、コントラストの低下を防止す
ることができる。When the above-mentioned various particles containing dyes and pigments are used as core particles, light transmission of the spacer particles can be suppressed, so that a decrease in contrast can be prevented.
【００３４】なお、核粒子は、表面が疎水化しているも
のが好ましい。このため、核粒子表面がシランカップリ
ング剤などにより疎水化されていてもよい。The core particles preferably have a hydrophobic surface. For this reason, the core particle surface may be hydrophobized by a silane coupling agent or the like.
【００３５】核粒子の圧縮弾性率は、１０％Ｋ値として
５００〜６０００Ｋｇｆ／ｍｍ2の範囲にあることが望
ましい。The compression modulus of the core particles is desirably in the range of 500 to 6000 kgf / mm 2 as a 10% K value.
【００３６】核粒子の１０％Ｋ値が５００Ｋｇ／ｍｍ2
未満の場合は、被覆層が硬くても、粒子として柔らかい
ために、液晶セル内部の液晶層の厚さを均一に保持でき
ないことがあり、しかも個々の粒子にかかる圧力を低減
して変形を抑制するために散布個数を増加させる必要が
生じたり、これに伴う品質および経済性が低下したりす
ることがある。The 10% K value of the core particles is 500 kg / mm 2
If it is less than 1, the thickness of the liquid crystal layer inside the liquid crystal cell may not be able to be maintained uniformly because the coating layer is soft, but the deformation may be suppressed by reducing the pressure applied to the individual particles. In some cases, the number of sprays may need to be increased, and the quality and economic efficiency may be reduced.
【００３７】核粒子の１０％Ｋ値が６０００Ｋｇ／ｍｍ
2を超えると、被覆層が軟らかくても、粒子として硬す
ぎるために、粒子径の変動による応力の違いを吸収して
電極間距離を高精度に均一に保つことができなくなった
り、低温気泡が発生したりすることがある。The core particles have a 10% K value of 6000 kg / mm.
If it exceeds 2 , even if the coating layer is soft, it is too hard as particles. Or may occur.
【００３８】このような核粒子の平均粒子径は０．０１
〜２０μｍ、好ましくは０．１〜１０μｍ、特に好まし
くは０．５〜１０μｍの範囲にあることが望ましい。The average particle diameter of such core particles is 0.01
It is desirably in the range of from 20 to 20 μm, preferably from 0.1 to 10 μm, particularly preferably from 0.5 to 10 μm.
【００３９】また核粒子の粒子径変動係数は０.５〜１
０％の範囲にあることが好ましい。さらに好ましい範囲
は０.５〜３％である。The particle diameter variation coefficient of the core particles is 0.5 to 1
It is preferably in the range of 0%. A more preferred range is 0.5 to 3%.
【００４０】粒子径変動係数が０．５％未満のものは得
ることが困難であり、また高温色ムラを起こすことがあ
る。If the coefficient of variation of the particle diameter is less than 0.5%, it is difficult to obtain, and high-temperature color unevenness may occur.
【００４１】［ポリオルガノシロキサン被覆層］本発明
に係るポリオルガノシロキサン被覆弾性微粒子は、ポリ
オルガノシロキサン被覆層が、下記式（１）で表される
有機珪素化合物の２種以上の混合物であって、有機珪素
化合物の直接ケイ素原子に結合した炭化水素基（Ｒ1-Ｓ
i基）の分解温度が互いに異なる有機珪素化合物の２種
以上の混合物の加水分解物・縮重合物からなる。[Polyorganosiloxane Coated Layer] In the polyorganosiloxane coated elastic fine particles according to the present invention, the polyorganosiloxane coated layer is a mixture of two or more kinds of organosilicon compounds represented by the following formula (1). , A hydrocarbon group (R 1 -S
It is composed of a hydrolyzate / polycondensate of a mixture of two or more kinds of organic silicon compounds having different decomposition temperatures of i)).
【００４２】 Ｒ1 nＳi(ＯＲ2)4-n （１） （式中、Ｒ1は置換または非置換の炭化水素基から選ば
れる炭素数１〜１０の炭化水素基を示し、Ｒ2は水素原
子、炭素数１〜５のアルキル基、炭素数２〜５のアシル
基を示し、ｎは１〜３の整数である） 本発明でいう有機珪素化合物の直接ケイ素原子に結合し
た炭化水素基（Ｒ1-Ｓi基）の分解温度とは、式（１）
で表される珪素化合物の直接ケイ素原子に結合した炭化
水素基（Ｒ1）が加熱分解によって、脱離する温度をい
い、示差熱分析法（ＤＴＡ・ＴＧＡ）により求めること
ができる。具体的には、式（１）で表される有機珪素化
合物のＳi-ＯＲ2基を完全に加水分解したものを洗浄・
乾燥したのち、示差熱分析することによって求められ
る。なお、Ｓi-ＯＲ2基が完全に加水分解された有機珪
素化合物は、空気中で、一定の速度（１０℃／ｍｉｎ）
で昇温すると、約１００℃以上の温度で、Ｒ1の分解脱
離による重量減少と燃焼による発熱ピークが同時に観測
され、このときの発熱ピークの発熱開始温度（ＴL）と
発熱終了温度（ＴH）、すなわち（ＴL＋ＴH）／２Ｔと
の中間の温度を、温度を珪素化合物の分解温度をいう。R 1 n Si (OR 2 ) 4-n (1) (wherein, R 1 represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, and R 2 represents A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and n is an integer of 1 to 3) The hydrocarbon group directly bonded to a silicon atom of the organosilicon compound according to the present invention. The decomposition temperature of (R 1 -Si group) is represented by the formula (1)
Is the temperature at which the hydrocarbon group (R 1 ) directly bonded to the silicon atom of the silicon compound desorbs by thermal decomposition, and can be determined by differential thermal analysis (DTA · TGA). More specifically, the organosilicon compound represented by the formula (1) is obtained by completely hydrolyzing the Si-OR 2 group.
After drying, it is determined by differential thermal analysis. The organosilicon compound in which the Si-OR 2 group has been completely hydrolyzed is converted at a constant rate (10 ° C./min) in air.
At a temperature of about 100 ° C. or higher, a weight loss due to decomposition and desorption of R 1 and an exothermic peak due to combustion are simultaneously observed. At this time, the exothermic peak temperature (T L ) and the exothermic end temperature (T L ) T H ), that is, an intermediate temperature between (T L + T H ) / 2T, and the temperature refers to the decomposition temperature of the silicon compound.
【００４３】このような式（１）で表される有機珪素化
合物の具体例としては、メチルトリメトキシシラン、メ
チルトリエトキシシラン、メチルトリイソプロポキシシ
ラン、メチルトリス（メトキシエトキシ）シラン、エチ
ルトリメトキシシラン、ビニルトリメトキシシラン、ビ
ニルトリエトキシシラン、フェニルトリメトキシシラ
ン、γ−クロロプロピルトリメトキシシラン、γ−グリ
シドキシプロピルトリメトキシシラン、メチルトリアセ
トキシシラン、フェニルトリアセトキシシラン等のオル
ガノトリアルコキシシラン化合物、オルガノトリアセト
キシシラン化合物：ジメトキシジメチルシラン、ジエト
キシ-３-グリシドキシプロピルメチルシラン、ジメトキ
シジフェニルシラン、ジアセトキシジメチルシラン等の
ジオルガノジアルコキシシラン化合物等：トリメチルメ
トキシシラン、トリメチルエトキシシラン、トリメチル
シラノール等のトリオルガノアルコキシシシラン化合物
等が挙げられる。Specific examples of the organosilicon compound represented by the formula (1) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltris (methoxyethoxy) silane, and ethyltrimethoxysilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, organotrialkoxysilane compounds such as phenyltriacetoxysilane , Organotriacetoxysilane compounds: diorganodialkoxy such as dimethoxydimethylsilane, diethoxy-3-glycidoxypropylmethylsilane, dimethoxydiphenylsilane, diacetoxydimethylsilane Silane compounds such as: trimethyl methoxy silane, trimethyl ethoxy silane, tri organo alkoxysilane silane compounds such as trimethyl silanol, and the like.
【００４４】このような有機珪素化合物は、加水分解に
より、Ｒ1基が残留し、ＯＲ2基は加水分解によってアル
コールに転換し、生成したＳｉ−ＯＨ基は脱水反応をと
もなうポリシロキサン結合（Ｓi−Ｏ）を形成して、Ｒ1
基が残留した弾性体を形成する。このような弾性体の圧
縮弾性率、弾性復元率は加熱処理後の残存する直接ケイ
素原子に結合した炭化水素基（Ｒ1基）に由来する炭素
量に依存する。In such an organosilicon compound, the R 1 group remains by hydrolysis, the OR 2 group is converted into an alcohol by hydrolysis, and the generated Si—OH group is converted into a polysiloxane bond (Si) by a dehydration reaction. —O) to form R 1
The base forms an elastic body that remains. The compression modulus and elastic recovery of such an elastic body depend on the amount of carbon derived from the hydrocarbon group (R 1 group) directly bonded to the remaining silicon atom after the heat treatment.
【００４５】本発明では、前記したように式（１）で表
される有機珪素化合物から選ばれる２種以上の混合物で
あって、少なくとも２種の珪素化合物の直接ケイ素原子
に結合した炭化水素基の分解温度が互いに異なる珪素化
合物の混合物の加水分解・重縮合物が用いられる。分解
温度は、最も高い有機珪素化合物の分解温度と最も低い
有機珪素化合物の分解温度との差が２０℃以上あること
が好ましく、特に５０℃以上あることが好ましい。分解
温度の差が２０℃未満の場合は乾燥・加熱処理後に得ら
れる微粒子の圧縮弾性率、弾性復元率が粒子間、バッチ
間の変動が大きくなることがある。In the present invention, as described above, a mixture of two or more kinds selected from the organosilicon compounds represented by the formula (1), wherein the hydrocarbon group directly bonded to the silicon atom of at least two kinds of silicon compounds Of a mixture of silicon compounds having different decomposition temperatures from each other. Regarding the decomposition temperature, the difference between the decomposition temperature of the highest organic silicon compound and the decomposition temperature of the lowest organic silicon compound is preferably 20 ° C. or more, and particularly preferably 50 ° C. or more. When the difference in the decomposition temperature is less than 20 ° C., the compression elastic modulus and elastic recovery rate of the fine particles obtained after the drying / heating treatment may vary greatly between particles and between batches.
【００４６】有機珪素化合物の混合比率は所望の圧縮弾
性率、弾性復元率などによって、特に限定されるもので
はないが、分解温度の最も低い珪素化合物または分解温
度の最も高い珪素化合物が混合物中に５〜９５モル％の
範囲にあることが好ましい。上記範囲にない場合は、圧
縮弾性率、弾性復元率が粒子間、バッチ間で変動し再現
性良く得られず、本発明の効果が充分に発現しないこと
がある。The mixing ratio of the organosilicon compound is not particularly limited by the desired compression modulus, elastic recovery, etc., but the silicon compound having the lowest decomposition temperature or the silicon compound having the highest decomposition temperature is contained in the mixture. It is preferably in the range of 5 to 95 mol%. When it is not within the above range, the compression elastic modulus and the elastic recovery rate fluctuate between particles and between batches and cannot be obtained with good reproducibility, and the effect of the present invention may not be sufficiently exhibited.
【００４７】また、上記なような式（１）で表される有
機珪素化合物とともに、下式（２）で表される有機珪素
化合物が含まれていてもよい。Further, an organic silicon compound represented by the following formula (2) may be contained together with the organic silicon compound represented by the above formula (1).
【００４８】 Ｓi(ＯＲ2)4 (2) （式中、Ｒ2は水素原子、炭素数１〜５のアルキル基、
炭素数２〜５のアシル基を示す）。また(2)で表される
有機珪素化合物としては、テトラメトキシシラン、テト
ラエトキシシラン、テトライソプロポキシシラン、テト
ラブトキシシラン等のテトラアルコキシシラン化合物、
テトラアセトキシシラン等のテトラアシルオキシシラン
等の化合物などが挙げられる。Si (OR 2 ) 4 (2) (wherein R 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
Represents an acyl group having 2 to 5 carbon atoms). Further, as the organic silicon compound represented by (2), tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetraalkoxysilane compounds such as tetrabutoxysilane,
Examples include compounds such as tetraacyloxysilanes such as tetraacetoxysilane.
【００４９】通常、(1)式で表される有機珪素化合物
は、(2)式で表される有機珪素化合物に比べて、分解温
度が高い。Usually, the decomposition temperature of the organosilicon compound represented by the formula (1) is higher than that of the organosilicon compound represented by the formula (2).
【００５０】以上のようなポリオルガノシロキサン被覆
層の圧縮弾性率は、１０％Ｋ値として１００〜１０００
Ｋｇｆ／ｍｍ2の範囲にあることが望ましい。このよう
なポリオルガノシロキサン被覆層の１０％Ｋ値は、前記
した核粒子の１０％Ｋ値よりも小さいことが望ましい。
なお、ポリオルガノシロキサン被覆層の１０％Ｋ値と
は、ポリオルガノシロキサン被覆層を形成する式（１）
で表される有機珪素化合物のみから粒子を形成し、この
粒子の１０％Ｋ値を測定して得られる値を意味する。The compression modulus of the polyorganosiloxane coating layer as described above is 100 to 1000 as a 10% K value.
It is desirably in the range of Kgf / mm 2 . The 10% K value of such a polyorganosiloxane coating layer is desirably smaller than the 10% K value of the core particles described above.
The 10% K value of the polyorganosiloxane coating layer is defined by the formula (1) for forming the polyorganosiloxane coating layer.
Means a value obtained by forming particles only from the organosilicon compound represented by and measuring the 10% K value of the particles.
【００５１】ポリオルガノシロキサン被覆層の１０％Ｋ
値が１００Ｋｇｆ／ｍｍ2未満の場合は、被覆層が柔ら
かいために、液晶セル内部の液晶層の厚さを均一に保持
できないことがあり、また個々の粒子にかかる圧力を低
減して変形を抑制するために散布個数を増加させる必要
が生じ、これに伴う品質および経済性が低下したりする
ことがある。10% K of polyorganosiloxane coating layer
If the value is less than 100 kgf / mm 2, the thickness of the liquid crystal layer inside the liquid crystal cell may not be kept uniform because the coating layer is soft, and the pressure applied to each particle is reduced to suppress deformation. Therefore, it is necessary to increase the number of sprays, and the quality and economic efficiency may be reduced.
【００５２】ポリオルガノシロキサン被覆層の１０％Ｋ
値が１０００Ｋｇｆ／ｍｍ2を超えると、被覆層として
は硬すぎるために、電極間距離を高精度に均一に保つこ
とができなくなったり、さらには液晶表示セルに低温気
泡が生じたりすることがある。10% K of polyorganosiloxane coating layer
If the value exceeds 1000 Kgf / mm 2 , the distance between the electrodes cannot be kept uniform with high accuracy because the coating layer is too hard, and low-temperature bubbles may be generated in the liquid crystal display cell. .
【００５３】ポリオルガノシロキサン被覆弾性微粒子 本発明に係るポリオルガノシロキサン被覆弾性微粒子
は、平均粒子径が０.５〜３０μｍの範囲にあることが
好ましく、特に２〜２０μｍの範囲にあることが好まし
い。なお、平均粒子径は液晶表示装置の種類および必要
とする液晶層の厚さによって、弾性特性を考慮して設定
することができるが、上記範囲をはずれるものは通常ス
ペーサーとして用いられない。 Elastic Fine Particles Coated with Polyorganosiloxane The elastic fine particles coated with polyorganosiloxane according to the present invention preferably have an average particle diameter in the range of 0.5 to 30 μm, particularly preferably 2 to 20 μm. The average particle diameter can be set in consideration of the elastic characteristics depending on the type of the liquid crystal display device and the required thickness of the liquid crystal layer, but those having a value outside the above range are not usually used as spacers.
【００５４】また、ポリオルガノシロキサン被覆層の厚
さは０.１〜１０μｍ、好ましくは０.２〜３μｍの範囲
にあることが望ましい。It is desirable that the thickness of the polyorganosiloxane coating layer is in the range of 0.1 to 10 μm, preferably 0.2 to 3 μm.
【００５５】被覆層の厚さが０.１μｍ未満では、ポリ
オルガノシロキサン被覆層の圧縮変形変位が小さいため
に、電極と被覆層の接触面が充分大きくならず、実質的
に核粒子をスペーサーとして用いた場合と同じになり、
電極を損傷したり、低温気泡発生の問題がある。If the thickness of the coating layer is less than 0.1 μm, since the compressive deformation displacement of the polyorganosiloxane coating layer is small, the contact surface between the electrode and the coating layer is not sufficiently large, and the core particles are substantially used as spacers. It is the same as when using
There is a problem of damaging the electrodes and generating low-temperature bubbles.
【００５６】また、ポリオルガノシロキサン被覆層の厚
さが１０μｍを超えると、核粒子の径に対して被覆層の
厚みが大きすぎて、外部からの不均一な圧力に対して電
極間距離を精密に一定に保つことができないことがあ
る。Further, when the thickness of the polyorganosiloxane coating layer exceeds 10 μm, the thickness of the coating layer is too large with respect to the diameter of the core particles, and the distance between the electrodes can be precisely controlled with respect to uneven pressure from the outside. May not be kept constant.
【００５７】このような核粒子とポリオルガノシロキサ
ン被覆層からなるポリオルガノシロキサン被覆弾性微粒
子の１０％Ｋ値は、１００〜６０００Ｋｇｆ／ｍｍ2、
好ましくは２００〜５０００Ｋｇｆ／ｍｍ2の範囲にあ
る。また、１０％Ｋ値の変動係数は１０％以下であるこ
とが好ましい。The 10% K value of the polyorganosiloxane-coated elastic fine particles comprising such core particles and the polyorganosiloxane coating layer is 100 to 6000 kgf / mm 2 ,
Preferably it is in the range of 200 to 5000 Kgf / mm 2 . Further, the coefficient of variation of the 10% K value is preferably 10% or less.
【００５８】ポリオルガノシロキサン被覆弾性微粒子の
粒子径変動係数は０.５〜１０％の範囲にあることが好
ましい。さらに好ましい範囲は０.５〜３％である。The coefficient of variation of the particle diameter of the polyorganosiloxane-coated elastic fine particles is preferably in the range of 0.5 to 10%. A more preferred range is 0.5 to 3%.
【００５９】粒子径変動係数が０．５％未満のものは得
ることが困難であり、また高温色ムラを起こすことがあ
り、粒子径変動係数が１０％を超えると、これをシール
用スペーサーとして用いた場合は基板間のギャップが不
均一となるためギャップ制御の精度が低下し、例えばシ
ール部近傍にWashoutと言われるような表示不良を起こ
すことがあり、面内用スペーサーとして用いた場合は液
晶層の厚さを均一に保持することができず保護膜を損傷
したり、画像ムラ等を起こすことがある。If the particle diameter variation coefficient is less than 0.5%, it is difficult to obtain, and high-temperature color unevenness may occur. If the particle diameter variation coefficient exceeds 10%, this is used as a sealing spacer. When used, the gap between the substrates becomes non-uniform, so that the accuracy of the gap control is reduced.For example, a display defect such as Washout may occur in the vicinity of the seal portion, and when used as an in-plane spacer, The thickness of the liquid crystal layer cannot be kept uniform, which may damage the protective film or cause image unevenness.
【００６０】このようなポリオルガノシロキサン被覆弾
性微粒子および前記した核粒子の粒径分布は走査型電子
顕微鏡（日本電子（株）製：ＪＳＭ-５３００型）によ
り写真を撮影し、この画像の２５０個の粒子について画
像解析装置（旭化成（株）製：ＩＰ-１０００）を用い
て測定される。The particle size distribution of the polyorganosiloxane-coated elastic fine particles and the core particles described above was photographed with a scanning electron microscope (JSM-5300, manufactured by JEOL Ltd.). Is measured using an image analyzer (IP-1000, manufactured by Asahi Kasei Corporation).
【００６１】また、各粒子径の変動係数は２５０個の粒
子の粒子径を用いて下記式から計算によって得られる。The coefficient of variation of each particle diameter is obtained by calculation from the following equation using the particle diameters of 250 particles.
【００６２】[0062]
【数１】 (Equation 1)
【００６３】また、１０％Ｋ値の評価方法は下記の通り
である。The evaluation method of the 10% K value is as follows.
【００６４】１０％Ｋ値は、測定器として微小圧縮試験
機（島津製作所製 ＭＣＴＭ−２０１）を用い、試料と
して粒子直径がＤである１個の微粒子を用いて、試料に
一定の負荷速度で荷重を負荷し、圧縮変位が粒子径の１
０％となるまで粒子を変形させ、１０％変位時の荷重と
圧縮変位（ｍｍ）を求める。粒径および求めた圧縮荷
重、圧縮変位を次式に代入して計算によって求められ
る。本発明では、１０個の粒子について１０％Ｋ値を測
定し、この平均値で評価した。The 10% K value was determined by using a micro-compression tester (MCTM-201 manufactured by Shimadzu Corporation) as a measuring device, using one fine particle having a particle diameter of D as a sample, and applying a constant loading speed to the sample. A load is applied, and the compression displacement is 1
The particles are deformed until they become 0%, and the load and the compression displacement (mm) at the time of 10% displacement are obtained. The particle size and the obtained compressive load and compressive displacement are substituted into the following equations to obtain the values by calculation. In the present invention, 10% K value was measured for 10 particles, and the average value was evaluated.
【００６５】 Ｋ＝（３／２1/2）・Ｆ・Ｓ-3/2・（Ｄ／２）-1/2 ここで、Ｆ：微粒子の１０％圧縮変形時の荷重値（Kg
f） Ｓ：微粒子の１０％圧縮変形時の圧縮変位（mm） Ｄ：粒子直径（mm） である。K = (3/2 1/2 ) ・FS・-3/2 （(D / 2) -1/2 Where, F: load value at the time of 10% compression deformation of fine particles (Kg
f) S: Compressive displacement (mm) at the time of 10% compressive deformation of fine particles D: Particle diameter (mm)
【００６６】具体的な測定条件としては、負荷速度定数
を１として、粒径によって（１）負荷速度を０．０２９
〜０．２７gf/secの範囲で変更し、（２）試験荷重を最
大１０gfとした。As specific measurement conditions, the load speed constant is set to 1, and (1) the load speed is set to 0.029 depending on the particle diameter.
(2) The test load was set to a maximum of 10 gf.
【００６７】また、上記で得られた各粒子の１０％Ｋ値
の変動係数は１０個の粒子の１０％Ｋ値を用いて、下記
式より計算によって算出した。The coefficient of variation of the 10% K value of each particle obtained above was calculated by the following equation using the 10% K value of 10 particles.
【００６８】[0068]
【数２】 (Equation 2)
【００６９】本発明に係るポリオルガノシロキサン被覆
弾性微粒子は、核粒子分散液に(i)分解温度の異なるＲ1
nＳi(ＯＲ2)で表される有機珪素化合物の混合物、また
は(ii)Ｒ1 nＳi(ＯＲ2)で表される有機珪素化合物とＳi
(ＯＲ2)4で表される有機珪素化合物との混合物を、添加
し、該混合物を加水分解・重縮合し、得られた積層微粒
子を、分解温度の低い珪素化合物の分解温度以上で加熱
処理することによって得られる。たとえば、以下に示す
方法でポリオルガノシロキサン被覆弾性微粒子を製造す
ることができる。The polyorganosiloxane-coated elastic fine particles according to the present invention contain (i) R 1 having different decomposition temperatures in a core particle dispersion.
n Si mixture of organic silicon compound represented by (OR 2), or (ii) an organic silicon compound represented by R 1 n Si (OR 2) and Si
A mixture with an organic silicon compound represented by (OR 2 ) 4 is added, the mixture is hydrolyzed and polycondensed, and the obtained laminated fine particles are heated at a temperature equal to or higher than the decomposition temperature of the silicon compound having a low decomposition temperature. It is obtained by doing. For example, polyorganosiloxane-coated elastic fine particles can be produced by the following method.
【００７０】ポリオルガノシロキサン被覆弾性微粒子の
製造方法 次いで、本発明に係るポリオルガノシロキサン被覆弾性
微粒子の製造方法について説明する。The elastic fine particles coated with polyorganosiloxane
Production Method Next, a method for producing the polyorganosiloxane-coated elastic fine particles according to the present invention will be described.
【００７１】具体的には、まず(a)疎水性核粒子を水ま
たは水と有機溶媒との混合溶媒に分散させて疎水性核粒
子の分散液を調製し、(b)上記分散液中で、界面活性剤
および加水分解用触媒の存在下に、上記式(1)で表され
る有機珪素化合物から選ばれる２種以上の混合物であっ
て、有機珪素化合物の直接ケイ素原子に結合した炭化水
素基の分解温度が互いに異なる有機珪素化合物の混合物
を加水分解し、加水分解物を疎水性核粒子表面に析出さ
せ、疎水性核粒子の表面にポリオルガノシロキサン被覆
層を形成してポリオルガノシロキサン被覆弾性微粒子分
散液を調製したのち、(c)ついで、ポリオルガノシロキ
サン被覆弾性微粒子分散液からポリオルガノシロキサン
被覆弾性微粒子を分離し、被覆層形成に用いた有機珪素
化合物の直接ケイ素原子に結合した炭化水素基の分解温
度のうち、最も低い分解温度以上の温度で加熱処理する
乾燥および／または加熱処理する。工程(a)：疎水性核粒子分散液の調製 Specifically, first, (a) the hydrophobic core particles are dispersed in water or a mixed solvent of water and an organic solvent to prepare a dispersion of the hydrophobic core particles, and (b) A mixture of two or more organic silicon compounds represented by the above formula (1) in the presence of a surfactant and a hydrolysis catalyst, wherein the hydrocarbon is directly bonded to a silicon atom of the organic silicon compound. A mixture of organic silicon compounds having different decomposition temperatures of groups is hydrolyzed, and the hydrolyzate is precipitated on the surface of the hydrophobic core particles, and a polyorganosiloxane coating layer is formed on the surface of the hydrophobic core particles to form a polyorganosiloxane coating. After preparing the elastic fine particle dispersion, (c) Then, the polyorganosiloxane-coated elastic fine particles are separated from the polyorganosiloxane-coated elastic fine particle dispersion, and directly separated into silicon atoms of the organosilicon compound used for forming the coating layer. Among the decomposition temperature of the combined hydrocarbon radical, dried and / or heat treatment, heat treatment at the lowest decomposition temperature or higher. Step (a): Preparation of hydrophobic core particle dispersion
【００７２】本発明に用いる疎水性核粒子としては、従
来公知の有機樹脂粒子、有機無機複合酸化物粒子（ポリ
オルガノシロキン粒子）、さらには従来公知の染料、顔
料を含む粒子のうち疎水性官能基を有する粒子を使用す
ることができる。さらに、無機酸化物粒子であっても、
粒子表面に水酸基を充分有する場合はシランカップリン
グ剤等で処理して表面に疎水性官能基を付与して、粒子
表面に水酸基を持たないか、持っていても不充分な場合
はアルカリ性溶液に接触させることによって水酸基を付
与（本発明では、これを核粒子の活性化という）した
後、同様にシランカップリング剤等で処理して表面に疎
水性官能基を付与して用いることができる。As the hydrophobic core particles used in the present invention, conventionally known organic resin particles, organic-inorganic composite oxide particles (polyorganoshiroquine particles), and among the particles containing conventionally known dyes and pigments, the hydrophobic core particles may be used. Particles having functional groups can be used. Furthermore, even with inorganic oxide particles,
If the particle surface has sufficient hydroxyl groups, it is treated with a silane coupling agent or the like to impart a hydrophobic functional group to the surface, and the particle surface does not have hydroxyl groups, or if it has insufficient hydroxyl groups, it is converted to an alkaline solution. After contacting to give a hydroxyl group (in the present invention, this is referred to as activation of core particles), it can be treated with a silane coupling agent or the like to impart a hydrophobic functional group to the surface and used.
【００７３】このような核粒子は、前記したように平均
粒子径が０.４〜２５μｍ、１０％Ｋ値が５００〜６０
００Ｋｇｆ／ｍｍ2の範囲にあり、粒子径変動係数が１
０％以下であることが好ましい。Such a core particle has an average particle diameter of 0.4 to 25 μm and a 10% K value of 500 to 60 as described above.
00Kgf / mm 2 and the particle diameter variation coefficient is 1
It is preferably 0% or less.
【００７４】上記疎水性核粒子を水または水と有機溶媒
との混合溶媒に分散させるが、有機溶媒としては、水と
相溶性の有機溶媒、例えば、アルコール類、グリコール
類、グリコールエーテル類、ケトン類などから選ばれる
１種または２種以上が用いられる。The hydrophobic core particles are dispersed in water or a mixed solvent of water and an organic solvent. Examples of the organic solvent include water-compatible organic solvents such as alcohols, glycols, glycol ethers and ketones. One or two or more kinds selected from the group or the like are used.
【００７５】混合溶媒中の有機溶媒の濃度は３０％以下
であることが好ましい。The concentration of the organic solvent in the mixed solvent is preferably 30% or less.
【００７６】また、分散液中の疎水性核粒子の濃度は粒
子径にもよるが１〜１０重量％の範囲にあることが好ま
しい。１重量％未満では生産性が低く、１０重量％を超
えると得られる粒子が凝集する傾向にある。The concentration of the hydrophobic core particles in the dispersion is preferably in the range of 1 to 10% by weight, though it depends on the particle size. If it is less than 1% by weight, the productivity is low, and if it exceeds 10% by weight, the obtained particles tend to aggregate.
【００７７】疎水性核粒子の分散液は必要に応じて超音
波を照射し、粒子を単分散させることができる。工程(b)：被覆層の形成 次に、ポリオルガノシロキサン被覆層を形成してポリオ
ルガノシロキサン被覆弾性微粒子分散液を調製する。The dispersion of the hydrophobic core particles can be irradiated with ultrasonic waves as necessary to monodisperse the particles. Step (b): Formation of coating layer Next, a polyorganosiloxane coating layer is formed to prepare a polyorganosiloxane-coated elastic fine particle dispersion.
【００７８】工程(a)の疎水性核粒子分散液に、次いで
界面活性剤を添加する。界面活性剤としてはイオン性界
面活性剤、非イオン性界面活性剤が使用できるが、アル
カリ性溶媒中で被覆層を形成する場合はアニオン性界面
活性剤が好ましい。A surfactant is then added to the hydrophobic core particle dispersion of step (a). As the surfactant, an ionic surfactant or a nonionic surfactant can be used, but when the coating layer is formed in an alkaline solvent, an anionic surfactant is preferable.
【００７９】この時の界面活性剤の添加量は、核粒子に
対して０.４〜４０重量％の範囲が好ましい。At this time, the addition amount of the surfactant is preferably in the range of 0.4 to 40% by weight based on the core particles.
【００８０】界面活性剤の量が上記範囲にない場合は、
次いで添加する珪素化合物の加水分解物が疎水性核粒子
表面に析出・縮重合して被覆層を形成する割合が低く、
新たな核が発生したり、ゲル状物が多く残存し、このた
め収率が低下したり、粒子成長が不均一となるため粒子
径変動係数の低い粒子が得られないことがあるので好ま
しくない。When the amount of the surfactant is not in the above range,
Then, the rate at which the hydrolyzate of the silicon compound to be added precipitates and condenses on the surface of the hydrophobic core particles to form a coating layer is low,
New nuclei are generated, a lot of gel-like substances remain, and therefore, the yield is reduced, or the particle growth becomes uneven, so that particles having a low coefficient of variation in particle diameter may not be obtained. .
【００８１】次いで、上記した２種以上の珪素化合物の
混合物を、必要に応じて有機溶媒に溶解した溶液を添加
し、さらに加水分解触媒としてアルカリを添加して珪素
化合物を加水分解させ、加水分解物を核粒子表面に析出
・縮重合させて被覆層を形成して、ポリオルガノシロキ
サン被覆弾性微粒子分散液を調製する。Next, a solution obtained by dissolving a mixture of the above-mentioned two or more kinds of silicon compounds in an organic solvent is added, if necessary, and an alkali is added as a hydrolysis catalyst to hydrolyze the silicon compounds. The product is deposited and polycondensed on the surface of the core particles to form a coating layer, thereby preparing a polyorganosiloxane-coated elastic fine particle dispersion.
【００８２】加水分解用触媒として用いるアルカリとし
ては、アルカリ金属の水溶液、アミン水溶液、アンモニ
ア水溶液、アンモニアガス等が挙げられるが、アンモニ
ア水溶液、アンモニアガスは加熱処理後、微粒子中に残
存せず、安価であるので好ましい。Examples of the alkali used as the hydrolysis catalyst include an aqueous solution of an alkali metal, an aqueous amine solution, an aqueous ammonia solution, and an ammonia gas. The aqueous ammonia solution and the ammonia gas do not remain in the fine particles after the heat treatment and are inexpensive. Is preferred.
【００８３】アルカリの添加量は、用いる珪素化合物の
種類および量によって異なるが、分散液のｐＨが好まし
くは７〜１３、さらに好ましくは８〜１２の範囲となる
ように連続的にあるいは断続的に添加することができ
る。The amount of the alkali added depends on the type and amount of the silicon compound to be used, but it is continuously or intermittently so that the pH of the dispersion is preferably in the range of 7 to 13, more preferably 8 to 12. Can be added.
【００８４】アルカリの添加時間は、特に制限はなく、
用いる珪素化合物の種類および量によって変えることが
できる。アルカリを添加した後、加水分解時の温度と同
温または高温に維持して球状微粒子を熟成する。この熟
成工程によって、得られる微粒子の粒子径がさらに均一
となる。熟成時の温度および時間は、約２０〜９５℃、
好ましくは５０〜９０℃の温度で約０．５〜２４時間維
持することが好ましい。The time for adding the alkali is not particularly limited.
It can be varied depending on the type and amount of the silicon compound used. After the alkali is added, the spherical fine particles are aged while maintaining the same or the same temperature as the hydrolysis. By this aging step, the particle diameter of the obtained fine particles becomes more uniform. The aging temperature and time are about 20-95 ° C,
Preferably, the temperature is maintained at 50 to 90 ° C. for about 0.5 to 24 hours.
【００８５】約２０℃未満では、用いる珪素化合物によ
っては加水分解速度が遅く、加水分解物が充分析出しな
いために、溶解したまま残留するシリカ成分が多くな
り、また単分散した粒子が得にくく、９５℃以上では粒
子同士の凝集が起こり、さらには融着した粒子が生成す
ることがある。工程(c)：分離・乾燥・加熱処理 工程(b)で得た分散液から粒子を分離し、必要に応じて
アルコール等の有機溶媒で洗浄し、ついで、乾燥および
／または加熱処理する。When the temperature is lower than about 20 ° C., the hydrolysis rate is slow depending on the silicon compound used, and the hydrolyzate is not sufficiently precipitated, so that the silica component remaining in the dissolved state increases, and monodispersed particles are hardly obtained. If the temperature is higher than 95 ° C., the particles may aggregate, and further, fused particles may be generated. Step (c): Separation / Drying / Heat Treatment The particles are separated from the dispersion obtained in the step (b), washed with an organic solvent such as alcohol if necessary, and then dried and / or heat-treated.
【００８６】乾燥および加熱処理温度は、所望する圧縮
弾性率（面内用、シール用）によって変えることができ
るが、被覆層の形成に用いる２種以上の珪素化合物の分
解温度のうち、最も低い分解温度以上の温度で加熱処理
することが好ましく、具体的には１００〜１２００℃の
範囲にある。The temperature for drying and heat treatment can be changed depending on the desired compression modulus (for in-plane use and for sealing), but the lowest decomposition temperature of the two or more silicon compounds used for forming the coating layer. The heat treatment is preferably performed at a temperature equal to or higher than the decomposition temperature, specifically, in the range of 100 to 1200 ° C.
【００８７】特に、最も低い分解温度と最も高い分解温
度の間の温度で加熱処理すると、所望の圧縮弾性率、弾
性復元率を有する弾性微粒子を再現性良く得ることがで
きるので好ましい。In particular, heat treatment at a temperature between the lowest decomposition temperature and the highest decomposition temperature is preferable because elastic fine particles having a desired compression elastic modulus and elastic recovery can be obtained with good reproducibility.
【００８８】加熱処理時の雰囲気は、含酸素ガス雰囲
気、不活性ガス雰囲気または真空下を選択することがで
きる。なお加熱処理を、空気中、低酸素含有ガス雰囲
気、不活性ガス雰囲気または真空下で行うと、黒色のポ
リオルガノシロキサン被覆弾性微粒子を得ることができ
る。 以上のような製造工程により、核粒子の表面にポ
リオルガノシロキサン被覆層を有する微粒子であって、
該微粒子の平均粒子径が０.５〜３０μｍの範囲にあ
り、被覆層の厚さが０.１〜５μｍ、被覆層の１０％Ｋ
値が１００〜１０００Ｋｇｆ／ｍｍ2の範囲にあり、核
粒子の１０％Ｋ値が５００〜６０００Ｋｇｆ／ｍｍ2の
範囲にあり、該核粒子およびポリオルガノシロキサン被
覆弾性微粒子の粒子径変動係数が１０％以下であること
を特徴とするがポリオルガノシロキサン被覆弾性微粒子
が製造される。The atmosphere during the heat treatment can be selected from an oxygen-containing gas atmosphere, an inert gas atmosphere, and a vacuum. Note that when the heat treatment is performed in air, in a low-oxygen-containing gas atmosphere, an inert gas atmosphere, or under vacuum, black polyorganosiloxane-coated elastic fine particles can be obtained. By the above manufacturing process, fine particles having a polyorganosiloxane coating layer on the surface of the core particles,
The average particle diameter of the fine particles is in the range of 0.5 to 30 μm, the thickness of the coating layer is 0.1 to 5 μm, and the
The value is in the range of 100 to 1000 Kgf / mm 2, the 10% K value of the core particles is in the range of 500 to 6000 Kgf / mm 2 , and the core particle and the polyorganosiloxane-coated elastic fine particles have a particle diameter variation coefficient of 10% or less. However, elastic fine particles coated with polyorganosiloxane are produced.
【００８９】液晶表示装置 最後に、本発明に係る液晶表示装置について、具体的に
説明する。Lastly, the liquid crystal display device according to the present invention will be specifically described.
【００９０】本発明に係る液晶表示装置は、一対の電極
を備えた液晶セルを有し、前記電極間に上記本発明に係
るポリオルガノシロキサン被覆弾性微粒子がスペーサー
として介在していることを特徴としている。The liquid crystal display device according to the present invention has a liquid crystal cell having a pair of electrodes, wherein the polyorganosiloxane-coated elastic fine particles according to the present invention are interposed as spacers between the electrodes. I have.
【００９１】上記液晶セルは、液晶層の周縁部に設けた
シール部および／または電極間全面（面内）に本発明に
係るポリオルガノシロキサン被覆弾性微粒子が介在し、
該微粒子により、液晶セルの電極間距離が一定に保持さ
れていることを除いて、公知の液晶セルと同様に構成さ
れている。In the liquid crystal cell, the polyorganosiloxane-coated elastic fine particles according to the present invention are interposed on the entire surface (in the plane) between the electrodes and the seal provided on the peripheral portion of the liquid crystal layer.
The configuration is the same as that of a known liquid crystal cell except that the distance between the electrodes of the liquid crystal cell is kept constant by the fine particles.
【００９２】本発明に係るポリオルガノシロキサン被覆
弾性微粒子を液晶セルのシール用スペーサーとして用い
る場合、該粒子を構成する核粒子の１０％Ｋ値は、１０
００〜６０００Ｋｇｆ／ｍｍ2、好ましくは２０００〜
５０００Ｋｇｆ／ｍｍ2の範囲にあることが望ましい。When the polyorganosiloxane-coated elastic fine particles according to the present invention are used as a spacer for sealing a liquid crystal cell, the 10% K value of the core particles constituting the particles is 10%.
00 to 6000 Kgf / mm 2 , preferably 2000 to
It is desirable to be in the range of 5000 kgf / mm 2 .
【００９３】核粒子の１０％Ｋ値が１０００Ｋｇｆ／ｍ
ｍ2未満の場合は、被覆層が硬くても、粒子として柔ら
かすぎるために、電極基板間距離を均一かつ一定に調整
できない問題があり、このため粒子密度を増加させると
かシール部面積を増加させるなどの必要が生じる。The 10% K value of the core particles is 1000 kgf / m.
In the case of less than m 2 , even if the coating layer is hard, even if the coating layer is too soft, there is a problem that the distance between the electrode substrates cannot be adjusted uniformly and uniformly because the particles are too soft. The need arises.
【００９４】核粒子の１０％Ｋ値が６０００Ｋｇ／ｍｍ
2を超えると、被覆層が軟らかくても、粒子として硬す
ぎるために、粒子径の変動による個々の粒子にかかる応
力の違いを吸収して電極間距離を高精度に均一に保つこ
とができなくなる。The 10% K value of the core particles is 6000 kg / mm
If it exceeds 2 , even if the coating layer is soft, it is too hard as particles, so it becomes impossible to absorb the difference in stress applied to individual particles due to fluctuations in particle diameter and keep the distance between the electrodes uniform with high precision .
【００９５】また、被覆層の１０％Ｋ値は１００〜１０
００Ｋｇｆ／ｍｍ2の範囲にあることが好ましく、さら
に好ましい範囲は１５０〜８００Ｋｇｆ／ｍｍ2であ
る。The 10% K value of the coating layer is 100 to 10%.
Is preferably in the range of 00Kgf / mm 2, more preferred range is 150~800Kgf / mm 2.
【００９６】被覆層の１０％Ｋ値が１００Ｋｇｆ／ｍｍ
2未満の場合は、被覆層が柔らかすぎて実質的に被覆層
を設けた効果がなく、核粒子のみによるギャップ調整と
なり、基板間距離を均一かつ一定に調整することができ
ない場合がある。The 10% K value of the coating layer is 100 kgf / mm.
If it is less than 2 , the coating layer is too soft to substantially provide the effect of providing the coating layer, and the gap is adjusted only by the core particles, so that the distance between the substrates may not be adjusted uniformly and uniformly.
【００９７】被覆層の１０％Ｋ値が１０００Ｋｇｆ／ｍ
ｍ2を超えても同様に被覆層による応力の吸収が小さい
ために被覆層を設けた効果がなく、核粒子のみによるギ
ャップ調整となり、基板間距離を均一かつ一定に調整す
ることができない場合がある。The 10% K value of the coating layer is 1000 kgf / m
m 2 without any effect of providing a coating layer to be small absorption of stress by similarly coating layer exceeds, becomes only by the gap adjusting core particles, it may not be able to adjust the distance between the substrates uniform and constant is there.
【００９８】本発明に係るポリオルガノシロキサン被覆
弾性微粒子を液晶セルの電極間面内スペーサーとして用
いる場合、該粒子を構成する核粒子の１０％Ｋ値は５０
０〜６０００Ｋｇｆ／ｍｍ2の範囲にあることが好まし
い。さらに好ましい範囲は５００〜２０００Ｋｇ／ｍｍ
2の範囲である。核粒子の１０％Ｋ値が前記の範囲にあ
れば、散布個数が少なくてすむとともに、液晶層の厚さ
を均一に保つことができる。When the polyorganosiloxane-coated elastic fine particles according to the present invention are used as spacers between electrodes of a liquid crystal cell, the 10% K value of the core particles constituting the particles is 50%.
It is preferably in the range of 0 to 6000 kgf / mm 2 . A more preferred range is 500 to 2000 kg / mm.
It is in the range of 2 . When the 10% K value of the core particles is in the above range, the number of sprayed particles can be reduced and the thickness of the liquid crystal layer can be kept uniform.
【００９９】また、ポリオルガノシロキサン被覆層の１
０％Ｋ値は１００〜５００Ｋｇｆ／ｍｍ2の範囲にある
ことが好ましく、さらに好ましい範囲は１００〜３００
Ｋｇｆ／ｍｍ2である。Further, the polyorganosiloxane coating layer 1
The 0% K value is preferably in the range of 100 to 500 kgf / mm 2 , and more preferably 100 to 300 kgf / mm 2.
Kgf / mm 2 .
【０１００】ポリオルガノシロキサン被覆層の１０％Ｋ
値が前記の範囲にあれば、応力によって被覆層が変形し
て面接触となるため電極面（電極面上に保護膜が形成さ
れている場合には保護膜）の損傷がなく、また低温気泡
の発生が低減される。10% K of polyorganosiloxane coating layer
When the value is in the above range, the coating layer is deformed by the stress to make surface contact, so that the electrode surface (the protective film when the protective film is formed on the electrode surface) is not damaged, and the low-temperature bubble is not generated. Is reduced.
【０１０１】本発明に係るポリオルガノシロキサン被覆
弾性微粒子のうち、黒色を有する粒子を液晶セルの電極
間面内スペーサーとして用いた場合、粒子の光透過（光
抜け）を抑制でき、またコントラストが向上し、表示性
能に向上させることができる。When the black particles among the polyorganosiloxane-coated elastic fine particles according to the present invention are used as the spacers between the electrodes of the liquid crystal cell, light transmission (light leakage) of the particles can be suppressed and the contrast can be improved. In addition, display performance can be improved.
【０１０２】このような黒色を有する粒子は、前記工程
(c)または(c')において加熱処理を低酸素含有ガス雰囲
気、不活性ガス雰囲気または真空下で行うことによって
得ることができる。The particles having such a black color are obtained by the above-described process.
It can be obtained by performing the heat treatment in (c) or (c ′) in a low oxygen-containing gas atmosphere, an inert gas atmosphere or under vacuum.
【０１０３】本発明に係るポリオルガノシロキサン被覆
弾性微粒子を液晶セルの電極間面内用またはシール用ス
ペーサーとして用いる場合、必要とされるセルギャップ
の大きさ、均一性などに応じてポリオルガノシロキサン
被覆弾性微粒子の粒子径および粒子径変動係数が選択さ
れる。In the case where the polyorganosiloxane-coated elastic fine particles according to the present invention are used for the inter-electrode surface of a liquid crystal cell or as a spacer for sealing, the polyorganosiloxane-coated elastic fine particles may be used depending on the required cell gap size and uniformity. The particle size and the particle size variation coefficient of the elastic fine particles are selected.
【０１０４】特に粒径が均一であることが望ましく、そ
の指標である粒子径変動係数は、０．５〜１０％の範囲
にあることが好ましく、特に好ましい範囲は０．５〜３
％である。In particular, it is desirable that the particle diameter is uniform, and the coefficient of variation of the particle diameter as an index is preferably in the range of 0.5 to 10%, and particularly preferably in the range of 0.5 to 3%.
%.
【０１０５】本発明に係るポリオルガノシロキサン被覆
弾性微粒子を液晶セルの電極間スペーサーとして用いる
場合、ポリオルガノシロキサン被覆弾性微粒子を一方の
電極面（電極面上に保護膜が形成されている場合には保
護膜の表面）に湿式法または乾式法で散布する。この時
の散布方法は特に限定されないが、ノズル等を用いて噴
霧する方法が一般的であり好ましい。ここで、散布され
た粒子の密度が均一であることが重要で、不均一である
場合は、液晶セル内部液晶層における厚さの不均一化、
これに伴う画像表示ムラ、低温気泡の問題がある。When the polyorganosiloxane-coated elastic fine particles according to the present invention are used as a spacer between electrodes of a liquid crystal cell, the polyorganosiloxane-coated elastic fine particles are used on one electrode surface (in the case where a protective film is formed on the electrode surface). (A surface of the protective film) by a wet method or a dry method. The method of spraying at this time is not particularly limited, but a method of spraying using a nozzle or the like is generally and preferably used. Here, it is important that the density of the dispersed particles is uniform. If the density is non-uniform, the thickness of the liquid crystal layer inside the liquid crystal cell becomes non-uniform,
There is a problem of image display unevenness and low-temperature bubbles accompanying this.
【０１０６】次いで一方の電極面（または保護膜の表
面）に散布されたポリオルガノシロキサン被覆弾性微粒
子上に他方の電極面（または保護膜の表面）を載置して
重ね合わせ、これにより形成されたセルギャップ中に液
晶材料を充填し、両電極面の周縁部をシール用樹脂で貼
り合わせ、密閉することによって、本発明に係る液晶表
示装置で用いられる液晶セルが得られる。Next, the other electrode surface (or the surface of the protective film) is placed on the polyorganosiloxane-coated elastic fine particles scattered on one electrode surface (or the surface of the protective film), and is superimposed thereon. A liquid crystal material used in the liquid crystal display device according to the present invention can be obtained by filling a liquid crystal material in the cell gap, bonding the peripheral portions of both electrode surfaces with a sealing resin, and sealing.
【０１０７】また、本発明に係る液晶表示装置で用いら
れる液晶セルは、本発明に係るポリオルガノシロキサン
被覆弾性微粒子が混合されているシール用樹脂を一方の
電極（または保護膜）の周縁部に液晶材料の注入口を除
いて塗布し、次いで他方の電極面（または保護膜の表
面）を載置して重ね合わせ、液晶材料の注入口から液晶
材料を注入した後、この液晶材料の注入口をシール用樹
脂で密閉する方法などでも得られる。Further, in the liquid crystal cell used in the liquid crystal display device according to the present invention, the sealing resin mixed with the polyorganosiloxane-coated elastic fine particles according to the present invention is applied to the periphery of one electrode (or protective film). The liquid crystal material is applied except for the injection port, and then the other electrode surface (or the surface of the protective film) is placed and overlapped. After the liquid crystal material is injected from the injection port of the liquid crystal material, the injection port of the liquid crystal material is injected. Can also be obtained by sealing with a sealing resin.
【０１０８】上記シール用樹脂中には前記した本発明に
係るシール用に好適なポリオルガノシロキサン被覆弾性
微粒子が混合されていることが好ましい。本発明に係る
ポリオルガノシロキサン被覆弾性微粒子は被覆層がポリ
オルガノシロキサンからなり、シール用樹脂との親和性
が高いため、疎水性を有するために樹脂に均一に分散さ
せることが可能となり、このためシール部内のポリオル
ガノシロキサン被覆弾性微粒子の量を均一にすることが
できる。It is preferable that the above-mentioned sealing resin is mixed with the above-mentioned polyorganosiloxane-coated elastic fine particles suitable for sealing according to the present invention. In the polyorganosiloxane-coated elastic fine particles according to the present invention, the coating layer is made of polyorganosiloxane, and has high affinity with the sealing resin. Therefore, the hydrophobic fine particles can be uniformly dispersed in the resin. The amount of the polyorganosiloxane-coated elastic fine particles in the seal portion can be made uniform.
【０１０９】[0109]
【発明の効果】本発明によれば、粒度分布が極めてシャ
ープであって、しかも圧縮弾性率などの弾性特性に優れ
た、核粒子とポリオルガノシロキサン被覆層からなる弾
性微粒子が提供される。 本発明に係るポリオルガノシ
ロキサン被覆弾性微粒子の製造方法によると、粒子間、
バッチ間のバラツキもなく均一な、所望の粒子径、粒子
径変動係数および弾性特性を有する微粒子を再現性よく
得ることができる。According to the present invention, there are provided elastic fine particles comprising a core particle and a polyorganosiloxane coating layer, which have an extremely sharp particle size distribution and are excellent in elastic properties such as compression elastic modulus. According to the method for producing polyorganosiloxane-coated elastic fine particles according to the present invention, between the particles,
Fine particles having a desired particle size, a particle size variation coefficient, and elastic characteristics that are uniform without variation between batches can be obtained with good reproducibility.
【０１１０】本発明に係るポリオルガノシロキサン被覆
弾性微粒子を液晶セルの電極間（面内用）スペーサーと
して用いると、弾性率の低い被覆層と弾性率の高い核粒
子からなり、核粒子および被覆粒子の粒度分布が共にシ
ャープであるので、電極（保護膜）を損傷することがな
く、液晶セルのセルギャップ、すなわち液晶セルの電極
間に形成された液晶層の厚さを均一に保持することがで
き、また、被覆粒子（核粒子）の圧縮弾性率が高いので
散布個数が少なくてすみ、被覆粒子が弾性を有するの
で、液晶セル内部に発生する低温気泡が防止され、この
結果、画像むらなどのない高性能の液晶表示装置が提供
できる。When the polyorganosiloxane-coated elastic fine particles of the present invention are used as an interelectrode (in-plane) spacer of a liquid crystal cell, they comprise a coating layer having a low elastic modulus and core particles having a high elastic modulus. Since the particle size distributions of both are sharp, the cell gap of the liquid crystal cell, that is, the thickness of the liquid crystal layer formed between the electrodes of the liquid crystal cell can be maintained uniformly without damaging the electrode (protective film). Also, since the compression elastic modulus of the coated particles (core particles) is high, the number of sprayed particles can be reduced, and since the coated particles have elasticity, low-temperature bubbles generated inside the liquid crystal cell can be prevented. And a high-performance liquid crystal display device without the need.
【０１１１】また、本発明に係るポリオルガノシロキサ
ン被覆弾性微粒子の内、黒色を有する微粒子を液晶セル
の電極間面内スペーサーとして用いた場合、粒子の光透
過（光抜け）を抑制でき、またコントラストが向上し、
表示性能に優れる液晶表示装置が提供できる。When the black fine particles among the polyorganosiloxane-coated elastic fine particles according to the present invention are used as the spacers between the electrodes of the liquid crystal cell, light transmission (light leakage) of the particles can be suppressed, and the contrast can be improved. Is improved,
A liquid crystal display device having excellent display performance can be provided.
【０１１２】また、本発明に係るポリオルガノシラン被
覆弾性微粒子をシール用スペーサーとして用いると、弾
性率の低い被覆層と弾性率の高い核粒子からなり、核粒
子および被覆粒子の粒度分布が共にシャープであるの
で、電極を損傷することなく液晶セルのセルギャップを
均一に保持することができ、また、シール用樹脂との親
和性が高いために樹脂に均一に分散させることができ、
被覆粒子（核粒子）の圧縮弾性率が高いので散布個数を
少なくすることができ、このためシール部の面積が小さ
く表示部の面積が大きい液晶表示装置が提供できる。When the polyorganosilane-coated elastic fine particles of the present invention are used as a sealing spacer, a coating layer having a low modulus of elasticity and a core particle having a high modulus of elasticity are formed, and the particle size distribution of both the core particles and the coated particles is sharp. Therefore, the cell gap of the liquid crystal cell can be maintained uniformly without damaging the electrodes, and can be uniformly dispersed in the resin because of high affinity with the sealing resin.
Since the compression elastic modulus of the coated particles (core particles) is high, the number of scattered particles can be reduced, so that a liquid crystal display device having a small area for the seal portion and a large area for the display portion can be provided.
【０１１３】[0113]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれら実施例に限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【０１１４】[0114]
【実施例１】核粒子の活性化工程 シリカ粒子（触媒化成工業（株）製：ＳＷ、粒子径４.
５μｍ、粒子径変動係数１．２％、１０％Ｋ値４８００
Ｋｇｆ／ｍｍ2）２０ｇを４００ｇの水に分散させ、濃
度１重量％のＮａＯＨ水溶液にて分散液のｐＨを１０に
調整した。その後この分散液を８０℃に昇温し、６０分
間加熱しながら撹拌した。ついで、３０℃まで冷却し、
イオン交換樹脂２０ｇを加え、分散液を撹拌しながらア
ルカリを除去したのち、アルカリを除去し、シリカ粒子
を分離し、洗浄・乾燥して活性化したシリカ粒子を得
た。Example 1 Activating step of core particles Silica particles (manufactured by Catalysis Chemical Industry Co., Ltd .: SW, particle size 4.
5 μm, coefficient of variation of particle diameter 1.2%, K value 4% 4800
Kgf / mm 2 ) 20 g was dispersed in 400 g of water, and the pH of the dispersion was adjusted to 10 with a 1% by weight aqueous NaOH solution. Thereafter, the dispersion was heated to 80 ° C. and stirred while heating for 60 minutes. Then cool to 30 ° C,
After adding 20 g of ion exchange resin and removing the alkali while stirring the dispersion, the alkali was removed, and the silica particles were separated, washed and dried to obtain activated silica particles.
【０１１５】疎水性核粒子の調製 上記の活性化したシリカ粒子１０ｇをメチルアルコール
６６.７ｇに分散させ、超音波を照射してシリカ粒子を
単分散させ、分散液を攪拌しながら、これにヘキサメチ
ルジシラザン５ｇとメチルアルコール５ｇの混合溶液を
添加し、１２時間攪拌した後、分離し、アルコールにて
洗浄し、ついで８０℃で２時間乾燥して疎水性核粒子
（Ａ）を調製した。Preparation of Hydrophobic Core Particles The activated silica particles (10 g) were dispersed in methyl alcohol (66.7 g) and irradiated with ultrasonic waves to monodisperse the silica particles. A mixed solution of 5 g of methyldisilazane and 5 g of methyl alcohol was added, stirred for 12 hours, separated, washed with alcohol, and then dried at 80 ° C. for 2 hours to prepare hydrophobic core particles (A).
【０１１６】ポリオルガノシロキサン被覆粒子の調製 上記で得た核粒子（Ａ）５ｇを濃度５重量％のｎ-ブタ
ノール水溶液２６３ｇに分散させ、この分散液に界面活
性剤（オクチルナフタレンスルフォン酸ナトリウム）
０.６ｇを加え超音波を照射して核粒子（Ａ）を溶媒に
単分散させた。この単分散液を緩やかに撹拌しながら、
メチルトリメトキシシラン（分解温度：４８５℃）２７
ｇとビニルトリメトキシラン（分解温度：１６０℃）３
ｇの混合液を添加した。これにより、下層が核粒子
（Ａ）の分散液層であり、その上層がメチルトリメトキ
シシランとビニルトリメトキシランの混合液層である２
層分離溶液を調製した。 Preparation of Polyorganosiloxane-Coated Particles 5 g of the core particles (A) obtained above were dispersed in 263 g of a 5% by weight aqueous solution of n-butanol, and a surfactant (sodium octylnaphthalene sulfonate) was added to the dispersion.
0.6 g was added and the mixture was irradiated with ultrasonic waves to monodisperse the core particles (A) in a solvent. While gently stirring this monodispersed liquid,
Methyltrimethoxysilane (decomposition temperature: 485 ° C) 27
g and vinyltrimethoxysilane (decomposition temperature: 160 ° C) 3
g of the mixture was added. Thus, the lower layer is a dispersion liquid layer of the core particles (A), and the upper layer is a mixed liquid layer of methyltrimethoxysilane and vinyltrimethoxylan.
A layer separation solution was prepared.
【０１１７】ついで濃度０.２８％のＮＨ3水溶液６.０
ｇを核粒子（Ａ）の分散液層に加えた。ＮＨ3添加後メ
チルトリメトキシシランとビニルトリメトキシランの混
合層がなくなるまで、約２時間撹拌しながらメチルトリ
メトキシシランとビニルトリメトキシランの加水分解を
行い、核粒子上にポリオルガノシロキサン被覆層の形成
を行った。Then, an aqueous NH 3 solution having a concentration of 0.28% 6.0 was prepared.
g was added to the dispersion layer of the core particles (A). After the addition of NH 3, the methyltrimethoxysilane and vinyltrimethoxylan are hydrolyzed with stirring for about 2 hours until the mixed layer of methyltrimethoxysilane and vinyltrimethoxylan disappears, and the polyorganosiloxane coating layer is formed on the core particles. Was formed.
【０１１８】ついで、微少のゲル状物を除去した後、８
０℃で１２時間静置してポリオルガノシロキサン被覆粒
子分散液を調製した。Then, after removing a minute gel-like substance, 8
The mixture was allowed to stand at 0 ° C. for 12 hours to prepare a polyorganosiloxane-coated particle dispersion.
【０１１９】ポリオルガノシロキサン被覆粒子の加熱処
理 粒子を取り出し、エタノールにて洗浄し、ついで８０℃
で２時間乾燥した後、３００℃で３時間、空気中で加熱
処理を行った。このようにしてポリオルガノシロキサン
被覆粒子（Ａ-１）を得た。さらに、オルガノシロキサ
ン被覆粒子（Ａ−１）と同じ操作を繰り返してポリオル
ガノシロキサン被覆粒子（A'-1）、(A'-2)、（A'-3）、
(A'-4)を得た。 Heat treatment of polyorganosiloxane-coated particles
The physical particles are taken out, washed with ethanol, and then at 80 ° C.
, And heat-treated in air at 300 ° C. for 3 hours. Thus, polyorganosiloxane-coated particles (A-1) were obtained. Further, the same operation as that of the organosiloxane-coated particles (A-1) was repeated to obtain polyorganosiloxane-coated particles (A'-1), (A'-2), (A'-3),
(A'-4) was obtained.
【０１２０】得られた各ポリオルガノシロキサン被覆粒
子について平均粒径、粒子径変動係数および１０％Ｋ
値、１０％Ｋ値の変動係数を測定および算出した。結果
を表１に示す。For each of the obtained polyorganosiloxane-coated particles, the average particle size, the particle size variation coefficient and the 10% K
Values and the coefficient of variation for the 10% K value were measured and calculated. Table 1 shows the results.
【０１２１】被覆層の１０％Ｋ値測定用粒子の調製 濃度５重量％のｎ-ブタノール水溶液２６３ｇを緩やか
に撹拌しながら、これにメチルトリメトキシシラン２７
ｇとビニルトリメトキシラン３ｇの混合液を添加した。
ついで濃度０.２８％のＮＨ3水溶液６.０ｇを下層のｎ-
ブタノール水溶液の層に加えた。ＮＨ3添加後メチルト
リメトキシシランとビニルトリメトキシランの混合層が
なくなるまで約２時間撹拌しながらメチルトリメトキシ
シランとビニルトリメトキシランの加水分解を行い、つ
いで、微少のゲル状物を除去した後、８０℃で１２時間
静置してポリオルガノシロキサン粒子分散液を調製し
た。Preparation of 10% Particles for K Value Measurement of Coating Layer 263 g of an aqueous solution of n-butanol having a concentration of 5% by weight was slowly stirred while adding methyltrimethoxysilane 27.
g and 3 g of vinyltrimethoxysilane.
Then, 6.0 g of a 0.28% aqueous NH 3 solution was added to the lower layer of n-
Added to the layer of aqueous butanol solution. After the addition of NH 3, the methyltrimethoxysilane and vinyltrimethoxylan were hydrolyzed with stirring for about 2 hours until the mixed layer of methyltrimethoxysilane and vinyltrimethoxylan disappeared, and then a small gel-like substance was removed. Thereafter, the mixture was allowed to stand at 80 ° C. for 12 hours to prepare a polyorganosiloxane particle dispersion.
【０１２２】粒子を取り出し、エタノールにて洗浄し、
ついで８０℃で２時間乾燥した後、３００℃で３時間、
空気中で加熱処理を行った。このようにしてポリオルガ
ノシロキサン被覆粒子（Ａ-１）の被覆層のみからなる
ポリオルガノシロキサン粒子（Ａ-２）を得た。The particles are taken out, washed with ethanol,
Then, after drying at 80 ° C for 2 hours, at 300 ° C for 3 hours,
Heat treatment was performed in air. Thus, polyorganosiloxane particles (A-2) consisting only of the coating layer of the polyorganosiloxane-coated particles (A-1) were obtained.
【０１２３】得られたポリオルガノシロキサン粒子（Ａ
-２）について、粒径が３μｍ以上の任意に選択した粒
子１０個について１０％Ｋ値を測定し、この時の平均値
を表１に示す。The resulting polyorganosiloxane particles (A
Regarding -2), 10% K value was measured for 10 arbitrarily selected particles having a particle size of 3 μm or more, and the average value at this time is shown in Table 1.
【０１２４】[0124]
【実施例２〜４】メチルトリメトキシシランとビニルト
リメトキシランを表１の混合量とした以外は、実施例１
と同様にしてポリオルガノシロキサン被覆粒子（Ｂ-
１）、（Ｃ-１）および（Ｄ-１）を得た。Examples 2 to 4 Example 1 was repeated except that the mixing amounts of methyltrimethoxysilane and vinyltrimethoxysilane were as shown in Table 1.
In the same manner as described above, polyorganosiloxane-coated particles (B-
1), (C-1) and (D-1) were obtained.
【０１２５】得られた各粒子について平均粒径、粒子径
変動係数および１０％Ｋ値、１０％Ｋ値の変動係数を測
定および算出した。結果を表１に示す。For each of the obtained particles, the average particle diameter, the particle diameter variation coefficient, and the variation coefficient of 10% K value and 10% K value were measured and calculated. Table 1 shows the results.
【０１２６】また、メチルトリメトキシシランとビニル
トリメトキシランを表１の混合量とした以外は、実施例
１と同様にしてポリオルガノシロキサン被覆粒子（Ｂ-
２）、（Ｃ-１）および（Ｄ-１）の被覆層のみからなる
ポリオルガノシロキサン粒子（Ｂ-２）、（Ｃ-２）およ
び（Ｄ-２）を得、１０％Ｋ値を測定した。結果を表１
に示す。Further, the same procedure as in Example 1 was carried out except that the mixing amounts of methyltrimethoxysilane and vinyltrimethoxysilane were as shown in Table 1, and the particles coated with polyorganosiloxane (B-
2) Obtain polyorganosiloxane particles (B-2), (C-2) and (D-2) consisting only of the coating layers of (C-1) and (D-1) and measure the 10% K value did. Table 1 shows the results
Shown in
【０１２７】[0127]
【実施例５】核粒子の調製 内容積２Ｌの容器に純水１,３１６ｇを入れ、撹拌しな
がら０±１℃に温度調節する。さらに、あらかじめ温度
５℃に調整したメチルトリメトキシシラン１５０ｇを静
かに加え、メチルトリメトキシシランと純水が上下２層
に分離した状態とした。その後、上層のメチルトリメト
キシシランの温度が１±１℃になるまで撹拌しながら冷
却した。ついで、純水２７.９ｇにブチルアルコール０.
７ｇと濃度２８％のアンモニア水０.３ｇを加え、これ
にアニオン系界面活性剤（オクチルナフタレンスルフォ
ン酸ナトリウム）１.５ｇを加え、温度を５±１℃に調
整した界面活性剤混合溶液を調製した。この界面活性剤
混合溶液を、上下２層に分離した下層を撹拌しながらこ
の下層に６０分で添加した。引き続き２時間撹拌を継続
してポリオルガノシロキサン粒子の分散液を調製した。
ついで粒子を分離し、アルコールで洗浄し、１１０℃で
２時間乾燥した。得られた粒子の平均粒子径は５.６μ
ｍであった。Example 5 Preparation of Core Particles Into a container having an inner volume of 2 L, 1,316 g of pure water was added, and the temperature was adjusted to 0 ± 1 ° C. while stirring. Further, 150 g of methyltrimethoxysilane previously adjusted to a temperature of 5 ° C. was gently added, so that methyltrimethoxysilane and pure water were separated into two upper and lower layers. Thereafter, the mixture was cooled with stirring until the temperature of the upper layer methyltrimethoxysilane reached 1 ± 1 ° C. Then, 27.9 g of pure water was added to 0.2 butyl alcohol.
7 g and 0.3 g of 28% aqueous ammonia were added, and 1.5 g of an anionic surfactant (sodium octylnaphthalene sulfonate) was added thereto to prepare a surfactant mixed solution whose temperature was adjusted to 5 ± 1 ° C. did. This surfactant mixed solution was added to this lower layer in 60 minutes while stirring the lower layer, which was separated into upper and lower layers. Subsequently, stirring was continued for 2 hours to prepare a dispersion of polyorganosiloxane particles.
The particles were then separated, washed with alcohol and dried at 110 ° C. for 2 hours. The average particle size of the obtained particles is 5.6 μm.
m.
【０１２８】この粒子を１０００℃で１時間空気中で焼
成して黒色の核粒子を得た。核粒子の平均粒子径、粒子
径変動係数および１０％Ｋ値、１０％Ｋ値変動係数を表
１に示す。The particles were fired in air at 1000 ° C. for 1 hour to obtain black core particles. Table 1 shows the average particle diameter, the particle diameter variation coefficient, and the 10% K value and the 10% K value variation coefficient of the core particles.
【０１２９】ついで、上記黒色の核粒子を用いた以外は
実施例１と同様に、活性化処理、疎水化処理を行い、被
覆層を形成したのち、５００℃で３時間、窒素雰囲気下
で、加熱処理をしてポリオルガノシロキサン被覆粒子
（Ｅ-１）を得た。Next, an activation treatment and a hydrophobic treatment were carried out in the same manner as in Example 1 except that the above-mentioned black core particles were used, and a coating layer was formed. Heat treatment was performed to obtain polyorganosiloxane-coated particles (E-1).
【０１３０】得られた粒子（Ｅ-１）について平均粒
径、粒径変動係数および１０％Ｋ値、１０％Ｋ値変動係
数を測定および算出した。結果を表１に示す。For the obtained particles (E-1), the average particle diameter, the particle diameter variation coefficient, and the 10% K value and the 10% K value variation coefficient were measured and calculated. Table 1 shows the results.
【０１３１】[0131]
【実施例６】シリカ粒子（触媒化成工業（株）製：Ｓ
Ｗ、粒子径６.５μｍ、粒子径変動係数０．９％、１０
％Ｋ値４８００Ｋｇｆ／ｍｍ2）２０ｇを用い、メチル
トリメトキシシランを４.５ｇ、ビニルトリメトキシシ
ランを０.５ｇ用いた以外は実施例１と同様に、活性化
処理、疎水化処理、被覆層の形成を行った。ついで、１
２０℃で２時間乾燥した後、５００℃で３時間、窒素雰
囲気下で加熱処理をしてポリオルガノシロキサン被覆粒
子（Ｆ-１）を得た。Example 6 Silica particles (manufactured by Catalyst Chemical Industry Co., Ltd .: S
W, particle size 6.5 μm, particle size variation coefficient 0.9%, 10
% K value 4800 Kgf / mm 2 ) Activation treatment, hydrophobization treatment, coating layer in the same manner as in Example 1 except that 20 g, 4.5 g of methyltrimethoxysilane and 0.5 g of vinyltrimethoxysilane were used. Was formed. Then 1
After drying at 20 ° C. for 2 hours, heat treatment was performed at 500 ° C. for 3 hours under a nitrogen atmosphere to obtain polyorganosiloxane-coated particles (F-1).
【０１３２】得られた粒子（Ｆ-１）について平均粒
径、粒子径変動係数および１０％Ｋ値、１０％Ｋ値変動
係数を測定および算出した。結果を表１に示す。With respect to the obtained particles (F-1), the average particle diameter, the coefficient of variation in particle diameter, and the 10% K value and the 10% K value variation coefficient were measured and calculated. Table 1 shows the results.
【０１３３】[0133]
【比較例１】ポリオルガノシロキサン被覆粒子の調製 シリカ粒子（触媒化成工業（株）製：ＳＷ、粒子径４.
５μｍ、粒子径変動係数１．２％、１０％Ｋ値４８００
Ｋｇｆ／ｍｍ2）５ｇを濃度５重量％のｎ-ブタノール水
溶液２６３ｇに分散させ、超音波を照射してシリカ粒子
を溶媒に単分散させた。この単分散液を緩やかに撹拌し
ながら、メチルトリメトキシシラン２７ｇとビニルトリ
メトキシラン３ｇの混合液を添加した。この時、下にシ
リカ核粒子の分散液の層、その上にメチルトリメトキシ
シランとビニルトリメトキシランの混合液の層を形成し
た。Comparative Example 1 Preparation of Polyorganosiloxane-Coated Particles Silica Particles (manufactured by Catalyst Chemical Industry Co., Ltd .: SW, particle size 4.
5 μm, coefficient of variation of particle diameter 1.2%, K value 4% 4800
5 g of Kgf / mm 2 ) was dispersed in 263 g of an aqueous solution of n-butanol having a concentration of 5% by weight, and the mixture was irradiated with ultrasonic waves to monodisperse silica particles in a solvent. While gently stirring the monodispersed liquid, a mixed liquid of 27 g of methyltrimethoxysilane and 3 g of vinyltrimethoxysilane was added. At this time, a layer of a dispersion liquid of silica core particles was formed below, and a layer of a mixed liquid of methyltrimethoxysilane and vinyltrimethoxylan was formed thereon.
【０１３４】ついで濃度０.２８％のＮＨ3水溶液６.０
ｇをシリカ核粒子の分散液の層に加えた。ＮＨ3添加後
メチルトリメトキシシランとビニルトリメトキシランの
混合層がなくなるまで約２時間撹拌しながらメチルトリ
メトキシシランとビニルトリメトキシランの加水分解を
行った。この時、分散液は白濁しゲル状物の生成が認め
られた。粒子を取り出し、エタノールにて洗浄し、つい
で８０℃で２時間乾燥して得られたポリオルガノシロキ
サン粒子（Ｇ-１）の平均粒子径は４.６μｍで、実質的
な被覆層の形成は認められなかった。このため加熱処理
および１０％Ｋ値の測定は実施しなかった。Then, an aqueous NH 3 solution having a concentration of 0.28% 6.0 was prepared.
g was added to the layer of dispersion of silica core particles. After the addition of NH 3, the hydrolysis of methyltrimethoxysilane and vinyltrimethoxylan was performed while stirring for about 2 hours until the mixed layer of methyltrimethoxysilane and vinyltrimethoxylan disappeared. At this time, the dispersion became cloudy and the formation of a gel-like substance was recognized. The particles were taken out, washed with ethanol, and then dried at 80 ° C. for 2 hours. The obtained polyorganosiloxane particles (G-1) had an average particle size of 4.6 μm, and the formation of a substantial coating layer was recognized. I couldn't. Therefore, the heat treatment and the measurement of the 10% K value were not performed.
【０１３５】[0135]
【比較例２】内容積２Ｌの容器に純水１,３１６ｇを入
れ、撹拌しながら０±１℃に温度調節する。さらに、あ
らかじめ温度５℃に調整したメチルトリメトキシシラン
１５０ｇを静かに加え、メチルトリメトキシシランと純
水が上下２層に分離した状態とした。その後、上層のメ
チルトリメトキシシランの温度が１±１℃になるまで撹
拌しながら冷却した。ついで、純水２７.９ｇにブチル
アルコール０.７ｇと濃度２８％のアンモニア水０.３ｇ
を加え、温度を５±１℃に調整した混合溶液を、上下２
層に分離した下層を撹拌しながらこの下層に６０分で添
加した。引き続き２時間撹拌を継続してポリオルガノシ
ロキサン粒子の分散液とした。（粒径５.０μｍ、粒子
径変動係数１０.４％） この分散液の液温を０±１℃に維持しながら、メチルト
リメトキシシラン６０１ｇと、５±１℃に温度調整した
純水２３５３ｇ、ブチルアルコール５９ｇ、濃度２８％
のアンモニア水０．５ｇの混合液をそれぞれ２４時間で
添加してポリオルガノシロキサン粒子分散液を調製し
た。Comparative Example 2 1,316 g of pure water was placed in a container having an internal volume of 2 L, and the temperature was adjusted to 0 ± 1 ° C. while stirring. Further, 150 g of methyltrimethoxysilane previously adjusted to a temperature of 5 ° C. was gently added, so that methyltrimethoxysilane and pure water were separated into two upper and lower layers. Thereafter, the mixture was cooled with stirring until the temperature of the upper layer methyltrimethoxysilane reached 1 ± 1 ° C. Then, 0.7 g of butyl alcohol and 0.3 g of 28% ammonia water were added to 27.9 g of pure water.
And adjust the temperature of the mixed solution to 5 ± 1 ° C.
The lower layer separated into layers was added to the lower layer with stirring in 60 minutes. Subsequently, stirring was continued for 2 hours to obtain a dispersion of polyorganosiloxane particles. (Particle size 5.0 μm, particle size variation coefficient 10.4%) While maintaining the dispersion at a temperature of 0 ± 1 ° C., 601 g of methyltrimethoxysilane and 2353 g of pure water whose temperature was adjusted to 5 ± 1 ° C. , Butyl alcohol 59g, concentration 28%
A mixture of 0.5 g of aqueous ammonia was added over 24 hours to prepare a polyorganosiloxane particle dispersion.
【０１３６】ついで粒子を分離し、アルコールで洗浄
し、１１０℃で２時間乾燥した後、窒素雰囲気下、４４
０℃で３時間で１時間加熱処理したポリオルガノシロキ
サン粒子（Ｈ-１）を得た。Next, the particles were separated, washed with alcohol and dried at 110 ° C. for 2 hours.
Polyorganosiloxane particles (H-1) heat-treated at 0 ° C. for 3 hours for 1 hour were obtained.
【０１３７】得られた粒子について平均粒径、粒子径変
動係数、１０％Ｋ値および１０％Ｋ値の変動係数を測定
および算出し、結果を表１に示す。With respect to the obtained particles, the average particle diameter, the particle diameter variation coefficient, the 10% K value, and the variation coefficient of the 10% K value were measured and calculated, and the results are shown in Table 1.
【０１３８】[0138]
【比較例３】比較例２において、粒子を分離し、アルコ
ールで洗浄し、１１０℃で２時間乾燥した後、窒素雰囲
気下で行う加熱処理を、６５０℃で３時間にしたポリオ
ルガノシロキサン粒子（Ｈ-２）を得た。さらに、オル
ガノシロキサン粒子（Ｈ−２）と同じ操作を繰り返して
ポリオルガノシロキサン被覆粒子（H'-1）、(H'-2)、
（H'-3）、(H'-4)を得た。Comparative Example 3 Polyorganosiloxane particles obtained in Comparative Example 2 were separated, washed with alcohol, dried at 110 ° C. for 2 hours, and then heat-treated at 650 ° C. for 3 hours under a nitrogen atmosphere. H-2) was obtained. Further, the same operation as that of the organosiloxane particles (H-2) was repeated to obtain polyorganosiloxane-coated particles (H'-1), (H'-2),
(H′-3) and (H′-4) were obtained.
【０１３９】得られた各粒子について平均粒径、粒子径
変動係数、１０％Ｋ値および１０％Ｋ値の変動係数を測
定および算出し、結果を表１に示す。For each of the obtained particles, the average particle diameter, the particle diameter variation coefficient, the 10% K value and the variation coefficient of the 10% K value were measured and calculated, and the results are shown in Table 1.
【０１４０】[0140]
【比較例４、５】比較例２において、粒子を分離し、ア
ルコールで洗浄し、１１０℃で２時間乾燥した後、窒素
雰囲気下で行う加熱処理を、それぞれ７００℃で３時
間、１０００℃で１時間にしたポリオルガノシロキサン
粒子（Ｈ-３）および（Ｈ-４）を得た。Comparative Examples 4 and 5 In Comparative Example 2, the particles were separated, washed with alcohol, dried at 110 ° C. for 2 hours, and then heat-treated in a nitrogen atmosphere at 700 ° C. for 3 hours and at 1000 ° C. for 3 hours. Polyorganosiloxane particles (H-3) and (H-4) obtained for 1 hour were obtained.
【０１４１】得られた粒子について平均粒径、粒子径変
動係数、１０％Ｋ値および１０％Ｋ値の変動係数を測定
および算出し、結果を表１に示す。For the obtained particles, the average particle diameter, the particle diameter variation coefficient, the 10% K value and the variation coefficient of the 10% K value were measured and calculated, and the results are shown in Table 1.
【０１４２】[0142]
【実施例７】液晶表示装置の液晶セルに用いられる一対
の透明電極付透明基板を準備した。この透明電極付透明
基板は、ガラス基板の片面に透明電極としてのＩＴＯ薄
膜、液晶材料に含まれている液晶性化合物分子を所定方
向に配向させる配向膜がこの順序で形成されている。Example 7 A pair of transparent substrates with transparent electrodes used for a liquid crystal cell of a liquid crystal display device were prepared. In this transparent substrate with a transparent electrode, an ITO thin film as a transparent electrode and an alignment film for aligning liquid crystal compound molecules contained in a liquid crystal material in a predetermined direction are formed on one surface of a glass substrate in this order.
【０１４３】一方の透明電極付透明基板に形成された配
向膜面に実施例１で得られたポリオルガノシロキサン被
覆弾性粒子（Ａ−１）を散布密度が約１３０個／ｍｍ2
となるように均一に散布した。The polyorganosiloxane-coated elastic particles (A-1) obtained in Example 1 were sprayed onto the surface of the alignment film formed on one transparent substrate with a transparent electrode at a density of about 130 particles / mm 2.
And sprayed uniformly.
【０１４４】次いで、散布したポリオルガノシロキサン
被覆弾性粒子（Ａ−１）上に、他方の透明電極付透明基
板に形成された配向膜面を接触させ、両透明電極付透明
基板を重ね合わせた。 こうして両透明電極付透明基板
の配向膜間に形成された隙間に液晶材料を充填し、つぎ
に実施例６で得たポリオルガノシロキサン被覆弾性粒子
（Ｆ−１）を混合したシール用樹脂を用いて両基板の周
縁部を貼り合わせ、密閉することにより液晶セルを作成
した。また、作成した液晶セルはＳＴＮモードで駆動さ
れるようになっている。Next, the surface of the alignment film formed on the other transparent substrate with a transparent electrode was brought into contact with the dispersed polyorganosiloxane-coated elastic particles (A-1), and both transparent substrates with a transparent electrode were overlapped. The gap formed between the alignment films of the transparent substrates with both transparent electrodes is filled with a liquid crystal material in this manner, and then the sealing resin mixed with the polyorganosiloxane-coated elastic particles (F-1) obtained in Example 6 is used. The liquid crystal cell was prepared by bonding the peripheral portions of both substrates together and sealing them. Further, the created liquid crystal cell is driven in the STN mode.
【０１４５】以上のようにして作成した液晶セルを室温
から−４０℃に冷却する操作を１０回繰り返し、毎回−
４０℃で気泡の観察を行ったが、液晶セルの内部に低温
気泡は観察されなかった。The operation of cooling the liquid crystal cell prepared as described above from room temperature to −40 ° C. was repeated 10 times,
The bubbles were observed at 40 ° C., but no low-temperature bubbles were observed inside the liquid crystal cell.
【０１４６】また、以上のようにして作成した液晶セル
を液晶表示装置に取り付けて液晶表示装置を駆動させた
が、表示ムラは全く観察されなかった。When the liquid crystal cell prepared as described above was mounted on a liquid crystal display and the liquid crystal display was driven, no display unevenness was observed.
【０１４７】[0147]
【実施例８】一方の透明電極付透明基板に形成された配
向膜面に実施例５で得られたポリオルガノシロキサン被
覆弾性粒子（Ｆ−１）を散布した以外は実施例７と同様
にして液晶セルおよび液晶表示装置を作成し、実施例７
と同様に低温気泡の発生および表示ムラの観察を行った
が、何れも観察されず、コントラストも良好であった。Example 8 The same procedure as in Example 7 was carried out except that the polyorganosiloxane-coated elastic particles (F-1) obtained in Example 5 were sprayed on the surface of the alignment film formed on one transparent substrate with a transparent electrode. Example 7 A liquid crystal cell and a liquid crystal display device were prepared, and
Observation of the occurrence of low-temperature air bubbles and display unevenness was performed in the same manner as in Example 1. However, none of them was observed, and the contrast was good.
【０１４８】[0148]
【比較例６】一方の透明電極付透明基板に形成された配
向膜面に比較例２で得られたポリオルガノシロキサン粒
子（Ｈ−１）を散布し、比較例４で得られたポリオルガ
ノシロキサン粒子（Ｈ−３）を混合したシール用樹脂を
用いた以外は実施例７と同様にして液晶セルおよび液晶
表示装置を作成し、実施例７と同様に低温気泡の発生お
よび表示ムラの観察を行ったところ、６回目の冷却操作
以降で液晶セルの内部に低温気泡が観察され、また、液
晶表示装置を駆動させたところ表示画像ムラが観察され
た。Comparative Example 6 The polyorganosiloxane particles obtained in Comparative Example 4 were sprayed with the polyorganosiloxane particles (H-1) obtained in Comparative Example 2 on the alignment film surface formed on one transparent substrate with a transparent electrode. A liquid crystal cell and a liquid crystal display device were prepared in the same manner as in Example 7 except that the sealing resin mixed with the particles (H-3) was used. As a result, low-temperature air bubbles were observed inside the liquid crystal cell after the sixth cooling operation, and when the liquid crystal display device was driven, display image unevenness was observed.
【０１４９】[0149]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小 松 通 郎 福岡県北九州市若松区北湊町13番２号 触 媒化成工業株式会社若松工場内 Ｆターム(参考） 2H089 LA07 LA19 MA05X NA17 PA06 QA14 SA06 4J002 CP03W CP03X DJ016 FB096 GQ00 GS00 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshiro Komatsu 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu City, Fukuoka Prefecture 4J002 CP03W CP03X DJ016 FB096 GQ00 GS00
Claims (4)
サン被覆層とからなる積層微粒子であって、 該ポリオルガノシロキサン被覆層が、下記式（１）で表
される有機珪素化合物の２種以上の混合物の加水分解物
・縮重合物からなり、かつ、 該混合物が、有機珪素化合物の直接ケイ素原子に結合し
た炭化水素基（Ｒ1−Ｓｉ基）の分解温度が互いに異な
る２種以上の有機珪素化合物の混合物であることを特徴
とするポリオルガノシロキサン被覆弾性微粒子。 Ｒ1 nＳi(ＯＲ2)4-n （１） （式中、Ｒ1は置換または非置換の炭化水素基から選ば
れる炭素数１〜１０の炭化水素基を示し、Ｒ2は水素原
子、炭素数１〜５のアルキル基、炭素数２〜５のアシル
基を示し、ｎは１〜３の整数である）1. A laminated fine particle comprising core particles and a polyorganosiloxane coating layer on the surface of the core particles, wherein the polyorganosiloxane coating layer comprises at least two kinds of organosilicon compounds represented by the following formula (1). And a mixture of two or more organic compounds having different decomposition temperatures of hydrocarbon groups (R 1 -Si groups) directly bonded to silicon atoms of the organosilicon compound. Polyorganosiloxane-coated elastic fine particles, which are a mixture of silicon compounds. R 1 n Si (OR 2 ) 4-n (1) (wherein, R 1 represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, R 2 represents a hydrogen atom, Represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and n is an integer of 1 to 3)
子が、 (i)平均粒子径が０.５〜３０μｍの範囲にあり、 (ii)被覆層の厚さが０.１〜１０μｍの範囲にあり、 (iii)下記式[I]で定義されるポリオルガノシロキサン被
覆弾性微粒子の１０％Ｋ値が１００〜６０００Kgf/mm2
の範囲にあり、 (iv)核粒子の１０％Ｋ値が５００〜６０００Kgf/mm2の
範囲にあり、 (v)該核粒子およびポリオルガノシロキサン被覆弾性微
粒子の粒子径変動係数が１０％以下であることを特徴と
する請求項１に記載のポリオルガノシロキサン被覆弾性
微粒子。 Ｋ＝(３／２1/2)・Ｆ・Ｓ-3/2・(Ｄ／２)-1/2 …[I] 式中、 Ｆ：微粒子の１０％圧縮変形時の荷重値（Kg
f） Ｓ：微粒子の１０％圧縮変形時の圧縮変位（mm） Ｄ：粒子直径（mm） を示
す。2. The elastic fine particles coated with polyorganosiloxane, wherein (i) the average particle diameter is in the range of 0.5 to 30 μm, (ii) the thickness of the coating layer is in the range of 0.1 to 10 μm, (iii) The 10% K value of the polyorganosiloxane-coated elastic fine particles defined by the following formula [I] is 100 to 6000 kgf / mm 2.
(Iv) the 10% K value of the core particles is in the range of 500 to 6000 kgf / mm 2 , and (v) the core particles and the polyorganosiloxane-coated elastic fine particles have a particle diameter variation coefficient of 10% or less. The polyorganosiloxane-coated elastic fine particles according to claim 1, wherein: K = (3/2 1/2 ) ・FS -3 / 2 ・ (D / 2) -1/2 ... [I] where, F: load value at the time of 10% compression deformation of fine particles (Kg
f) S: Compressive displacement (mm) at the time of 10% compressive deformation of fine particles D: Particle diameter (mm)
との混合溶媒に分散させて疎水性核粒子の分散液を調製
し、 (b)上記分散液中で、界面活性剤および加水分解用触媒
の存在下に、 上記式(1)で表される有機珪素化合物から選ばれる２種
以上の混合物であって、有機珪素化合物の直接ケイ素原
子に結合した炭化水素基の分解温度が互いに異なる有機
珪素化合物の混合物を加水分解し、加水分解物を疎水性
核粒子表面に析出させ、疎水性核粒子の表面にポリオル
ガノシロキサン被覆層を形成してポリオルガノシロキサ
ン被覆弾性微粒子分散液を調製したのち、 (c)ついで、ポリオルガノシロキサン被覆弾性微粒子分
散液からポリオルガノシロキサン被覆弾性微粒子を分離
し、 被覆層形成に用いた有機珪素化合物の直接ケイ素原子に
結合した炭化水素基の分解温度のうち、最も低い分解温
度以上の温度で加熱処理することを特徴とするポリオル
ガノシロキサン被覆弾性微粒子の製造方法。3. A dispersion of hydrophobic core particles is prepared by dispersing (a) the hydrophobic core particles in water or a mixed solvent of water and an organic solvent, and (b) a surfactant in the dispersion. And in the presence of a hydrolysis catalyst, a decomposition temperature of a hydrocarbon group directly bonded to a silicon atom of a mixture of two or more kinds selected from the organosilicon compounds represented by the above formula (1). Hydrolyze a mixture of organic silicon compounds different from each other, precipitate the hydrolyzate on the surface of the hydrophobic core particles, form a polyorganosiloxane coating layer on the surface of the hydrophobic core particles, and disperse the polyorganosiloxane-coated elastic fine particles. (C) Then, the polyorganosiloxane-coated elastic fine particles are separated from the polyorganosiloxane-coated elastic fine particle dispersion, and the hydrocarbons directly bonded to silicon atoms of the organosilicon compound used for forming the coating layer are formed. A method for producing polyorganosiloxane-coated elastic fine particles, wherein a heat treatment is performed at a temperature equal to or higher than the lowest decomposition temperature among the decomposition temperatures of elementary groups.
極間および／または液晶層周縁部に請求項１または２に
記載のポリオルガノシロキサン被覆弾性微粒子がスペー
サーとして介在していることを特徴とする液晶表示装
置。4. A liquid crystal cell having a pair of electrodes, wherein the polyorganosiloxane-coated elastic fine particles according to claim 1 are interposed between the electrodes and / or at the periphery of the liquid crystal layer as spacers. A liquid crystal display device characterized by the above-mentioned.
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|---|---|---|---|
| JP01243999A JP3524008B2 (en) | 1999-01-20 | 1999-01-20 | Method for producing elastic particles coated with polyorganosiloxane and liquid crystal display |
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| JP3524008B2 JP3524008B2 (en) | 2004-04-26 |
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