JP2007171655A - Silicon-containing fine particles, display liquid for electrophoretic display device, and electrophoretic display element including the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide particulate containing silicon which is not flocculated even in a solvent having a low dielectric constant, a display liquid for an electrophoretic display device, and an electrophoretic display element using the display liquid. <P>SOLUTION: Particulate containing silicon is obtained by co-hydrolysis reaction of polydimethylsiloxane-polymethacryloxy-propyltrimethoxy silane copolymer and tetraalkoxy silane in a solution, and the display liquid for an electrophoretic display device using the particulates, and the electrophoretic display element including the display liquid are disclosed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to silicon-containing fine particles useful as display particles used in a display element using electrophoresis, a display liquid containing the particles, and an electrophoretic display element using the display liquid.

Conventionally, display elements using electrophoresis are known. It consists of two transparent substrates such as ITO electrodes facing each other at a certain interval, and enclosing a suspension obtained by dispersing electrophoretic particles (display particles) in a dispersion medium, An electrophoretic display element was developed by applying voltage between the electrode plates to move the display particles to the transparent electrode plate side or the opposite side, and recognizing the contrast of the display particles from the transparent electrode plate side. (See Patent Documents 1 and 2).
Such an electrophoretic display element is required to use a dispersion medium having a low dielectric constant in order to prevent an electric current from flowing between electrodes when a voltage is applied, thereby causing an electrolysis reaction or the like. . However, a dispersion medium having a low dielectric constant is generally a solvent that is insoluble in water.
On the other hand, particles that can be used in electrophoretic display elements have a hydrophilic surface and are easily dispersed in water or alcohol, but tend to aggregate in water-insoluble solvents. When particles agglomerate, the apparent particle diameter increases and sedimentation or levitation tends to occur. After displaying on the electrophoretic display element, the particles collected near the electrode cause sedimentation or levitation, which is a cause of failure to maintain display storability.
JP-A-63-244095 JP-A-1-86116

  The present invention has been made in view of the above-described circumstances, and provides silicon-containing fine particles that do not aggregate even in a solvent having a low dielectric constant, a display liquid for an electrophoretic display device, and an electrophoretic display element using the display liquid. For the purpose.

  In order to achieve such an object, the present inventor has found that silicon-containing fine particles obtained by cohydrolyzing a specific copolymer and a specific tetraalkoxysilane solve the above-mentioned problems and completed the present invention. did. Furthermore, in order to obtain display particles having an arbitrary color, silicon obtained by cohydrolyzing a specific copolymer and a specific tetraalkoxysilane in the presence of colored fine particles mainly composed of an inorganic compound. The present invention has been completed by finding that it is effective to use the fine particles. The present invention is as follows.

1. (A) silicon obtained by cohydrolysis reaction of at least one copolymer represented by formula (1) and at least one tetraalkoxysilane represented by (b) formula (2) in a solution Containing fine particles.

In the formula (1), n is an integer of ^{1 to} 1,000; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each hydrogen, 30, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene, which has 2 to 20 carbon atoms, and any hydrogen is May be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene, any hydrogen may be replaced by halogen or alkyl having 1-10 carbons well, and any -CH 2 in the alkyl _- is _{-O -, - CH 2 = CH} 2 - or may also be substituted or unsubstituted replaced by phenylene aryl, and substituted or unsubstituted aryl , Arbitrary hydrogen may be replaced by fluorine arbitrary -CH ₂ - _{-O -, - CH 2 = CH} 2 - or independently constituted arylalkyl, from between the alkylene which may be replaced by a cycloalkylene Z is a group having 2 to 20 carbon atoms, an arbitrary —CH ₂ — in which —CH ₂ — may be replaced by —O—, or an arbitrary —CH _2- is alkenylene which may be replaced by -O-; X is halogen; and P ¹ is obtained by polymerization of at least one addition polymerizable monomer having a hydrolyzable group directly attached to silicon. Is a chain of structural units. In the formula (2), R ⁸ is phenyl or alkyl having 1 to 20 carbons.

2. In the copolymer represented by the formula (1), P ¹ is a structural unit obtained by polymerization of at least one silane coupling agent having at least one functional group selected from vinyl, acryloyl, methacryloyl and styryl. 2. The silicon-containing fine particle according to 1 above, which is a chain.

3. In the copolymer represented by the formula (1), P ¹ has a hydrolyzable group directly bonded to silicon, a group of acrylic acid ester and methacrylic acid ester, and a hydrolyzable group directly bonded to silicon. 2. The silicon-containing fine particle according to 1 above, which is a chain of structural units obtained by polymerization of at least one addition polymerizable monomer selected from the group of styrene derivatives.

4). 2. The copolymer represented by the formula (1), wherein P ¹ is a chain of structural units obtained by polymerization of at least one addition-polymerizable monomer represented by the formula (A). Silicon-containing fine particles.

In the formula (A), R ^A , R ^B and R ^C are each independently alkyl, alkoxy, alkenyloxy or acyloxy having 1 to 4 carbon atoms, and at least one of R ^A , R ^B and R ^C One is alkoxy having 1 to 4 carbon atoms, alkoxy, alkenyloxy, or acyloxy; R ^D is hydrogen or methyl; X ^A is alkylene having 2 to 20 carbon atoms; Any —CH ₂ — except may be replaced by —O—, —NH— or —CH (OH) —.

5. 2. The copolymer represented by the formula (1), wherein P ¹ is a chain of structural units obtained by polymerization of at least one addition-polymerizable monomer represented by the formula (A). Silicon-containing fine particles.

In the formula (A), R ^A , R ^B and R ^C are independently methyl, ethyl, methoxy, ethoxy, 1-propoxy, 2-propoxy, 2-propenyloxy or acetyloxy, and R ^A , R ^At least one of ^B 1 and R ^C is methoxy, ethoxy, 1-propoxy, 2-propoxy, 2-propenyloxy, or acetyloxy; R ^D is hydrogen or methyl; X ^A is —CH ₂ CH ₂ CH ₂ —, — (CH ₂ CH ₂ O) mCH ₂ CH ₂ CH ₂ — or —CH (OH) CH ₂ NHCH ₂ CH ₂ CH ₂ —. Here, m is an integer of 1 to 3.

6). 2. The silicon according to 1 above, wherein in the copolymer represented by the formula (1), P ¹ is a chain of structural units obtained by polymerization of at least one addition polymerizable monomer represented by the formula (B). Containing fine particles.

In the formula (B), R ^E , R ^F , and R ^G are each alkyl having 1 to 4 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—, and R ^E , R ^F, at least one of R ^G _{are, -O-CH 3, -O-} CH 2 CH 3, -O-CH 2 CH 2 CH 3, -O-CH (CH 3) it is _2; R ^H is hydrogen or methyl; X ^B is 2 to 20 carbon atoms, any -CH ₂ - alkylene good be replaced by -O-, arylene having 6 to 20 carbon atoms, or carbon atoms, 7 It is a divalent group defined by removing any two hydrogens from ˜20 arylalkyl, and arbitrary —CH ₂ — may be replaced by —O—.

7). The silicon-containing fine particles according to any one of 1 to 6 above, wherein in the tetraalkoxysilane represented by the formula (2), R ⁸ is alkyl having 1 to 4 carbon atoms.

8). (A) at least one copolymer represented by formula (1) and (b) at least one tetraalkoxysilane represented by formula (2), and (c) fine particles mainly composed of an inorganic compound. Silicon-containing fine particles obtained by cohydrolysis reaction in solution in the presence.

In the formula (1), n is an integer of ^{1 to} 1,000; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each hydrogen, 30, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene, which has 2 to 20 carbon atoms, and any hydrogen is May be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene, any hydrogen may be replaced by halogen or alkyl having 1-10 carbons well, and any -CH 2 in the alkyl _- is _{-O -, - CH 2 = CH} 2 - or may also be substituted or unsubstituted replaced by phenylene aryl, and substituted or unsubstituted aryl , Arbitrary hydrogen may be replaced by fluorine arbitrary -CH ₂ - _{-O -, - CH 2 = CH} 2 - or independently constituted arylalkyl, from between the alkylene which may be replaced by a cycloalkylene Z is a group having 2 to 20 carbon atoms, an arbitrary —CH ₂ — in which —CH ₂ — may be replaced by —O—, or an arbitrary —CH _2- is alkenylene which may be replaced by -O-; X is halogen; and P ¹ is obtained by polymerization of at least one addition polymerizable monomer having a hydrolyzable group directly attached to silicon. Is a chain of structural units. In the formula (2), R ⁸ is phenyl or alkyl having 1 to 20 carbons.

9. 8. The silicon-containing fine particles according to any one of 1 to 7 above, wherein the average particle diameter is 50 to 1,000 nm.
10. 9. The silicon-containing fine particles according to 8 above, having an average particle size of 50 to 10,000 nm.
11. 11. A display liquid for electrophoretic display devices, comprising the silicon-containing fine particles according to any one of 1 to 10 above and a dispersion medium.
12 12. An electrophoretic display device comprising the display liquid as described in 11 above sealed between a pair of opposingly arranged electrode plates, at least one of which is transparent.

  The silicon-containing fine particles of the present invention have a diorganopolysiloxane moiety that has an affinity for water-insoluble organic solvents, so that they are stably dispersed without causing aggregation even in water-insoluble organic solvents. Is done. Moreover, since it does not contain an obstructing component, it has a feature that these processes are easy. Therefore, the display liquid for an electrophoretic display device of the present invention containing such fine particles is a stable suspension, and the electrophoretic display element of the present invention using such a display liquid is excellent in display stability. It is a thing.

First, terms used in the present invention will be described. “Arbitrary” means that not only the position but also the number can be arbitrarily selected. The description that any —CH ₂ — may be replaced by —O— does not include the case where a plurality of consecutive —CH ₂ — are replaced by —O—. For example, alkyl in which any —CH ₂ — may be replaced by —O— or —CH═CH— includes alkoxy, alkoxyalkyl, alkenyl, alkyloxyalkenyl and alkenyl in addition to alkyl when not substituted. Oxyalkyl is included.
Alkyl and alkylene may both be straight-chain groups or branched groups. This also applies when any —CH ₂ — is replaced by another divalent group. For example, all of alkyl, alkenylene, alkenyl and alkylene in the above-mentioned alkyloxyalkenyl and alkenyloxyalkyl may be a straight-chain group or a branched group. Both cycloalkyl and cycloalkenyl may or may not be a bridged ring structure group. A (meth) acrylic acid derivative is used as a general term for an acrylic acid derivative and a methacrylic acid derivative. (Meth) acrylate is used as a general term for acrylate and methacrylate. (Meth) acryloyloxy is used as a general term for acryloyloxy and methacryloyloxy.

Preferred specific examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 in} the formula (1) will be described.
When R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are alkyl, the carbon number is 1-30. A preferable carbon number is 1-20. Any hydrogen in the alkyl may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene. Preferred examples of such alkyl include unsubstituted alkyl having 1 to 20 carbons, alkoxyalkyl having 2 to 20 carbons, and a group in which one —CH ₂ — is substituted with cycloalkylene in 1 to 8 carbons. And in these groups mentioned here, any hydrogen is replaced by fluorine. The preferred number of carbon atoms in the cycloalkylene is 3-8.

  Examples of unsubstituted alkyl having 1 to 30 carbons are methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 1,1,2 -Trimethylpropyl, heptyl, octyl, 2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, triacontyl and the like.

  Examples of fluorinated alkyls having 1 to 30 carbons are 2-fluoroethyl, 2,2-difluoroethyl, 3,3,3-trifluoropropyl, hexafluoropropyl, nonafluoro-1,1,2,2 -Tetrahydrohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro- 1H, 1H, 2H, 2H-tetradecyl and the like.

  Examples of alkoxyalkyls having 2 to 29 carbons and fluorinated alkoxyalkyls include 3-methoxypropyl, methoxyethoxyundecyl, 2-fluoroethyloxypropyl, 2,2,2-trifluoroethyloxypropyl, 2- Fluoro-1-fluoromethylethyloxypropyl, 2,2,3,3-tetrafluoropropyloxypropyl, 2,2,3,3,3-pentafluoropropyloxypropyl, hexafluoroisopropyloxypropyl, heptafluoroisopropyloxy Propyl, hexafluorobutyloxypropyl, heptafluorobutyloxypropyl, octafluoroisobutyloxypropyl, octafluoropentyloxypropyl, 2-fluoroethyloxybutyl, 2,2,2-trifluoro Ethyloxybutyl, 2-fluoro-1-fluoromethylethyloxybutyl, 2,2,3,3-tetrafluoropropyloxybutyl, 2,2,3,3,3-pentafluoropropyloxybutyl, hexafluoroisopropyloxy Butyl, hexafluorobutyloxybutyl, heptafluorobutyloxybutyl, octafluoroisobutyloxybutyl, octafluoropentyloxybutyl, 2-fluoroethyloxyisobutyl, 2,2,2-trifluoroethyloxyisobutyl, 2-fluoro-1 -Fluoromethylethyloxyisobutyl, 2,2,3,3-tetrafluoropropyloxyisobutyl, 2,2,3,3,3-pentafluoropropyloxyisobutyl, hexafluoroisopropyloxyisobutyl, Sa-fluoro-butyloxy isobutyl, heptafluorobutyl oxy isobutyl, octafluoroisobutyl oxy isobutyl, a octafluoropentyloxy isobutyl and the like.

Examples of alkyl having 1 to 8 carbon atoms and wherein one —CH ₂ — is replaced by cycloalkylene are cyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl, 2-bicycloheptyl, cyclooctyl and the like. Cyclohexyl is an example where methyl —CH ₂ — is replaced by cyclohexylene. Cyclohexylmethyl is an example in which —CH ₂ — at the β-position of ethyl is replaced by cyclohexylene.

When R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are alkenyl, the carbon number is 2-20. Any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene. Preferred examples of such alkenyl include alkenyl having 2 to 20 carbon atoms, alkenyloxyalkyl having 3 to 20 carbon atoms, alkyloxyalkenyl having 3 to 20 carbon atoms, and having 1 to 1 carbon atoms. 8 and alkyl in which one —CH ₂ — is replaced by cycloalkenylene, and groups in which any hydrogen in these groups listed here is replaced by fluorine. The preferred number of carbon atoms of cycloalkenylene is 3-8.
Examples of alkenyl having 2 to 20 carbon atoms are vinyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl, 21-docosenyl and the like. An example of an alkenyloxyalkyl having 3 to 20 carbon atoms is allyloxyundecyl. Examples of alkyl having 1 to 8 carbon atoms and wherein one —CH ₂ — is replaced by cycloalkenylene are 2- (3-cyclohexenyl) ethyl, 5- (bicycloheptenyl) ethyl, 2- And cyclopentenyl, 3-cyclohexenyl, 5-norbornen-2-yl, 4-cyclooctenyl and the like.

In the case where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ in formula (1) are substituted or unsubstituted aryl, any hydrogen is halogen or 1-10 Phenyl optionally substituted with alkyl having carbon and unsubstituted naphthyl. Preferred examples of halogen are fluorine, chlorine and bromine. In alkyl, which is a phenyl substituent, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH— or phenylene. That is, specific examples of preferable aryl include phenyl, unsubstituted naphthyl, alkylphenyl, alkyloxyphenyl, alkenylphenyl, phenyl having at least one —CH ₂ — substituted with phenylene as a substituent, and these In this group, any hydrogen is replaced with a halogen. In the present invention, when simply expressed as phenyl without particular notice, it means unsubstituted phenyl.

  Examples of halogenated phenyl are pentafluorophenyl, 4-chlorophenyl, 4-bromophenyl and the like.

  Examples of alkylphenyl are 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl. 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 4- (1-methylethyl) phenyl, 4- (1,1-dimethylethyl) phenyl, 4- (2-ethylhexyl) phenyl, 2,4,6-tris (1-methylethyl) phenyl and the like.

  Examples of alkyloxyphenyl are (4-methoxy) phenyl, (4-ethoxy) phenyl, (4-propoxy) phenyl, (4-butoxy) phenyl, (4-pentyloxy) phenyl, (4-heptyloxy) phenyl , (4-decyloxy) phenyl, (4-octadecyloxy) phenyl, 4- (1-methylethoxy) phenyl, 4- (2-methylpropoxy) phenyl, 4- (1,1-dimethylethoxy) phenyl, and the like. . Examples of alkenylphenyl are 4-vinylphenyl, 4- (1-methylvinyl) phenyl, 4- (3-butenyl) phenyl and the like.

Examples of phenyl having as substituent an alkyl in which at least one —CH ₂ — is replaced by phenylene are 4- (2-phenylvinyl) phenyl, 4-phenoxyphenyl, 3- (phenylmethyl) phenyl, biphenyl, terphenyl Etc. 4- (2-phenylvinyl) phenyl, in ethyl ethyl phenyl, one -CH ₂ - is replaced by phenylene, another -CH ₂ - is an example for which it is replaced by -CH = CH-.

  Examples of phenyl in which some of the hydrogens on the benzene ring are replaced by halogens, and other hydrogens are replaced by alkyl, alkyloxy or alkenyl include 3-chloro-4-methylphenyl, 2,5-dichloro-4-methyl Phenyl, 3,5-dichloro-4-methylphenyl, 2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl, 3-bromo-4-methylphenyl, 2, 5-dibromo-4-methylphenyl, 3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl, 3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl, 3 , 5-Dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl, 2,3-difluoro-4-ethoxyphenyl Le, 2,3-difluoro-4-propoxy-phenyl, 4-vinyl-2,3,5,6-tetrafluorophenyl, and the like.

Next, an example in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ in formula (1) are substituted or unsubstituted arylalkyl will be described. Substituted or unsubstituted arylalkyl is substituted or unsubstituted aryl, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— or cycloalkylene. An arylalkyl composed of alkylene which may be substituted.

In the arylalkyl alkylene, any hydrogen may be replaced with fluorine and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene. A preferred example of arylalkyl is phenylalkyl. At this time, any hydrogen of the phenyl may be replaced by halogen or alkyl having 1 to 12 carbons. In this alkyl, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH—, cycloalkylene, or phenylene. And the preferable carbon number of alkylene is 1-12, and a more preferable carbon number is 1-8.

  Examples of unsubstituted phenylalkyl are phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 11-phenylundecyl, 1-phenylethyl, 2-phenyl Phenylpropyl, 1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl, 1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2-phenylpropyl, 1-phenylhexyl, etc. It is.

  Examples of phenylalkyl in which at least one hydrogen of phenyl is replaced by fluorine are 4-fluorophenylmethyl, 2,3,4,5,6-pentafluorophenylmethyl, 2- (2,3,4,5,6 -Pentafluorophenyl) ethyl, 3- (2,3,4,5,6-pentafluorophenyl) propyl, 2- (2-fluorophenyl) propyl, 2- (4-fluorophenyl) propyl and the like.

  Examples of phenylalkyl in which at least one hydrogen of phenyl is replaced by chlorine are 4-chlorophenylmethyl, 2-chlorophenylmethyl, 2,6-dichlorophenylmethyl, 2,4-dichlorophenylmethyl, 2,3,6-trichlorophenylmethyl 2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl, 2,3,4,6-tetrachlorophenylmethyl, 2,3,4,5,6-pentachlorophenylmethyl, 2- ( 2-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2,4,5-chlorophenyl) ethyl, 2- (2,3,6-chlorophenyl) ethyl, 3- (3-chlorophenyl) propyl, 3- (4-Chlorophenyl) propyl, 3- (2,4,5-trichlorophenyl) propi 3- (2,3,6-trichlorophenyl) propyl, 4- (2-chlorophenyl) butyl, 4- (3-chlorophenyl) butyl, 4- (4-chlorophenyl) butyl, 4- (2,3,6) -Trichlorophenyl) butyl, 4- (2,4,5-trichlorophenyl) butyl, 1- (3-chlorophenyl) ethyl, 1- (4-chlorophenyl) ethyl, 2- (4-chlorophenyl) propyl, 2- ( 2-chlorophenyl) propyl, 1- (4-chlorophenyl) butyl and the like.

  Examples of phenylalkyl in which at least one hydrogen of phenyl is replaced by bromine are 2-bromophenylmethyl, 4-bromophenylmethyl, 2,4-dibromophenylmethyl, 2,4,6-tribromophenylmethyl, 2, 3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl, 2- (4-bromophenyl) ethyl, 3- (4-bromophenyl) propyl, 3- (3 -Bromophenyl) propyl, 4- (4-bromophenyl) butyl, 1- (4-bromophenyl) ethyl, 2- (2-bromophenyl) propyl, 2- (4-bromophenyl) propyl and the like.

  Examples of phenylalkyl in which at least one hydrogen of phenyl is replaced by alkyl having 1 to 12 carbons are 2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl, 4-dodecylphenylmethyl, 3 , 5-dimethylphenylmethyl, 2- (4-methylphenyl) ethyl, 2- (3-methylphenyl) ethyl, 2- (2,5dimethylphenyl) ethyl, 2- (4-ethylphenyl) ethyl, 2- (3-ethylphenyl) ethyl, 1- (4-methylphenyl) ethyl, 1- (3-methylphenyl) ethyl, 1- (2-methylphenyl) ethyl, 2- (4-methylphenyl) propyl, 2- (2-methylphenyl) propyl, 2- (4-ethylphenyl) propyl, 2- (2-ethylphenyl) propyl, 2- 2,3-dimethylphenyl) propyl, 2- (2,5-dimethylphenyl) propyl, 2- (3,5-dimethylphenyl) propyl, 2- (2,4-dimethylphenyl) propyl, 2- (3 4-dimethylphenyl) propyl, 2- (2,5-dimethylphenyl) butyl, (4- (1-methylethyl) phenyl) methyl, 2- (4- (1,1-dimethylethyl) phenyl) ethyl, 2 -(4- (1-methylethyl) phenyl) propyl, 2- (3- (1-methylethyl) phenyl) propyl and the like.

  Examples of phenylalkyl having 1 to 12 carbons and an alkyl in which at least one hydrogen is replaced by fluorine as a phenyl substituent are 3- (trifluoromethyl) phenylmethyl, 2- (4-tri Fluoromethylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) ethyl, 1- (3-tri Fluoromethylphenyl) ethyl, 1- (4-trifluoromethylphenyl) ethyl, 1- (4-nonafluorobutylphenyl) ethyl, 1- (4-tridecafluorohexylphenyl) ethyl, 1- (4-heptadeca Fluorooctylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) propi 1-methyl-1- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) propyl, 1-methyl-1- (4-tridecafluorohexylphenyl) ethyl, 2- ( 4-heptadecafluorooctylphenyl) propyl, 1-methyl-1- (4-heptadecafluorooctylphenyl) ethyl and the like.

Examples of phenylalkyl having 1 to 12 carbons and an alkyl in which one —CH ₂ — is replaced by —CH═CH— as a substituent of phenyl are 2- (4-vinylphenyl) ethyl, 1- (4-vinylphenyl) ethyl, 1- (2- (2-propenyl) phenyl) ethyl and the like.

Examples of phenylalkyl having 1 to 12 carbons and having one —CH ₂ — substituted by —O— as a phenyl substituent include 4-methoxyphenylmethyl, 3-methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2- (4-methoxyphenyl) ethyl, 3- (4-methoxyphenyl) propyl, 3- (2-methoxyphenyl) propyl, 3- (3,4-dimethoxyphenyl) propyl, 11- (4-methoxyphenyl) undecyl, 1- (4-methoxyphenyl) ethyl, 2- (3- (methoxymethyl) phenyl) ethyl, 3- (2-nonadecafluorodecenyloxyphenyl) propyl and the like.

Phenyl having an alkyl of 1 to 12 carbons, wherein one —CH ₂ — may be replaced by cycloalkylene, and another —CH ₂ — may be replaced by —O— Examples of alkyl are cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylphenylpropyl, cyclohexyloxyphenylmethyl and the like.

1 to 12 the number of carbons, one -CH ₂ - phenylalkyl having a substituent of phenyl alkyl which may be replaced by -O- - is replaced by phenylene, and another -CH ₂ Examples of 2- (4-phenoxyphenyl) ethyl, 2- (4-phenoxyphenyl) propyl, 2- (2-phenoxyphenyl) propyl, 4-biphenylylmethyl, 3-biphenylylethyl, 4-biphenylyl And ethyl, 4-biphenylylpropyl, 2- (2-biphenylyl) propyl, 2- (4-biphenylyl) propyl, and the like.

  Examples of phenylalkyl in which at least two hydrogens of phenyl are replaced by different groups are 3- (2,5-dimethoxy-3,4,6-trimethylphenyl) propyl, 3-chloro-2-methylphenylmethyl, 4- Chloro-2-methylphenylmethyl, 5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl, 2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl, 2, 3-dichloro-4-methylphenylmethyl, 2,5-dichloro-4-methylphenylmethyl, 3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl, 2, 3,5,6-tetrachloro-4-methylphenylmethyl, (2,3,4,6-tetrachloro-5-methylphenyl) Til, 2,3,4,5-tetrachloro-6-methylphenylmethyl, 4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl, 2,4-dichloro-3 , 5-dimethylphenylmethyl, 2,6-dichloro-3,5-dimethylphenylmethyl, 2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl, 4-bromo 2-methylphenylmethyl, 5-bromo-2-methylphenylmethyl, 6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenylmethyl, 2 , 3,5-tribromo-4-methylphenylmethyl, 2,3,5,6-tetrabromo-4-methylphenylmethyl, 11- (3-chloro 4-methoxyphenyl) undecyl and the like.

  The most preferred examples of phenyl in phenylalkyl are unsubstituted phenyl and phenyl having at least one of fluorine, alkyl having 1 to 4 carbons, vinyl and methoxy as a substituent.

In the alkylene constituting phenylalkyl, examples of phenylalkyl in which at least one —CH ₂ — is replaced by —O—, —CH═CH— or cycloalkylene are 3-phenoxypropyl, 1-phenylvinyl, 2-phenyl And vinyl, 3-phenyl-2-propenyl, 4-phenyl-4-pentenyl, 13-phenyl-12-tridecenyl, phenylcyclohexyl, phenoxycyclohexyl and the like.

In the alkylene constituting phenylalkyl, examples of phenylalkenyl in which at least one —CH ₂ — is replaced by —CH═CH— and the hydrogen of phenyl is replaced by fluorine or methyl are 4-fluorophenylvinyl, 2, 3-difluorophenyl vinyl, 2,3,4,5,6-pentafluorophenyl vinyl, 4-methylphenyl vinyl and the like.

More preferred specific examples of R ¹ and R ² are methyl, phenyl and 3,3,3-trifluoropropyl.

More preferred specific examples of R ³ and R ⁴ are methyl or phenyl.

More preferred specific examples of R ⁵ are methyl, ethyl, propyl, n-butyl, s-butyl, t-butyl, phenyl and phenylmethyl.

R ⁶ and R ⁷ are preferably alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or aralkyl having 7 to 20 carbon atoms, and a more preferred specific example is methyl.

In the formula (1), X is halogen, and preferred examples thereof are chlorine, bromine and iodine, and bromine is particularly preferred. Z is alkylene having 2 to 20 carbons or alkenylene having 3 to 8 carbons. In these alkylene and alkenylene, arbitrary —CH ₂ — may be replaced by —O—. Preferred examples of Z are —C ₃ H ₆ —O—C ₂ H ₄ —O—, —C ₃ H ₆ —O—, or —C ₂ H ₄ —O—.
Moreover, in Formula (1), n is an integer of 1-1000, Preferably it is 5-500, More preferably, it is 10-200.

P ¹ is a chain of structural units obtained by polymerization of at least one addition polymerizable monomer having a hydrolyzable group directly bonded to silicon.

P ¹ may be a chain of structural units obtained by polymerization of at least one silane coupling agent having at least one functional group selected from vinyl, (meth) acryloyl, and styryl.

P ¹ is at least an addition polymerizable monomer selected from the group of (meth) acrylic acid ester having a hydrolyzable group directly bonded to silicon and the group of styrene derivatives having a hydrolyzable group directly bonded to silicon. It may be a chain of structural units obtained by one polymerization.

Further, P ¹ may be a chain of structural units obtained by polymerization of at least one addition polymerizable monomer represented by the formula (A).

In the formula (A), R ^A , R ^B and R ^C are each independently alkyl, alkoxy, alkenyloxy or acyloxy having 1 to 4 carbon atoms, but at least R ^A , R ^B and R ^C One is alkoxy, alkenyloxy, or acyloxy having 1 to 4 carbon atoms, R ^D is hydrogen or methyl; X ^A is alkylene having 2 to 20 carbon atoms, and the terminal of this alkylene Any —CH ₂ — except for may be replaced by —O—, —NH— or —CH (OH) —.

More preferably,
In formula (A), R ^A , R ^B , R ^C are independently methyl, ethyl, methoxy, ethoxy, 1-propoxy, 2-propoxy, 2-propenyloxy, or acetyloxy, but R ^A , At least one of R ^B and R ^C is methoxy, ethoxy, 1-propoxy, 2-propoxy, 2-propenyloxy, or acetyloxy; R ^D is hydrogen or methyl; X ^A is —CH ₂ CH ₂ CH ₂ —, — (CH ₂ CH ₂ O) mCH ₂ CH ₂ CH ₂ — or —CH (OH) CH ₂ NHCH ₂ CH ₂ CH ₂ —. Here, m is an integer of 1 to 3.

Further, P ¹ may be a chain of structural units obtained by polymerization of at least one addition polymerizable monomer represented by the formula (B).

In the formula (B), R ^E , R ^F , and R ^G are each alkyl having 1 to 4 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—, and R ^E , R ^F, at least one of R ^G _{are, -O-CH 3, -O-} CH 2 CH 3, -O-CH 2 CH 2 CH 3, -O-CH (CH 3) it is _2; R ^H is hydrogen or methyl; X ^B is 2 to 20 carbon atoms, any -CH ₂ - alkylene good be replaced by -O-, arylene having 6 to 20 carbon atoms, or carbon atoms, 7 It is a divalent group defined by removing any two hydrogens from ˜20 arylalkyl, and arbitrary —CH ₂ — may be replaced by —O—.

  Specific examples of a group of (meth) acrylic acid ester having a hydrolyzable group directly bonded to silicon and a styrene derivative having a hydrolyzable group directly bonded to silicon include 3-methacryloxymethyltrimethoxysilane and 3-methacryloxymethyl Triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltris (methoxyethoxy) silane, methacryloxymethyltrimethoxysilane 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropylmethyldimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (3 -Acryloxypropyl) tris (trimethylsiloxy) silane, bis (triethoxysilyl) ethylene, 1,3- [bis (3-triethoxysilylpropyl) polyethyleneoxy] -2-methylenepropane, 1,1-bis (tri Methoxysilylmethyl) ethylene, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, butenyltrimethoxysilane, butenyltriethoxysilane, 7-octenyltrimethoxysilane, 7- Octenyl triethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane and 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane.

  The above monomers may be used alone or a plurality thereof may be copolymerized. The copolymerization may be random copolymerization or block copolymerization. Further, a monomer having at least one addition polymerizable double bond as described below may be added to the above monomer.

One example of a monomer having one addition polymerizable double bond is a (meth) acrylic acid derivative. Specific examples are (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) Acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 2- (meth) acryloyloxyethyl isocyanate, (meth) acrylate 2-aminoethyl, 2- (2-bromopropanoyloxy) ethyl (meth) acrylate 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate, 1- (meth) acryloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) Ethane, (1- (4-((4- (meta Acryloxy) ethoxyethyl) phenylethoxy) piperidine, 3- (3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^{7 , 13]} octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15- hepta isobutyl - pentacyclo [9.5.1.1 ^{3, 9} .1 ^5,15 .1 ^7,13 ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1] ^{.1,3,9 .1,5,15 .1,7,13} ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^{3,9 .1,5,15.1,7,13} ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaethylpentacyclo [9.5]. .1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13, 15-heptaisobutylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3-[(3 5,7,9,11,13,15-heptaisooctylpentaci B [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3, 5, 7, 9 , 11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 -[(3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) Dimethylsilyl] propyl (meth) acrylate, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethyl ethyl (Meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate And 2- (meth) acryloyloxyethylphosphorylcholine.

Another example of a monomer having one addition polymerizable double bond is a styrenic monomer. Specific examples thereof include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, m-chloromethylstyrene, o-aminostyrene, p-styrene chlorosulfonic acid, styrenesulfonic acid and salts thereof. , Vinylphenylmethyldithiocarbamate, 2- (2-bromopropanoyloxy) styrene, 2- (2-bromoisobutyryloxy) styrene, 1- (2-((4-vinylphenyl) methoxy) -1-phenyl Ethoxy) -2,2,6,6-tetramethylpiperidine, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- hept isobutyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- hept isooctyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13 ] octasiloxane, 3- (3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1]. ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^3,9 .1 ^{5 , 15.1 7,13]} octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9} .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15- Descriptor phenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3 - ((3,5,7,9,11, 13,15- hepta ethylpentamethylene cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5 , 7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1- Yloxy) dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-) Descriptor cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, and 3 - ((3,5,7, 9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene.

  Other examples of monomers having one addition polymerizable double bond are fluorine-containing vinyl monomers (perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc.), maleic anhydride, maleic acid, maleic acid Monoalkyl and dialkyl esters, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide monomers (maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, Stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc.), monomers having nitrile groups (acrylonitrile, methacrylonitrile, etc.), monomers having amide groups (acrylamide, methacrylamide, etc.), Nyl ester monomers (vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc.), olefins (ethylene, propylene, etc.), conjugated diene monomers (butadiene, isoprene, etc.), halogen Vinyl chloride (such as vinyl chloride), vinylidene halide (such as vinylidene chloride), allyl halide (such as allyl chloride), allyl alcohol, vinyl pyrrolidone, vinyl pyridine, N-vinyl carbazole, methyl vinyl ketone, and vinyl isocyanate. . Furthermore, the macromonomer which has one polymerizable double bond in 1 molecule and whose main chain is a macromer of styrene, (meth) acrylic acid ester or alkylene glycol is also mentioned.

  Examples of monomers having two addition polymerizable double bonds are divinylbenzene and di (meth) acrylate monomers. Examples of di (meth) acrylate monomers include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di ( Meth) acrylate, trimethylolpropane di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobispheno A, bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol di (meth) acrylate, hydroxypivalate ester neopentyl glycol The derivatives di (meth) acrylate and bis [(meth) acryloyloxypropyl] tetramethyldisiloxane. Furthermore, a macromonomer which has two polymerizable double bonds in the molecule and whose main chain is a macromer of styrene, (meth) acrylic acid ester or alkylene glycol is also exemplified.

Examples of monomers having three or more addition polymerizable double bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( (Meth) acrylate, tris (2-hydroxyethylisocyanate) tri (meth) acrylate, tris (diethylene glycol) trimaleate tri (meth) acrylate, 3,7,14-tris [((((meth) acryloyloxypropyl) dimethylsiloxy)] -1,3,5,7,9,11,14- hepta ethyl tricyclo [7.3.3.1 ^{5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl ) Dimethylsiloxy)]-1,3 , 7,9,11,14- hepta isobutyl tricyclo [7.3.3.1 ^{5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- hepta isooctyl tricyclo [7.3.3.1 ^{5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl ) dimethylsiloxy)] - 1,3,5,7,9,11,14- hept cyclopentanol tilt Li cyclo [7.3.3.1 ^{5 and 11]} hept siloxane, 3,7,14- tris [((( meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- heptaphenyl tricyclo [7.3.3.1 ^{5 and 11]} hept siloxane, octakis (3- (meth A) Leroy oxy dimethyl siloxy) octasilsesquioxane, and octakis (3- (meth) acryloyloxy propyl) is octasilsesquioxane. Furthermore, the macromonomer which has three or more polymerizable double bonds in a molecule | numerator, and a principal chain is a macromer of styrene, (meth) acrylic acid ester, or alkylene glycol is mentioned.

  The molecular weight of the copolymer represented by the formula (1) is a polydimethylsiloxane conversion value determined by GPC (gel permeation chromatography method), preferably 100 to 75,000, more preferably 500 to 50,000. 1,000 to 20,000 is more preferable.

The polymer in the formula (1) is obtained by polymerization with the addition polymerizable monomer using a polysiloxane derivative having an α-haloester group represented by the formula (3) as a polymerization initiator (Japanese Patent Application No. 2005). -79207).

  The group having an α-haloester group means a group having α-halocarbonyloxy at the terminal. A siloxane derivative having an α-haloester group has excellent polymerization initiating ability in the presence of a transition metal complex and can continue to maintain living polymerizability. Can be started. In particular, it is possible to develop excellent living polymerizability for (meth) acrylic acid derivatives or styrene derivatives.

In the formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Z ¹ and X ¹ have the same meaning as those symbols in the formula (1).

Preferable examples of the transition metal complex used as the polymerization catalyst are metal complexes having a group metal of Group 7, Group 8, Group 9, Group 10 or Group 11 of the periodic table as a central metal. Further preferred catalysts are a zero-valent copper complex, a monovalent copper complex, a divalent ruthenium complex, a divalent iron complex and a divalent nickel complex. Of these, a copper complex is preferable. Examples of monovalent copper compounds are cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, pyridylmethanimine (N- (n-propyl) -2-pyridylmethane, Imine), polyamines (tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc.), or polycyclic alkaloids such as L-(-)-sparteine are added as ligands. . A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Examples of other suitable catalysts include divalent iron bistriphenylphosphine complexes (FeCl ₂ (PPh ₃ ) ₂ ), divalent nickel bistriphenylphosphine complexes (NiCl ₂ (PPh ₃ ) ₂ ), and 2 Bivalent bistributylphosphine complex of nickel (NiBr ₂ (PBu ₃ ) ₂ ).

A solvent may be used for the polymerization reaction. Examples of solvents used are hydrocarbons (eg benzene, xylene, toluene, etc.), ethers (eg diethyl ether, THF, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbons (eg methylene chloride, chloroform, Chlorobenzene, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, etc.), nitriles (eg, acetonitrile, propio) Nitriles, benzonitriles, etc.), esters (eg, ethyl acetate, butyl acetate, etc.), carbonate solvents (eg, ethylene carbonate, propylene carbonate, etc.), amide solvents (eg, N, N-dimethylformamide, , N-dimethylacetamide, etc.), hydrochlorofluorocarbon solvents (eg, HCFC-141b, HCFC-225, etc.), hydrofluorocarbon solvents (eg, HFCs, etc.), perfluorocarbon solvents (eg, perfluoropentane, perfluoro). Hexane, etc.), alicyclic hydrofluorocarbon solvents (example: fluorocyclopentane, fluorocyclobutane, etc.), oxygen-containing fluorine solvents (example: fluoroether, fluoropolyether, fluoroketone, fluoroalcohol, etc.), and water. . The compounds in parentheses listed here are preferred examples of the respective solvents. These may be used alone or in combination of two or more. Polymerization can also be carried out in an emulsion system or a system using supercritical fluid CO ₂ as a medium. In addition, the solvent which can be used is not restrict | limited to these examples.

  Atom transfer radical polymerization can be performed under reduced pressure, normal pressure, or increased pressure, depending on the type of addition polymerizable monomer and the type of solvent. The polymerization catalyst or generated radical may be deactivated when it comes into contact with oxygen. In such a case, the polymerization rate decreases or a good living polymer cannot be obtained. Therefore, it is important to perform the polymerization in an inert gas atmosphere such as nitrogen or argon. In this reaction, it is necessary to previously remove dissolved oxygen in the polymerization system under reduced pressure. And it is also possible to transfer to a superposition | polymerization process as it is under reduced pressure after the removal process of dissolved oxygen. A conventional method can be adopted for the atom transfer radical polymerization, and it is not particularly limited by the polymerization method. For example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk-suspension polymerization method, or the like can be employed. And polymerization temperature is the range of 0-200 degreeC, and preferable polymerization temperature is the range of room temperature-150 degreeC.

  The polymer obtained by using the compound (3) as a polymerization initiator by the above method can be represented by the formula (1). In the following description, the polymer represented by the formula (1) is represented by the polymer (1).

P ¹ in the formula (1) is a chain of structural units obtained by polymerization of an addition polymerizable monomer having a hydrolyzable group directly bonded to silicon.

  By selecting the kind of addition polymerizable monomer to be used, the structure of the polymer (1) can be controlled. For example, when the monomer is homopolymerized, a siloxane bonded with a homopolymer is obtained. When a plurality of monomers are simultaneously added and polymerized, a siloxane having a random copolymer bonded thereto is obtained. If a method of adding monomers sequentially, for example, a method of completing polymerization by adding a second monomer after the polymerization of the first monomer is completed, the block copolymer is bonded. Siloxane can be obtained. By repeating this stepwise polymerization using a plurality of monomers, it is possible to obtain a siloxane having a multiblock copolymer bonded thereto. And it can also be set as the crosslinked polymer which has a three-dimensional network structure by coexisting a polyfunctional monomer as needed.

  When a normal addition polymerizable monomer is polymerized, a siloxane having a hyperbranched polymer bonded thereto can be obtained by using a compound having a polymerizable functional group and a function as an initiator at the same time. Examples of such compounds are 2- (2-bromopropanoyloxy) ethyl (meth) acrylate, 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate, 2- (2-bromopropanoyloxy) ) Styrene, and 2- (2-bromoisobutyryloxy) styrene. After copolymerization of an addition-polymerizable monomer having an initiating group that does not participate in atom transfer radical polymerization, the resulting polymer is used as an initiator for addition in another polymerization mode (for example, nitroxyl polymerization or photo-iniferter polymerization). A polymerizable monomer can be polymerized to form a graft copolymer. Examples of addition polymerizable monomers having initiating groups not involved in atom transfer radical polymerization are 1- (2- (4-vinylphenylmethoxy) -1-phenylethoxy) -2,2,6,6-tetramethyl Piperidine, 1- (meth) acryloyloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) ethane, (1- (4- (4- (meth) acryloyl) Oxyethoxyethyl) phenylethoxy) piperidine, and vinylphenylmethyldithiocarbamate.

  By using together with an organometallic compound having addition polymerizability such as a (meth) acryl group or a styryl group, a structural unit containing a metal atom can be introduced into the structure of the polymer. Examples of the organometallic compound having addition polymerization are polydimethylsiloxane and silsesquioxane derivatives. Furthermore, as a silicon compound and a titanium compound having an addition polymerizable functional group and hydrolyzable, 3-methacryloxymethyltrimethoxysilane, styryltrimethoxysilane, titanium methacrylate triisopropoxide and (2-methylmethacryloxyethoxy) ) Triisopropoxy titanate.

  After copolymerization of a monomer having an oxetanyl group, such as 3-ethyl-3- (meth) acryloyloxymethyloxetane, the obtained polymer is used as an initiator to diphenyl-4-thiophenoxyphenylsulfonium hexafluoro. When antimonate or (4-pentadecyloxyphenyl) phenyliodonium haxafluoroantimonate is added, photocationic polymerization can be performed.

  Next, a method for purifying the polymer (1) will be described. This polymer is isolated and purified by efficiently removing unreacted addition polymerizable monomers. Although there are various methods, a purification method by reprecipitation operation is preferable. This purification method is performed as follows. First, a solvent that does not dissolve the polymer (1) but dissolves the unreacted monomer, a so-called precipitant, is added to this solution in the polymerization reaction solution containing the polymer (1) and the unreacted monomer. In addition, only the polymer (1) is precipitated. A preferred amount of the precipitating agent is 20 to 50 times based on the weight of the polymerization reaction solution.

  A preferred precipitant is a solvent that is compatible with the solvent used in the polymerization, does not dissolve the polymer (1) at all, dissolves only unreacted monomers, and has a relatively low boiling point. Examples of preferred precipitating agents are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitants are methanol and hexane. And in order to raise the removal efficiency of an unreacted monomer further, what is necessary is just to increase the repetition frequency of reprecipitation operation. By this method, only the polymer (1) can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.

  Since the transition metal complex which is a polymerization catalyst remains in the polymer (1) isolated by the above method, problems such as coloring of the polymer, influence on physical properties and environmental safety may occur. Therefore, it is necessary to remove this catalyst residue at the end of the polymerization reaction. The catalyst residue can be removed by an adsorption treatment using activated carbon or the like. Examples of adsorbents other than activated carbon are ion exchange resins (acidic, basic or chelate type), and inorganic adsorbents.

  Next, the tetraalkoxysilane represented by the following formula (2) will be described.

The phenyl in R ⁸ of formula (2) or the linear or branched alkyl having 1 to 20 carbon atoms is preferably phenyl or a linear or branched alkyl having 1 to 4 carbon atoms.
Specific examples thereof include tetraphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra n-propoxysilane, and tetrabutoxysilane.

  Cohydrolysis of the copolymer and tetraalkoxysilane is carried out in the presence of an organic solvent. The type of reaction is not particularly limited, but a method of simultaneously dropping a copolymer and a tetraalkoxysilane in an organic solvent containing water, a method of simultaneously dropping water, a copolymer, and a tetraalkoxysilane in an organic solvent, Examples thereof include a method of dropping water into an organic solvent containing a coalescence and tetraalkoxysilane. The reaction temperature is -20 to 50 ° C, preferably -10 to 30 ° C. The reaction time is a few minutes to a few tens hours, preferably 5 minutes to 2 hours.

The ratio of the copolymer in all alkoxysilanes used in the present invention is 0.01 to 50% by weight, preferably 5 to 25% by weight.
When the ratio of the copolymer is 0.01% by weight or more, the ratio of, for example, dialkylpolysiloxane forming the particle surface is not too small, and as a result, the solvophilic property of the particles is maintained.
In addition, when the copolymer is 50% by weight or less, the ratio of, for example, a dialkylpolysiloxane portion that forms the particle surface is not too large, and a single condensate of only the copolymer is not formed. The lipophilic nature of the particles is maintained.

  The amount of water used in the present invention is preferably 0.5 mol or more and 200 mol or less, more preferably 20 mol or less, with respect to 1 mol of all alkoxysilanes. It is because a hydrolysis reaction will advance easily that it is 0.5 mol or more. Moreover, it is because the dispersibility of each raw material improves that it is 200 mol or less. The water to be used is preferably one that has been sufficiently purified by ion exchange or the like to remove impurities.

  In the method of the present invention, a catalyst can be used together with the water. The catalyst that can be suitably used is not particularly limited as long as it changes the pH of water. Specifically, examples of the acid include nitric acid, oxalic acid, and acetic acid, and examples of the alkali include ammonia and triethylamine. And ethylenediamine. The amount to be used is not particularly limited.

  The solvent that can be used for the hydrolysis is not particularly limited, but a solvent that dissolves water during the reaction is preferable. Examples include alcohols such as methanol, ethanol, isopropanol and n-butanol, acetates such as ethyl acetate and butyl acetate, tetrahydrofuran, ethyl cellosolve, butyl cellosolve, cellosolve acetate, propylene glycol methyl ether and propylene glycol. Examples include ethers such as methyl ether acetate, and ketones such as acetone, methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methyl isobutyl ketone, and diacetone alcohol. Moreover, in order to adjust the polarity of reaction, these solvents can also be used in combination of 2 or more types, and hydrocarbons, such as toluene, xylene, n-hexane, and cyclohexane, can also be combined with these solvents.

  The average particle size of the silicon-containing fine particles can be controlled by a reaction engineering technique. Specifically, adjustment of the addition amount of the catalyst, adjustment of the dropping speed of the dropping liquid, and the like. When the Z average particle diameter is 50 nm or more, the particle diameter becomes equal to or greater than the wavelength of light, and light reflection becomes easy. Further, when the Z average particle diameter is 1000 nm or less, sedimentation of the particles can be prevented and stable dispersion can be maintained. For this reason, as display particles, the Z average particle diameter is preferably 50 to 1000 nm, and more preferably 100 to 500 nm.

In order to obtain display particles having an arbitrary color used in a display liquid for an electrophoretic display device, colored fine particles mainly composed of an inorganic compound are dispersed in an organic solvent in advance, and a specific common material is present in the presence of the fine particles. Silicon-containing fine particles can be prepared by cohydrolyzing a polymer and a specific alkoxysilane. Thereby, display particles colored in various colors can be created.
The colored fine particles mainly composed of an inorganic compound used here are pigment pigments that are insoluble in a medium mainly composed of an inorganic compound, generally called an inorganic pigment. The particles mainly composed of these inorganic compounds are usually highly hydrophilic and even if said to be oleophilic, they are difficult to disperse in a low-polarity medium used in electrophoretic display elements. Examples of such colored fine particles mainly composed of inorganic compounds include zinc oxide, titanium oxide, calcium carbonate, barium sulfate, red lead, molybdenum red, iron oxide, cadmium red, yellow lead oxide, yellow lead, cadmium yellow, and bitumen. , Ultramarine, etc.

  These colored fine particles may be used alone, or a plurality of them may be mixed in order to produce a desired color. Any shape of particles can be used. Those having a very large particle size are not suitable for electrophoretic display elements. If the particle diameter is less than 50 nm, it becomes too short of the wavelength of visible light, and a sufficient color does not appear even if the particle concentration is increased. On the other hand, when the particle diameter exceeds 10,000 nm, the electrophoretic speed becomes slow or the color unevenness when displayed is caused. For this reason, the average particle size of the particles mainly composed of the inorganic compound provided to the present invention is preferably 50 to 10,000 nm, and more preferably 100 to 1,000 nm.

  When cohydrolysis of the copolymer and tetraalkoxysilane is performed together with particles mainly composed of an inorganic compound, it is performed in the presence of an organic solvent. The type of reaction is not particularly limited, but a method of simultaneously dropping a copolymer and tetraalkoxysilane into an organic solvent containing particles mainly composed of water and an inorganic compound, and an organic solvent containing particles mainly composed of an inorganic compound. Examples thereof include a method in which water, a copolymer, and a tetraalkoxysilane are dropped simultaneously, and a method in which water is dropped in an organic solvent containing particles mainly composed of a copolymer, a tetraalkoxysilane, and an inorganic compound. The reaction temperature is -20 to 50 ° C, preferably -10 to 30 ° C. The reaction time is a few minutes to a few tens hours, preferably 5 minutes to 2 hours.

  The copolymer used in the present invention is preferably in a weight ratio of 100 to 1 with respect to the particles 100 mainly composed of an inorganic compound. If it exceeds 100, it is economically wasteful, and particles different from those bonded to the surface of particles mainly composed of an inorganic compound are produced, resulting in poor color. If it is less than 1, the surface of the particle mainly composed of an inorganic compound cannot be sufficiently covered.

  The silicon-containing fine particles thus prepared have a negative zeta potential because silanol is present on the surface of the particles and dissociates. Therefore, when this dispersion is injected between two translucent electrode plates such as an ITO electrode, if the voltage on the display side is positive, the particles move to the display surface and the voltage on the display side is negative. Then, the particles move to the non-display side.

  The dispersion medium used for the display liquid for electrophoretic display devices is an aromatic compound such as saturated hydrocarbon, toluene, xylene, halogenated hydrocarbon, silicone, olive oil, coconut oil, castor oil or liquid paraffin. Any mixture of these compounds can also be used. Of these, saturated hydrocarbons are preferred, and specific examples thereof include paraffins such as n-pentane, n-hexane, n-heptane, and n-octane, isooctane, Isopar C, Isopar E, Isopar G, Isopar L, Examples include isoparaffins such as Isopar M, Isopar H, Isopar J, Isopar K, Isopar L, Isopar P, and Isopar V (all registered trademarks of Exxon), and cycloparaffins such as cyclopentane, cyclohexane, and methylcyclohexane. A small amount of a solvent having a weak polar group may be added to such an extent that the object of the present invention is not impaired.

  The silicon-containing fine particles thus prepared are particles in which a portion of silicon dioxide that does not dissolve in an organic solvent and a diorganopolysiloxane portion having an affinity for the organic solvent are chemically bonded. For this reason, it overcomes the disadvantage of silicon dioxide that the surface is hydrophilic and agglomerates without being dispersed in the water-insoluble organic solvent. It also overcomes the disadvantage of silicone (diorganopolysiloxane). In other words, since it is insoluble in an organic solvent, it maintains the shape of the particle in the organic solvent, is stably dispersed in the organic solvent, and does not cause aggregation. Are preferably used.

  Furthermore, the display liquid containing the silicon-containing fine particles of the present invention is different from the conventional method of creating a stable suspension by adding a surfactant or a dispersant, and a third component such as a surfactant or a dispersant. Therefore, there is an advantage that no interference is caused even when processing such as encapsulating in a capsule is performed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely and in detail, this invention is not limited by an Example.

Proton NMR spectrum ( ¹ H-NMR): JNM-GSX400 manufactured by JEOL Ltd. was used, measured at room temperature using chloroform-d as a solvent at 400 MHz and tetramethylsilane as an internal standard substance.

The meanings of symbols used in the examples are as follows.
Mn: number average molecular weight Mw: weight average molecular weight

All the molecular weight data in the examples are polydimethylsiloxane equivalent values determined by GPC (gel permeation chromatography). The GPC measurement conditions are shown below.
Apparatus: JASCO GULLIVER 1500 (intelligent differential refractometer RI-1530) manufactured by JASCO Corporation
Solvent: Tetrahydrofuran (THF)
Flow rate: 1 mL / min
Column temperature: 40 ° C
Shodex KF-G (GUARDCOLUMN) manufactured by Showa Denko KK and two Shodex KF-804L (exclusion limit molecular weight (polystyrene): 400,000) were connected in series.
Standard samples for calibration curves: Polymer Laboratories, Polymer Standards (PL), Polydimethylsiloxane

  In order to see the affinity of particles for solvents of different polarities, the particle size of the particles in both solvents was measured. That is, methanol is used as a solvent having a large polarity, n-hexane is used as a solvent having a small polarity, and a sample is diluted to a non-volatile content concentration of 10 to 100 ppm, and a zeta potential / particle size distribution measuring apparatus (Zeta Sizer 3000HS) manufactured by Malvern is And measured by Z average particle diameter.

Reference example 1
Synthesis method of polysiloxane compound having polymerization initiating group

Compound (A-2) having Mn = 10,000 having a hydroxyl group at one end: 50 g (5.15 mmol), triethylamine: 1.05 g (10.3 mmol, 2 mol per mol of —OH group) and dichloromethane : 200 g was charged into a 500 mL eggplant flask, and then stirred in a dry ice / methanol bath using a magnetic stirrer under an argon atmosphere. Next, 2.37 g (10.3 mmol, 2 mol per mol of —OH group) of weighed 2-bromo-2-methylpropanoyl bromide was quickly added, and the mixture was dried in a dry ice / methanol bath for 1 hour. Thereafter, the reaction was carried out at room temperature for 3 hours. Then 50 mL of MeOH was added. The reaction solvent was concentrated on a rotary evaporator. Purification was performed by dissolving the concentrate in 20 mL of dichloromethane and reprecipitating in 500 mL of MeOH. After repeating this reprecipitation operation several times, the compound (A-1) could be obtained by drying under reduced pressure.
¹ H-NMR (400 MHz, CDCl ₃ ) δ0 · 08 (m, 876H), 0.56 (m, 4H), 0.89 (t, 3H), 1.31 (m, 4H), 1.57 ( m, 2H), 1.95 (s, 6H), 3.45 (t, 2H), 3.67 (t, 2H), 4.32 (t, 2H).

Synthesis of polydimethylsiloxane-polymethacryloxypropyltrimethoxysilane copolymer <Preparation of polymerization solution>
Mn = 10,000 compound (A-1) / 3-methacryloxypropyltrimethoxysilane / L-(-)-in a 100 mL four-necked flask connected with a reflux condenser, a magnetic stirrer, a gas inlet tube and a thermometer Sparteine / p-xylene solution was added, and argon substitution in the reactor was performed by bubbling with argon gas for 5 minutes at room temperature. After adding cuprous bromide and bubbling with argon gas for 5 minutes, the reactor was immersed in an oil bath set at 70 ° C., and stirring was started. At this time, the ratios of the compound (A-1), 3-methacryloxypropyltrimethoxysilane, cuprous bromide and L-(-)-spartein in this polymer solution were 1: 40: 1: 2, and the amount of p-xylene used was such that the concentration of 3-methacryloxypropyltrimethoxysilane was 30 wt%.

<Polymerization>
The polymerization temperature was 70 ° C., and the polymerization time was 2.5 hours. A brown and viscous polymer could be obtained. Thereafter, a predetermined amount of the polymer solution was sampled and subjected to gas chromatography measurement. The monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the gas chromatographic measurement value of a known concentration of 3-methacryloxytrimethoxysilane / p-xylene solution. The obtained polymer was purified by reprecipitation using methanol. Next, a hexane solution of this polymer was prepared, and this was passed through a column filled with activated alumina, whereby the copper remaining in the polymer was removed by adsorption. This was dried under reduced pressure (80 ° C., 6 hours). Further, the number average molecular weight and molecular weight distribution were determined by GPC measurement. The monomer conversion obtained by the above measurement was 59.3%, the theoretical number average molecular weight was 15,490, the number average molecular weight was 15,030, and the molecular weight distribution was 1.09.

Reference Example 2 (Creation of electrophoresis display cell)
As shown in FIG. 1, ITO glass 10 was obtained by sputtering ITO on a borosilicate glass having a thickness of 1.1 mm and a thickness of 30 mm × 30 mm and indicated by the colored portion in FIG. 1. The resistance value of ITO was 10 Ω / cm ² . Thereafter, silicon dioxide 11 was sputtered on the portions indicated by the colored portions in FIG. 2 to insulate them. An ultraviolet curable resin 12 in which silica beads having an average particle diameter of 0.1 mm are mixed is applied to the colored portion shown in FIG. 3, and two ITO glasses 10 and 10 ′ are sputtered with ITO as shown in FIG. After being laminated so that the square electrodes in the center part of the upper and lower glass were overlapped with each other, ultraviolet rays were irradiated to create an electrophoretic display cell 20. In the display test, an electric wire was connected to the white portion of FIG. 2 that was not sputtered with silicon dioxide, and a DC voltage was applied.

Example 1
30 mL of THF was charged into a 100 mL reactor equipped with a stirrer. The dropping tank A was charged with a mixed solution of 4.5 mL of tetramethoxysilane, 0.90 g of the copolymer of Reference Example 1 and 3.6 mL of THF. The dropping tank B was filled with a mixed solution of 0.9 mL of water, 0.9 mL of concentrated aqueous ammonia, and 7.2 mL of methanol.
While stirring the reactor, the solution in the dropping tank A and the solution in the dropping tank B were dropped over 1 hour at room temperature. The resulting liquid was a milky white uniform suspension.
When the particle size distribution of the fine particles was measured in methanol, the Z average particle size was 121 nm. Moreover, when measured in n-hexane, the Z average particle diameter was 119 nm.

Example 2
29 mL of THF and 1 mL of n-hexane were charged into a 100 mL reactor equipped with a stirrer. The dropping tank A was charged with a mixed solution of 4.5 mL of tetramethoxysilane, 0.90 g of the copolymer of Reference Example 1 and 3.6 mL of THF. The dropping tank B was filled with a mixed solution of 0.9 mL of water, 0.9 mL of concentrated aqueous ammonia, and 7.2 mL of methanol.
While stirring the reactor, the solution in the dropping tank A and the solution in the dropping tank B were dropped over 1 hour at room temperature. The resulting liquid was a milky white uniform suspension.
When the particle size distribution of the fine particles was measured in methanol, the Z average particle size was 103 nm. Moreover, when measured in n-hexane, the Z average particle diameter was 113 nm.

Example 3
A dispersion obtained by dispersing a mixture of 30 mL of THF and 1.5 g of R-960 (surface-coated titanium oxide manufactured by DuPond) by ultrasonic irradiation was added to a 100 mL reactor equipped with a stirrer. The dropping tank A was charged with 5.0 mL of tetramethoxysilane and 1.0 g of the copolymer of Reference Example 1 in which THF was added to prepare a mixed solution of 15.0 mL. The dropping tank B was filled with 5.0 mL of water and 5.0 mL of concentrated ammonia water in which methanol was added to form a mixed solution of 50.0 mL.
While stirring the inside of the reactor, the solution in the dropping tank A and the solution in the dropping tank B were simultaneously added dropwise at a rate of 0.1 mL / min over 10 minutes at room temperature. The resulting liquid was a milky white uniform suspension.
Three drops of the resulting suspension was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. Even after standing for 10 minutes, only the n-hexane layer was suspended, and the aqueous layer did not become cloudy.
R-960, 10 mg was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. The transition from the n-hexane layer to the aqueous layer was observed immediately after the addition of water, and after standing for 10 minutes, the n-hexane layer became transparent and the aqueous layer was suspended in milky white.
This indicates that a silicone layer was formed on the surface of R-960 and the particles were hydrophobized.

Example 4
Example 1 A reactor with 30 ml of THF and 1.5 g of NanoTek Black (SHI Kasei Co., Ltd., metal oxide-based black fine particles) was ultrasonically dispersed in a 100 ml reactor equipped with a stirrer. By the same operation as 3, a black uniform suspension was obtained.
Three drops of the resulting black suspension was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. Even after standing for 10 minutes, only the n-hexane layer was suspended, and the aqueous layer did not become cloudy.
NanoTek Black, 10 mg, was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. The transition from the n-hexane layer to the aqueous layer was observed immediately after the addition of water, and after standing for 10 minutes, the n-hexane layer became transparent, the aqueous layer suspended in black, and black on the container surface. Particles adhered.
This indicates that a silicone layer was formed on the surface of the NanoTek Black, and the particles were hydrophobized.

Example 5
Example 3 except that a 100 mL reactor equipped with a stirrer was charged with a dispersion obtained by ultrasonically irradiating a mixture of 30 mL of THF and 1.5 g of NanoTek White (white titanium fine particles manufactured by CI Kasei Co., Ltd.). By the same operation, a milky white uniform suspension was obtained.
Three drops of the resulting milky white suspension was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. Even after standing for 10 minutes, only the n-hexane layer was suspended, and the aqueous layer did not become cloudy.
NanoTek White, 5 mg, was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. The transition from the n-hexane layer to the aqueous layer was observed immediately after the addition of water, and after standing for 10 minutes, the n-hexane layer became transparent and the aqueous layer was suspended in milky white.
This indicates that a silicone layer was formed on the surface of NanoTek White and the particles were hydrophobized.

Example 6
A 100 mL reactor equipped with a stirrer was operated in the same manner as in Example 3 except that a dispersion obtained by ultrasonically irradiating a mixture of 30 mL of THF and 1.5 g of nickel titanate yellow (Yumin pigment Pigment Yellow 58 manufactured by Schminke) was ultrasonically dispersed. A yellowish-white uniform suspension was obtained.
3 drops of the produced yellowish white suspension was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. Even after standing for 10 minutes, only the n-hexane layer was suspended, and the aqueous layer did not become cloudy.
Nickel titanate yellow, 5 mg, was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. The transition from the n-hexane layer to the aqueous layer was observed immediately after the addition of water, and after standing for 10 minutes, the n-hexane layer became transparent and the aqueous layer was suspended in yellowish white.
This indicates that a silicone layer was formed on the surface of nickel titanate yellow, and the particles were hydrophobized.

Example 7
The same operation as in Example 3 was conducted except that a dispersion obtained by ultrasonically irradiating a mixture of 30 mL of THF and 1.5 g of Ultra Marine Deep (Blue Pigment Pigment Blue 29, manufactured by Schminke) was introduced into a 100 mL reactor equipped with a stirrer. A blue uniform suspension was obtained.
Three drops of the resulting blue suspension was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. Even after standing for 10 minutes, only the n-hexane layer was suspended, and the aqueous layer did not become cloudy.
Ultramarine deep, 5 mg was dispersed in 2 mL of n-hexane, and 2 mL of water was gently added thereto. The transition from the n-hexane layer to the aqueous layer was observed immediately after the addition of water, and after standing for 10 minutes, the n-hexane layer became transparent and the aqueous layer suspended in blue.
This indicates that a silicone layer was formed on the surface of the ultramarine deep and the particles were hydrophobized.

Comparative Example 1
Implemented except that a mixture of 5.4 mL of tetramethoxysilane and 3.6 mL of tetrahydrofuran was added to the dropping tank A, and a mixture of 0.9 mL of water, 0.9 mL of concentrated ammonia water and 7.2 mL of methanol was added to the dropping tank B. A milky white homogeneous solution was obtained by the same operation as in Example 1.
When the particle size distribution of the produced fine particles was measured in methanol, the average particle size was 113 nm. Moreover, although it tried to measure in n-hexane, particle | grains aggregated and could not be measured.

Example 8
Isopar H2.0g was added to 6.4g of milky white suspension of Example 5, and the volatile matter was distilled off under reduced pressure, and 2.7g of white display liquid was obtained. 0.15 g of this white display liquid and 0.04 g of Isopar H dispersion (hereinafter referred to as CB dispersion) of 4% by weight of carbon black (resin-coated carbon black manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and stirred for 10 minutes with a rotor. This dispersion was injected into the electrophoretic display cell of Reference Example 2.
When a DC voltage was applied so that the voltage on the display surface was −10 V, the display surface was black, and the reflectance at 550 nm was 3%. Further, when a DC voltage was applied so that the voltage on the display surface was +10 V, the display surface was white and the reflectance was 15%.
Further, the time until the display changed from white to black when the applied voltage was inverted from +50 V to −50 V was 0.5 seconds.

Example 9
Isopar H2.1g was added to 6.0g of yellowish white suspension of Example 6, and volatile matter was distilled off under reduced pressure to obtain 2.7g of yellow display liquid. 0.15 g of this yellow display liquid and 0.05 g of the CB dispersion were mixed and stirred with a rotor for 10 minutes. This dispersion was injected into the electrophoretic display cell of Reference Example 2. When a DC voltage was applied so that the voltage on the display surface was −10 V, the display surface was black, and the reflectance at 510 nm was 1%. Further, when a DC voltage was applied so that the voltage on the display surface was +10 V, the display surface was yellow and the reflectance was 10%.
The time until the display changed from yellow to black when the applied voltage was reversed from +50 V to −50 V was 0.2 seconds.

Example 10
Isopar H2.1g was added to 6.9g of blue suspension of Example 7, and the volatile matter was distilled off under reduced pressure, and 2.8g of blue display liquid was obtained. 0.10 g of this blue display liquid and 0.10 g of the CB dispersion liquid were mixed and stirred with a rotor for 10 minutes. This dispersion was injected into the electrophoretic display cell of Reference Example 2. When a DC voltage was applied so that the voltage on the display surface was −10 V, the display surface was black, and the reflectance at 600 nm was 2%. When a DC voltage was applied so that the voltage on the display surface was +10 V, the display surface was blue and the reflectance was 10%.

It is a figure for demonstrating the manufacturing procedure of the cell for electrophoretic displays used in the Example. It is a figure for demonstrating the manufacturing procedure of the cell for electrophoretic displays used in the Example. It is a figure for demonstrating the manufacturing procedure of the cell for electrophoretic displays used in the Example. It is a figure for demonstrating the manufacturing procedure of the cell for electrophoretic displays used in the Example.

Explanation of symbols

10, 10 'ITO glass 11 Silicon dioxide 12 UV curable resin 20 Electrophoretic display cell

Claims (12)

(A) silicon obtained by cohydrolysis reaction of at least one copolymer represented by formula (1) and at least one tetraalkoxysilane represented by (b) formula (2) in a solution Containing fine particles.

In the formula (1), n is an integer of ^{1 to} 1,000; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each hydrogen, 30, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene, which has 2 to 20 carbon atoms, and any hydrogen is May be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene, any hydrogen may be replaced by halogen or alkyl having 1-10 carbons well, and any -CH 2 in the alkyl _- is _{-O -, - CH 2 = CH} 2 - or may also be substituted or unsubstituted replaced by phenylene aryl, and substituted or unsubstituted aryl , Arbitrary hydrogen may be replaced by fluorine arbitrary -CH ₂ - _{-O -, - CH 2 = CH} 2 - or independently constituted arylalkyl, from between the alkylene which may be replaced by a cycloalkylene Z is a group having 2 to 20 carbon atoms, an arbitrary —CH ₂ — in which —CH ₂ — may be replaced by —O—, or an arbitrary —CH _2- is alkenylene which may be replaced by -O-; X is halogen; and P ¹ is obtained by polymerization of at least one addition polymerizable monomer having a hydrolyzable group directly attached to silicon. Is a chain of structural units. In the formula (2), R ⁸ is phenyl or alkyl having 1 to 20 carbons. In the copolymer represented by the formula (1), P ¹ is a structural unit obtained by polymerization of at least one silane coupling agent having at least one functional group selected from vinyl, acryloyl, methacryloyl and styryl. The silicon-containing fine particle according to claim 1, which is a chain. In the copolymer represented by the formula (1), P ¹ has a hydrolyzable group directly bonded to silicon, a group of acrylic acid ester and methacrylic acid ester, and a hydrolyzable group directly bonded to silicon. The silicon-containing fine particles according to claim 1, which are a chain of structural units obtained by polymerization of at least one addition polymerizable monomer selected from the group of styrene derivatives. 2. The copolymer represented by formula (1), wherein P ¹ is a chain of structural units obtained by polymerization of at least one addition-polymerizable monomer represented by formula (A). Silicon-containing fine particles.

In the formula (A), R ^A , R ^B and R ^C are each independently alkyl, alkoxy, alkenyloxy or acyloxy having 1 to 4 carbon atoms, and at least one of R ^A , R ^B and R ^C One is alkoxy having 1 to 4 carbon atoms, alkoxy, alkenyloxy, or acyloxy; R ^D is hydrogen or methyl; X ^A is alkylene having 2 to 20 carbon atoms; Any —CH ₂ — except may be replaced by —O—, —NH— or —CH (OH) —. 2. The copolymer represented by formula (1), wherein P ¹ is a chain of structural units obtained by polymerization of at least one addition-polymerizable monomer represented by formula (A). Silicon-containing fine particles.

In the formula (A), R ^A , R ^B and R ^C are independently methyl, ethyl, methoxy, ethoxy, 1-propoxy, 2-propoxy, 2-propenyloxy or acetyloxy, and R ^A , R ^At least one of ^B 1 and R ^C is methoxy, ethoxy, 1-propoxy, 2-propoxy, 2-propenyloxy, or acetyloxy; R ^D is hydrogen or methyl; X ^A is —CH ₂ CH ₂ CH ₂ —, — (CH ₂ CH ₂ O) mCH ₂ CH ₂ CH ₂ — or —CH (OH) CH ₂ NHCH ₂ CH ₂ CH ₂ —. Here, m is an integer of 1 to 3. The copolymer represented by formula (1), wherein P ¹ is a chain of structural units obtained by polymerization of at least one addition polymerizable monomer represented by formula (B). Silicon-containing fine particles.

In the formula (B), R ^E , R ^F , and R ^G are each alkyl having 1 to 4 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—, and R ^E , R ^F, at least one of R ^G _{are, -O-CH 3, -O-} CH 2 CH 3, -O-CH 2 CH 2 CH 3, -O-CH (CH 3) it is _2; R ^H is hydrogen or methyl; X ^B is 2 to 20 carbon atoms, any -CH ₂ - alkylene good be replaced by -O-, arylene having 6 to 20 carbon atoms, or carbon atoms, 7 It is a divalent group defined by removing any two hydrogens from ˜20 arylalkyl, and arbitrary —CH ₂ — may be replaced by —O—. The tetraalkoxysilane represented by the formula (2), wherein R ⁸ is alkyl having 1 to 4 carbon atoms, silicon-containing fine particles according to any one of claims 1 to 6. (A) at least one copolymer represented by formula (1) and (b) at least one tetraalkoxysilane represented by formula (2), and (c) fine particles mainly composed of an inorganic compound. Silicon-containing fine particles obtained by cohydrolysis reaction in solution in the presence.

In the formula (1), n is an integer of ^{1 to} 1,000; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each hydrogen, 30, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene, which has 2 to 20 carbon atoms, and any hydrogen is May be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene, any hydrogen may be replaced by halogen or alkyl having 1-10 carbons well, and any -CH 2 in the alkyl _- is _{-O -, - CH 2 = CH} 2 - or may also be substituted or unsubstituted replaced by phenylene aryl, and substituted or unsubstituted aryl , Arbitrary hydrogen may be replaced by fluorine arbitrary -CH ₂ - _{-O -, - CH 2 = CH} 2 - or independently constituted arylalkyl, from between the alkylene which may be replaced by a cycloalkylene Z is a group having 2 to 20 carbon atoms, an arbitrary —CH ₂ — in which —CH ₂ — may be replaced by —O—, or an arbitrary —CH _2- is alkenylene which may be replaced by -O-; X is halogen; and P ¹ is obtained by polymerization of at least one addition polymerizable monomer having a hydrolyzable group directly attached to silicon. Is a chain of structural units. In the formula (2), R ⁸ is phenyl or alkyl having 1 to 20 carbons.   The silicon-containing fine particles according to any one of claims 1 to 7, having an average particle diameter of 50 to 1,000 nm.   The silicon-containing fine particles according to claim 8, wherein the average particle diameter is 50 to 10,000 nm.   A display liquid for an electrophoretic display device, comprising the silicon-containing fine particles according to claim 1 and a dispersion medium.   An electrophoretic display device in which the display liquid according to claim 11 is sealed between a pair of opposingly arranged electrode plates, at least one of which is transparent.

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