Metal-containing siloxy compound, metal-containing siloxy-coated particles, method for producing the same, and dispersion composition

Abstract

The present application provides a compound used as a coating agent for providing a particle having excellent dispersibility and refractive index, a particle having a surface coated with the compound, a production method thereof, and a dispersion composition containing the particle. The compound according to the present application has a structure represented by Formula (1). In the formula, R 1 represents an organic group having 1 to 30 carbon atoms, R 2 represents OR 3 or a group represented by Formula (2), R 3 represents an organic group having 1 to 30 carbon atoms, n1 and n2 represent an integer of 0 or more, n1 + 2 x n2 represents a valence number determined by the kind of L, L represents aluminum, gallium, yttrium, titanium, zirconium, hafnium, bismuth, tin, vanadium, or tantalum, * represents a bonding site, and R 4 and R 5 represent an organic group having 1 to 30 carbon atoms which can have an oxygen atom. The particle according to the present application has a structure represented by Formula (1) on the surface.

Description

Technical Field

[0001] This invention relates to metal-containing siloxy compounds, metal-containing siloxy coated particles, methods for manufacturing the same, and dispersion compositions thereof. Background Technology

[0002] In the formation of optical components, high refractive index materials are used. For example, a composition obtained by dispersing metal oxide particles such as zirconium oxide in an organic component is used as a high refractive index material. As a method for improving the dispersibility of metal oxide particles, a method of coating the surface of the metal oxide particles with a coating agent is known. For example, organosilanes such as n-propyltrimethoxysilane are known (see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent No. 6698591 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] In recent years, with the increasing performance requirements of optical components, the required refractive index of high refractive index materials has also been continuously increasing.

[0008] The present invention was made in view of such conventional realities, and aims to provide a compound used as a coating agent for providing particles with excellent dispersibility and refractive index, particles whose surface is coated with the compound, a method for manufacturing the same, and a dispersion composition containing the particles.

[0009] Methods for solving problems

[0010] The inventors of this application conducted repeated and in-depth research to solve the aforementioned problems. As a result, they discovered that the above-mentioned problems could be solved using a specified metal-containing silanoxy compound, thus completing this invention. Specifically, this invention provides the following solution.

[0011] The first aspect of the present invention is a compound having the structure represented by the following formula (1).

[0012] [Chemical Formula 1]

[0013]

[0014] (in the formula,

[0015] R 1 Organic groups representing 1 to 30 carbon atoms

[0016] R 2 OR3 The group shown, or the group shown in formula (2) below,

[0017] R 3 Organic groups representing 1 to 30 carbon atoms

[0018] n1 and n2 each independently represent integers greater than or equal to 0, where n1 + 2 × n2 is the valence determined by the type of L.

[0019] L represents aluminum, gallium, yttrium, titanium, zirconium, hafnium, bismuth, tin, vanadium, or tantalum.

[0020] * indicates a connection key.

[0021] [Chemical Formula 2]

[0022]

[0023] (where R is in the formula) 4 and R 5 This refers to organic groups with 1 to 30 carbon atoms that can have oxygen atoms.

[0024] The second aspect of the present invention is a particle having a structure represented by the above formula (1) on its surface.

[0025] The third aspect of the present invention is a dispersion composition containing the above-mentioned particles.

[0026] The fourth aspect of the present invention is a manufacturing method, which is a method for manufacturing particles having a structure represented by the above formula (1) on their surface.

[0027] The aforementioned manufacturing method includes a particle coating step in which particles having hydroxyl groups on their surface are reacted with a compound represented by formula (30) to obtain particles having the structure represented by formula (1) on their surface, or...

[0028] The aforementioned manufacturing method has the following characteristics:

[0029] A first reaction step involves reacting particles having hydroxyl groups on their surface with a compound represented by formula (4) to obtain particles having a structure represented by formula (5) on their surface; and,

[0030] A second reaction step involves reacting the particles obtained in the first reaction step with a compound represented by the following formula (6) to obtain particles having the structure represented by the above formula (1) on their surface.

[0031] [Chemical Formula 3]

[0032]

[0033] (where R is in the formula) 1 R 2As mentioned above, n1, n2, and L, R 60 and R 70 (This refers to organic groups with 1 to 30 carbon atoms.)

[0034] [Chemical Formula 4]

[0035]

[0036] (where R is in the formula) 1 R 60 and R 70 As mentioned above, R 8 (This refers to organic groups with 1 to 30 carbon atoms.)

[0037] [Chemical Formula 5]

[0038]

[0039] (where R is in the formula) 1 and R 8 As mentioned above.

[0040] R 9 OL(R 2 ) n1 (O) n2 (6)

[0041] (where R is in the formula) 2 As mentioned above, n1, n2, and L, R 9 (This refers to organic groups with 1 to 30 carbon atoms.)

[0042] Invention Effects

[0043] According to the present invention, it is possible to provide a compound used as a coating agent for providing particles with excellent dispersibility and refractive index, particles whose surface is coated with the compound, a method for manufacturing the compound, and a dispersion composition containing the particles. Detailed Implementation

[0044] <Compounds having the structure represented by formula (1)>

[0045] The compounds involved in this invention have the structure represented by the above formula (1). These compounds can be used as coating agents to provide particles with excellent dispersibility and refractive index.

[0046] In the above equation (1), R is... 1The organic group represented by the number of carbon atoms 1 to 30 is not particularly limited. Examples include alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 3 to 30 carbon atoms, alkenyl groups with 2 to 30 carbon atoms, aryl groups with 6 to 30 carbon atoms, and alkoxyalkyl groups with 2 to 30 carbon atoms. Among these, alkyl groups with 1 to 30 carbon atoms or alkoxyalkyl groups with 2 to 30 carbon atoms are preferred from the perspective of the dispersibility of the obtained particles.

[0047] As R 1 The alkyl group having 1 to 30 carbon atoms is not particularly limited. Examples include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, n-eicosyl, etc. Considering the ease of synthesis of the above compounds and the dispersibility of the obtained particles, alkyl groups having 6 to 24 carbon atoms are preferred, and alkyl groups having 8 to 20 carbon atoms are more preferred.

[0048] As R 1 The cycloalkyl group represented by carbon atoms is not particularly limited. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, cyclooctadecyl, and cycloeicosyl. Considering the ease of synthesis of the above compounds and the dispersibility of the obtained particles, cycloalkyl groups with carbon atoms of 6 to 24 are preferred, and cycloalkyl groups with carbon atoms of 8 to 20 are more preferred.

[0049] As R 1 The alkenyl group with 2 to 30 carbon atoms is not particularly limited. Examples include vinyl and allyl groups. Considering the ease of synthesis of the above compounds and the dispersibility of the obtained particles, alkenyl groups with 6 to 24 carbon atoms are preferred, and alkenyl groups with 8 to 20 carbon atoms are more preferred.

[0050] As R 1 The aryl group with 6 to 30 carbon atoms is not particularly limited. Examples include phenyl and naphthyl groups. Considering the ease of synthesis of the above compounds and the dispersibility of the obtained particles, aryl groups with 8 to 24 carbon atoms are preferred, and aryl groups with 10 to 20 carbon atoms are more preferred.

[0051] As R 1 The alkoxyalkyl group with 2 to 30 carbon atoms is not particularly limited. Examples include methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl. Considering the ease of synthesis of the above compounds and the dispersibility of the obtained particles, an alkoxyalkyl group with 6 to 24 carbon atoms is preferred, and an alkoxyalkyl group with 8 to 20 carbon atoms is more preferred.

[0052] In equation (1) above, n1 represents the existence of multiple R when n is an integer greater than 2. 2 They can be the same or different.

[0053] In the above equation (1), R is... 2 For example, examples can be given by OR 3 It means that R represents and R 3 The group can be an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkoxyalkyl group having 2 to 30 carbon atoms, and examples may also include alkyl acetoacetate ester group having 5 to 30 carbon atoms, 2,4-pentanedione syn (i.e., acetylacetonate group), and 2,2,6,6-tetramethyl-3,5-heptadecanedione syn.

[0054] As R 2 The aforementioned alkyl acetoacetate group with 5 to 30 carbon atoms is not particularly limited. For example, methyl acetoacetate group and ethyl acetoacetate group can be mentioned. Considering the ease of synthesis and stability, ethyl acetoacetate group is preferred.

[0055] Considering factors such as the dispersion of the obtained particles, R 2 Preferably, it is a group represented by the formula (2) above.

[0056] In the above formula (1), considering the refractive index of the obtained particles, L is preferably yttrium, titanium, zirconium or hafnium, and more preferably titanium or zirconium.

[0057] In equation (2) above, R is used as 4 or R 5 The organic group represented by the number of carbon atoms 1 to 30 is not particularly limited. Examples include alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 3 to 30 carbon atoms, alkenyl groups with 2 to 30 carbon atoms, aryl groups with 6 to 30 carbon atoms, and alkoxyalkyl groups with 2 to 30 carbon atoms. Considering the dispersibility of the obtained particles, alkyl groups with 1 to 30 carbon atoms or alkoxyalkyl groups with 2 to 30 carbon atoms are preferred. R 4 or R 5 In the case of an oxygen atom, it is preferable that the oxygen atom is directly bonded to the P in P (=O) in formula (2), that is, the organic group having 1 to 30 carbon atoms is preferably bonded to the aforementioned P through the oxygen atom, and the aforementioned organic group is preferably an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms. In formula (2), R can be 4 and R 5 Both have oxygen atoms that are directly bonded to P in P (=O), and can also R 4 and R 5 Only one of them has that oxygen atom.

[0058] As R 4 or R 5 The alkyl group representing 1 to 30 carbon atoms is not particularly limited; for example, examples can be given for R. 1 Specifically, considering the ease of synthesis of the above-mentioned compounds and the dispersibility of the obtained particles, alkyl groups with 4 to 18 carbon atoms are preferred, and alkyl groups with 6 to 12 carbon atoms are more preferred.

[0059] As R 4 or R 5 The cycloalkyl group represented has 3 to 30 carbon atoms, without particular limitation. For example, examples can be given for R. 1 Specifically, considering the ease of synthesis of the above-mentioned compounds and the dispersibility of the obtained particles, cycloalkyl groups with 4 to 18 carbon atoms are preferred, and cycloalkyl groups with 6 to 12 carbon atoms are more preferred.

[0060] As R 4 or R 5 The alkenyl group representing 2 to 30 carbon atoms is not particularly limited; for example, examples can be given for R. 1 Specifically, considering the ease of synthesis of the above-mentioned compounds and the dispersibility of the obtained particles, alkenyl groups with 4 to 18 carbon atoms are preferred, and alkenyl groups with 6 to 12 carbon atoms are more preferred.

[0061] As R 4 or R 5 The aryl group represents 6 to 30 carbon atoms, without particular limitation. For example, examples can be given for R... 1 Specifically, considering the ease of synthesis of the above-mentioned compounds and the dispersibility of the obtained particles, aryl groups with 6 to 18 carbon atoms are preferred, and aryl groups with 6 to 12 carbon atoms are more preferred.

[0062] As R 4 or R 5 The alkoxyalkyl group representing 2 to 30 carbon atoms is not particularly limited; for example, examples can be given for R. 1 Specifically, considering the ease of synthesis of the above-mentioned compounds and the dispersibility of the obtained particles, alkoxyalkyl groups with 4 to 18 carbon atoms are preferred, and alkoxyalkyl groups with 6 to 12 carbon atoms are more preferred.

[0063] Considering ease of synthesis and reactivity as a coating agent, compounds having the structure represented by formula (1) are preferably represented by formula (3), and more preferably by formula (30).

[0064] In the above equation (3), R is used as 6 or R7 The organic group represented by the number of carbon atoms is not particularly limited. Examples include alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 3 to 30 carbon atoms, alkenyl groups with 2 to 30 carbon atoms, aryl groups with 6 to 30 carbon atoms, and alkoxyalkyl groups with 2 to 30 carbon atoms. Examples of each group can be given for R. 1 The specific examples of the groups are preferably alkyl groups having 1 to 30 carbon atoms.

[0065] As R 6 or R 7 The alkyl group representing 1 to 30 carbon atoms is not particularly limited; for example, examples can be given for R. 1 Specifically, considering reactivity with the coating agent, the alkyl groups shown are preferably alkyl groups with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, and tert-hexyl.

[0066] In the above formula (30), R 60 or R 70 Organic groups representing 1 to 30 carbon atoms and R in formula (3) above. 6 or R 7 The organic groups representing 1 to 30 carbon atoms are the same as those described.

[0067] For example, the following compounds can be cited as compounds represented by the above formula (3).

[0068] [Chemical Formula 6]

[0069]

[0070] (where R is in the formula) 1 R 2 n1, n2, L, R 60 and R 70 As mentioned above.

[0071] Specific examples of compounds having the structure represented by formula (1) above are described below, but are not limited to these.

[0072] [Chemical Formula 7]

[0073]

[0074] (In the formula, R represents an alkylene group having 1 to 3 carbon atoms, R' represents an alkyl group having 1 to 3 carbon atoms, and n represents a number greater than or equal to 0, for example, a number greater than or equal to 0 and less than 10, preferably a number greater than or equal to 0 and less than 5.)

[0075] Compounds having the structure represented by formula (1) above can be manufactured using any organic synthesis reaction, for example, according to the following path 1.

[0076] [Path 1]

[0077] [Chemical Formula 8]

[0078]

[0079] (where R is in the formula) 1 R 2 n1, n2, L, R 8 R 9 (And *as mentioned above.)

[0080] In path 1, in the absence or presence of a catalyst, a compound having the structure represented by formula (5) above is subjected to hydrolytic condensation with a compound represented by formula (6) above in water or a mixed solvent (referred to as a mixture of water and organic solvents, hereinafter the same) to obtain a compound having the structure represented by formula (1) above.

[0081] Catalysts can be either acid catalysts or base catalysts. Examples of acid catalysts include inorganic acids, aliphatic sulfonic acids, aromatic sulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids. Specifically, examples include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, and benzoic acid. Examples of base catalysts include, for example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylethanolamine, N,N- Diethylethanolamine, N-(β-aminoethyl)ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-n-butylethanolamine, N-n-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, methylpyridine, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc.

[0082] The preferred amount of catalyst used is 10 moles relative to 1 mole of the compound represented by formula (6) above. -6 10 moles, more preferably 10 -55 moles, more preferably 10 moles -4 One mole ~ 1 mole.

[0083] OR in the compound represented by the above formula (6) 9 For each mole of the indicated group, the amount of water used is preferably 0.01 to 100 moles, more preferably 0.05 to 50 moles, even more preferably 0.1 to 30 moles, and particularly preferably 0.5 to 5 moles.

[0084] As organic solvents, preferred options include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methylpentyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, and 3-methoxy Methyl propionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, acetylacetone, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl neopentanoyl acetate, methyl isobutanoyl acetate, methyl hexanoyl acetate, methyl lauroyl acetate, 1,2-ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2,3-pentanediol, glycerol, diethylene glycol, hexanediol, etc., and mixtures of two or more of them.

[0085] The amount of organic solvent used is preferably 0 to 1,000 ml, and particularly preferably 0 to 500 ml, relative to 1 mole of the compound represented by formula (6) above.

[0086] The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C, and the reaction time is preferably 10 minutes to 3 hours, more preferably 20 minutes to 1 hour.

[0087] The compound represented by the above formula (3) can be manufactured, for example, according to the following path 2.

[0088] [Path 2]

[0089] [Chemical Formula 9]

[0090]

[0091] (where R is in the formula) 1 R 2 n1, n2, L, R 6 R 7 R 60 R70 R 8 and R 9 As mentioned above.

[0092] In path 2, similarly to path 1, the compound represented by formula (4) above is hydrolyzed and condensed with the compound represented by formula (6) above to obtain the compound represented by formula (3) above.

[0093] In equation (5) above, R 8 The organic groups representing 1 to 30 carbon atoms are the same as those in formula (3) above for R. 6 or R 7 The organic groups representing 1 to 30 carbon atoms are the same as those described.

[0094] In the above equation (6), R is... 9 The organic group represented by the number of carbon atoms is not particularly limited. Examples include alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 3 to 30 carbon atoms, alkenyl groups with 2 to 30 carbon atoms, aryl groups with 6 to 30 carbon atoms, and alkoxyalkyl groups with 2 to 30 carbon atoms. Examples of each group can be given for R. 1 The specific examples of the groups are preferably alkyl groups having 1 to 30 carbon atoms.

[0095] As R 9 The alkyl group representing 1 to 30 carbon atoms is not particularly limited; for example, examples can be given for R. 6 or R 7 The specific examples of groups, etc., are discussed in terms of ease of synthesis and compatibility with OR. 8 Considering the reactivity of the indicated groups, alkyl groups with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, and tert-hexyl, are preferred.

[0096] <Particles having a structure represented by equation (1) on their surface>

[0097] The particles involved in this invention have the structure represented by the above formula (1). The above particles have excellent dispersibility and refractive index, and therefore can be suitable for use in high refractive index materials.

[0098] Particles having the structure represented by formula (1) on their surface have, for example, the following morphology: the structure represented by formula (1) is introduced onto the surface of a particle that does not have the structure represented by formula (1) on its surface. There are no particular limitations on particles that do not have the structure represented by formula (1) on their surface; for example, particles with hydroxyl groups on their surface can be cited. There are no particular limitations on particles with hydroxyl groups on their surface; for example, metal oxide particles such as titanium oxide particles, zirconium oxide particles, and hafnium oxide particles; and other particles with high refractive indices such as Si particles can be cited.

[0099] The particle size of the particles involved in this invention is not particularly limited, but considering factors such as dispersibility, it is preferably 1 to 20 nm, more preferably 2 to 15 nm, and even more preferably 4 to 10 nm. It should be noted that, in this specification, the particle size refers to the particle size measured by observing the particles using TEM.

[0100] When determining the average diameter of a dispersion composition containing the particles of the present invention, the average diameter can be determined using a dynamic light scattering (DLS) device such as the Malvern Zetasizer Nano S. For example, when the particles of the present invention are dispersed in a dispersion medium such as PGMEA at a concentration of 5% by mass or less, the average diameter is monodisperse and ranges from 20 nm or less.

[0101] The dispersion composition of the present invention includes, for example, a combination of the particles of the present invention with a known organic solvent or a known liquid monomer, wherein the dispersibility of the particles of the present invention is maintained.

[0102] The structure represented by equation (1) above is bonded to the particle via at least one connecting bond. There is no particular limitation on the form in which the structure represented by equation (1) is bonded to the particle; for example, forms (F1a) and (F1b) can be cited below. In form (F1a), the structure represented by equation (1) above is bonded to the particle via two connecting bonds. In contrast, in form (F1b), the structure represented by equation (1) above is bonded to the particle via one connecting bond.

[0103] [Chemical Formula 10]

[0104]

[0105] (where R is in the formula) 1 R 2 As mentioned above, n1, n2, and L represent particles, and p represents a particle.

[0106] [Method for manufacturing particles having a structure represented by formula (1) on their surface]

[0107] For particles having a structure represented by formula (1) on their surface, for example, as described above, they can be manufactured by a manufacturing method having a particle coating process (hereinafter also referred to as "manufacturing method 1") or a manufacturing method having a first reaction process and a second reaction process (hereinafter also referred to as "manufacturing method 2").

[0108] The particle coating process, the first reaction process, and the second reaction process can be carried out, for example, in water or a mixed solvent, with or without a catalyst. Examples of catalysts, examples of organic solvents, reaction temperatures, and reaction times are the same as those described in pathway 1.

[0109] Manufacturing method 1 can be implemented, for example, according to path 3 or 4 below.

[0110] [Path 3]

[0111] [Chemical Formula 11]

[0112]

[0113] (where R is in the formula) 1 R 2 n1, n2, L, R 6 R 7 (And p as mentioned above.)

[0114] In path 3, particles having hydroxyl groups on their surface are hydrolyzed and condensed with the compound represented by formula (3) above in water or a mixed solvent, with or without a catalyst, to obtain particles having the structure represented by formula (1) above on their surface in the form described above (F1a). Examples of catalysts, organic solvents, reaction temperatures, and reaction times are the same as those described in path 1.

[0115] The preferred amount of catalyst used is 10 moles relative to 1 mole of the compound represented by formula (3) above. -6 10 moles, more preferably 10 -5 5 moles, more preferably 10 moles -4 One mole ~ 1 mole.

[0116] OR in the compound represented by the above formula (3) 6 The groups and OR shown 7 For every 1 mole of the total number of groups shown, the amount of water used is preferably 0.01 to 100 moles, more preferably 0.05 to 50 moles, even more preferably 0.1 to 30 moles, and particularly preferably 1 to 5 moles.

[0117] The amount of organic solvent used is preferably 0 to 1,000 ml, and particularly preferably 0 to 500 ml, relative to 1 mole of the compound represented by formula (3) above.

[0118] [Path 4]

[0119] [Chemical Formula 12]

[0120]

[0121] (where R is in the formula) 1 R 2 n1, n2, L, R 6 R 7 (And p as mentioned above.)

[0122] In path 4, particles with hydroxyl groups on their surface are hydrolyzed and condensed with the compound represented by formula (3) above in water or a mixed solvent, with or without a catalyst, to obtain particles having the structure represented by formula (1) above on their surface in the form described above (F1b). Examples of catalysts, amounts of catalysts used, examples of organic solvents, amounts of organic solvents used, reaction temperatures, and reaction times are the same as those described in path 3.

[0123] It should be noted that in path 4, R 6 Preferably L(R) 2 ) n1 (O) n2 The group shown.

[0124] OR in the compound represented by the above formula (3) 7 For each mole of the indicated group, the amount of water used is preferably 0.01 to 100 moles, more preferably 0.05 to 50 moles, and even more preferably 0.1 to 30 moles.

[0125] Manufacturing method 2 can be implemented, for example, according to the following path 5.

[0126] [Path 5]

[0127] [Chemical Formula 13]

[0128]

[0129] (where R is in the formula) 1 R 2 n1, n2, L, R 60 R 70 R 8 R 9 (And p as mentioned above.)

[0130] In path 5, particles having hydroxyl groups on their surface are hydrolyzed and condensed with the compound represented by formula (4) in water or a mixed solvent, with or without a catalyst, to obtain particles having the structure represented by formula (5) on their surface in the form described above (F5a) (first reaction step). These particles are then hydrolyzed and condensed with the compound represented by formula (6) in water or a mixed solvent, with or without a catalyst, to obtain particles having the structure represented by formula (1) on their surface in the form described above (F1a) (second reaction step). Examples of catalysts and organic solvents are the same as those described in path 1.

[0131] Regarding the amount of catalyst used, in the case of the first reaction step, it is preferably 10 moles relative to 1 mole of the compound represented by formula (4) above, or in the case of the second reaction step, relative to 1 mole of the compound represented by formula (6) above. -6 10 moles, more preferably 10 -5 5 moles, more preferably 10 moles -4 One mole ~ 1 mole.

[0132] Regarding the amount of water used, in the case of the first reaction step, relative to the OR in the compound represented by the above formula (4) 60 The groups and OR shown 70 The total number of groups shown per mole, or in the case of the second reaction step, relative to the OR in the compound represented by the above formula (6). 9 The amount of each group shown is preferably 0.01 to 100 moles, more preferably 0.05 to 50 moles, even more preferably 0.1 to 30 moles, and particularly preferably 1 to 5 moles per mole.

[0133] Regarding the amount of organic solvent used, in the case of the first reaction step, it is preferably 0 to 1,000 ml relative to 1 mole of the compound represented by formula (4) above, or in the case of the second reaction step, it is preferably 0 to 500 ml relative to 1 mole of the compound represented by formula (6) above.

[0134] In both the first and second reaction steps, the reaction temperature is preferably 0–100°C, more preferably 5–80°C, and the reaction time is preferably 10 minutes–3 hours, more preferably 20 minutes–1 hour.

[0135] Example

[0136] The present invention will be described in more detail below through embodiments, but the present invention is not limited to these embodiments.

[0137] [Preparation of compounds having the structure represented by formula (1)]

[0138] The compound represented by 4-A (hereinafter also referred to as "compound 4-A") and the compound represented by 6-A (hereinafter also referred to as "compound 6-A") were hydrolyzed and condensed at room temperature for 60 minutes. The molar ratio of compound 4-A to compound 6-A was 1:1. The hydrolyzed and condensed reaction mixture was subjected to gel permeation chromatography (GPC), and a new peak appeared that was not observed when compound 4-A or compound 6-A was placed alone under the above conditions and then subjected to GPC. The number-average molecular weight converted to polystyrene for this new peak was calculated, and the result was 1300. Based on the above results and 1 The H-NMR results confirmed that the product corresponding to the aforementioned new peak yielded the compound represented by 3-A below. It should be noted that the aforementioned new peak has a shoulder; based on the number-average molecular weight calculated in polystyrene form based on this shoulder, the compound represented by 3-B below was also confirmed to have been generated. Furthermore, when the product was supplied to… 13 In the C-NMR results, peaks that were identified as (CH3O)1, (CH3O)2, or SiCH2 in the product were found in the region of 5-7 ppm where no peaks appeared when the raw material was supplied for the same measurement.

[0139] [Chemical Formula 14]

[0140]

[0141] [Preparation and evaluation of coated particles]

[0142] (Preparation of titanium dioxide particles)

[0143] Referring to Example 8 of International Publication No. 2020 / 106860, titanium oxide particles were recovered. TEM observation of the titanium oxide particles revealed them to be spherical with a particle size of 7 nm. In Table 1, these titanium oxide particles are referred to as "TiO2".

[0144] (Preparation of coated particles)

[0145] In a 20cc vial, the above-mentioned titanium oxide particles were mixed with compound 4-A in the proportions shown in Table 1 and stirred at 110°C for 30 minutes. Then, compound 6-A was further added to the above vial, and the mixture was stirred at 110°C for 20 minutes to obtain coated particles. It should be noted that, in Comparative Example 1, gelation occurred at this stage, making further evaluation impossible. Furthermore, the above reaction was carried out in a PGMEA. The washing conditions for the coated particles were as follows.

[0146] 1. Add n-heptane to the reaction system containing PGMEA to precipitate the coated particles, then centrifuge. (In the washing conditions row of Table 1, this is indicated as 1.)

[0147] 2. Next, the coated particles, after centrifugation, were collected, dispersed in tetrahydrofuran (THF), and heptane was added to precipitate the coated particles, followed by centrifugation. (This is indicated as 2 in the washing conditions row of Table 1.)

[0148] 3. After collecting the coated particles again via centrifugation, disperse them in tetrahydrofuran (THF), add heptane to precipitate the coated particles, and then centrifuge again. (This is indicated as 3 in the washing conditions row of Table 1.)

[0149] (Evaluation of the coated particles)

[0150] • Dispersion

[0151] For the filtered coated particles, an experiment was conducted based on the following steps: washing with a cleaning solution of n-heptane, drying at 25°C after filtration, redispersion in a dispersion medium of PGMEA, and filtration.

[0152] The dispersibility of the coated particles was evaluated using the following criteria. The results are shown in Table 1.

[0153] + (Good): Cleaning, drying, redispersing and filtration can all be achieved.

[0154] -(Defect): The coated particles are gelled, and at least one of the following processes—washing, drying, redispersing, and filtration—cannot be performed, making the following measurements impossible.

[0155] XPS

[0156] X-ray photoelectron spectroscopy (XPS) analysis was performed on the prepared coated particles to calculate the molar ratio of phosphorus to silicon in the coated particles. Based on this, the molar ratio of the portion of the coated particles derived from compound 6-A to the portion derived from compound 4-A was calculated. The results are shown in Table 1.

[0157] ·Cover rate

[0158] The filtered coated particles were redispersed in a dispersion medium, PGMEA, to prepare a 50% by mass dispersion. Thermogravimetric analysis (TGA) was performed on this dispersion to calculate the proportion of the solid components derived from compound 6-A and compound 4-A in the dispersion, which was taken as the coating percentage (by mass%). The results are shown in Table 1.

[0159] Refractive index

[0160] In the portion of the coated particles coated with titanium oxide particles (i.e., the sum of the portions derived from compound 6-A and compound 4-A), the higher the titanium content, the easier it is to further increase the refractive index of the coated particles. Since titanium is included in the portion derived from compound 6-A, it is reasonable to understand that the higher the amount of the portion derived from compound 6-A, the easier it is to further increase the refractive index of the coated particles. Therefore, the refractive index of the coated particles was evaluated using the XPS-based molar ratio of the portion derived from compound 6-A to the portion derived from compound 4-A (hereinafter also referred to as "compound 6-A / compound 4-A") as the following benchmark. The results are shown in Table 1.

[0161] ++ (Very good): Compound 6-A / Compound 4-A ratio is above 0.5.

[0162] + (Good): Compound 6-A / Compound 4-A exceeds 0 and is less than 0.5.

[0163] -(Poor): Compound 6-A / Compound 4-A is 0. Or, the coating particles are poorly dispersed.

[0164] • Particle size of the dispersion composition

[0165] The coated particles of Examples 1-5 were dispersed at a concentration of 5% by mass or less in a dispersion medium such as PGMEA to obtain dispersion compositions. The average diameter of the coated particles in the dispersion compositions was measured using a Malvern Zetasizer Nano S (Dynamic Light Scattering (DLS) device). As a result, the average diameter of the particles in Examples 1-5 was all 20 nm or less.

[0166] [Table 1]

[0167]

[0168] As shown in Table 1, the particles obtained in the examples have excellent dispersion and refractive index, while the particles obtained in the comparative examples have poor dispersion or refractive index.

Claims

1. A compound having the structure represented by the following formula (1), [Chemical Formula 1] In equation (1), R 1 Indicates an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms. R 2 The group represented by the following formula (2) is... n1 and n2 each independently represent integers greater than or equal to 0, where, n1+2×n2 is the valence determined by the types of L. L represents titanium or zirconium. * indicates a connection key; [Chemical Formula 2] In equation (2), R 4 and R 5 It refers to an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms that may have oxygen atoms.

2. The compound represented by the following formula (3), [Chemical Formula 3] In equation (3), R 1 Indicates an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms. R 2 The group represented by the following formula (2) is... n1 and n2 each independently represent integers greater than or equal to 0, where, n1+2×n2 is the valence determined by the types of L. L represents titanium or zirconium. R 6 and R 7 Each independently represents an alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or an L(R) group. 2 ) n1 (O) n2 The groups shown, [Chemical Formula 4] In equation (2), R 4 and R 5 It refers to an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms that may have oxygen atoms.

3. The compound according to claim 1 or 2, wherein, The compound is represented by the following formula (30), [Chemical Formula 4] In equation (30), R 1 R 2 As mentioned above, n1, n2, and L, R 60 and R 70 It refers to an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms.

4. A particle having a structure on its surface represented by the following formula (1), [Chemical Formula 5] In equation (1), R 1 Indicates an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms. R 2 The group represented by the following formula (2) is... n1 and n2 each independently represent integers greater than or equal to 0, where, n1+2×n2 is the valence determined by the types of L. L represents titanium or zirconium. * indicates a connection key; [Chemical Formula 6] In equation (2), R 4 and R 5 It refers to an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms that may have oxygen atoms.

5. A dispersion composition comprising the particles of claim 4.

6. A manufacturing method for producing particles having a structure on their surface represented by the following formula (1), The manufacturing method includes a particle coating step in which particles having hydroxyl groups on their surface are reacted with a compound represented by formula (30) to obtain particles having a structure represented by formula (1) on their surface, or... The manufacturing method has the following characteristics: A first reaction step involves reacting particles having hydroxyl groups on their surface with a compound represented by formula (4) to obtain particles having a structure represented by formula (5) on their surface; and A second reaction step involves reacting the particles obtained in the first reaction step with a compound represented by the following formula (6) to obtain particles having a structure represented by the following formula (1) on their surface. [Chemical Formula 7] In equation (1), R 1 Indicates an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms. R 2 The group represented by the following formula (2) is... n1 and n2 each independently represent integers greater than or equal to 0, where, n1+2×n2 is the valence determined by the types of L. L represents titanium or zirconium. * indicates a connection key; [Chemical Formula 8] In equation (2), R 4 and R 5 It refers to an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms that may have oxygen atoms; [Chemical Formula 9] In equation (30), R 1 R 2 As mentioned above, n1, n2, and L, R 60 and R 70 Indicates an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms; [Chemical Formula 10] In equation (4), R 1 R 60 and R 70 As mentioned above, R 8 Indicates an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms; [Chemical Formula 11] In equation (5), R 1 and R 8 As mentioned above; R 9 O-L(R 2 ) n1 (O) n2 (6) In equation (6), R 2 As mentioned above, n1, n2, and L, R 9 It refers to an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms.

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