JP5014895B2 - Method for producing silica-coated gold colloidal particles and silica-coated gold colloidal particles - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 481
- 239000002245 particle Substances 0.000 title claims description 393
- 239000000377 silicon dioxide Substances 0.000 title claims description 235
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical compound [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 title claims description 144
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000006185 dispersion Substances 0.000 claims description 103
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 50
- 239000000084 colloidal system Substances 0.000 claims description 37
- 239000011247 coating layer Substances 0.000 claims description 28
- 229910000077 silane Inorganic materials 0.000 claims description 27
- -1 silane compound Chemical class 0.000 claims description 27
- 230000002378 acidificating effect Effects 0.000 claims description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- 125000003277 amino group Chemical group 0.000 claims description 17
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 16
- 150000002894 organic compounds Chemical class 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 13
- 150000007942 carboxylates Chemical group 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 description 40
- 238000002360 preparation method Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000001054 red pigment Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000001509 sodium citrate Substances 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UZQJSDJLHIHJRJ-UHFFFAOYSA-N 3-[diethoxy(ethyl)silyl]propane-1-thiol Chemical compound CCO[Si](CC)(OCC)CCCS UZQJSDJLHIHJRJ-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、新規なシリカ被覆金コロイド粒子およびその製造方法に関する。 The present invention relates to a novel silica-coated gold colloidal particle and a method for producing the same.
従来、金粒子は、導電性材料、電子部品材料、触媒、バイオマーカー等に使用されるほかに、コロイド粒子にすると赤色を呈するため、顔料として、蛍光体顔料、化粧材料などにも用いられている。 Conventionally, gold particles are used for conductive materials, electronic component materials, catalysts, biomarkers, etc., and since they are red when colloidal particles are used, they are also used as phosphor pigments, cosmetic materials, etc. Yes.
しかしながら、金コロイド粒子を顔料として高温環境で使用する場合、具体的にはブラウン管等に用いると約４００℃の高温となり、容易に凝集したり、黒色に変色したりする問題があった。 However, when gold colloid particles are used as a pigment in a high-temperature environment, specifically, when used in a cathode ray tube or the like, there is a problem that the temperature becomes about 400 ° C. and easily aggregates or turns black.
そこで、金コロイドの表面を修飾する種々の試みがなされていた。本発明者らは、表面を安定化するために、シリカ層で、金コロイド粒子を被覆することを試みたが、シリカ被覆層を安定化するために加熱処理を行うと、金コロイド粒子が、凝集したり変色したりして、所望のものを得ることは困難であった。 Accordingly, various attempts have been made to modify the surface of colloidal gold. In order to stabilize the surface, the present inventors tried to coat gold colloid particles with a silica layer, but when heat treatment was performed to stabilize the silica coating layer, the gold colloid particles became It was difficult to obtain the desired product by agglomeration or discoloration.
このような情況のもと、金コロイド粒子表面にシリカ被覆層を形成する方法の出現が望まれていた。 Under such circumstances, the advent of a method for forming a silica coating layer on the surface of colloidal gold particles has been desired.
そこで、上記課題を解決するために本発明者らは、シリカ層の被覆方法について鋭意検討した結果、シリカコロイド粒子と金コロイド粒子の表面処理を特定の組み合わせとすることで、金属コロイド粒子表面にシリカコロイド粒子が層をなして結合した粒子が得られ、加熱処理しても凝集したり変色したりすることなく鮮明な赤色を維持できることを見出して本発明を完成するに至った。
[1]平均粒子径が５〜１００nmの範囲にあり、カルボキシル基および／またはカルボキシ
レート基含有有機化合物で表面処理された金コロイド粒子分散液と、
平均粒子径が４〜４０nmの範囲にあり、アミノ基含有シラン化合物で表面処理されたシリカコロイド粒子分散液とを混合することを特徴とするシリカ被覆金コロイド粒子の製造方法。
[2]平均粒子径が５〜１００nmの範囲にある金コロイド粒子分散液と、
平均粒子径が４〜４０nmの範囲にあり、メルカプト基含有シラン化合物で表面処理されてチオール基（−ＳＨ基）が導入されたシリカコロイド粒子分散液と
を混合するシリカ被覆金コロイド粒子の製造方法。
[3]分散液を混合後、さらに酸性珪酸液を添加して、シリカコロイド粒子の表面を被覆す
る[1]または[2]のシリカ被覆金コロイド粒子の製造方法。
[4]さらに、乾燥するおよび／または加熱処理する[1]〜[3]のシリカ被覆金コロイド粒子
の製造方法。
[5]平均粒子径が４〜４０nmの範囲にあるシリカコロイド粒子で、平均粒子径が５〜１０
０nmの範囲にある金コロイド粒子の表面を被覆されてなるシリカ被覆金コロイド粒子。
[6]さらにシリカ被覆層を形成してなる[5]のシリカ被覆金コロイド粒子。
[7]シリカ層（シリカコロイド粒子層と必要に応じて形成されたシリカ被覆層の合計）の
厚みが４〜５０nmの範囲にある[5]または[6]のシリカ被覆金コロイド粒子。
[8]前記シリカ被覆金コロイド粒子が赤色（波長：５２０〜５５０nm）を呈する[5]〜[7]
のシリカ被覆金コロイド粒子。
In order to solve the above problems, the present inventors have intensively studied the method of coating the silica layer. As a result, the surface treatment of the colloidal silica particles and the colloidal gold particles can be applied to the surface of the colloidal metal particles by a specific combination. Particles in which silica colloidal particles are combined in layers are obtained, and the present invention has been completed by finding that a vivid red color can be maintained without agglomeration or discoloration even when heat-treated.
[1] A colloidal gold particle dispersion having an average particle diameter in the range of 5 to 100 nm and surface-treated with a carboxyl group and / or carboxylate group-containing organic compound;
A method for producing silica-coated gold colloidal particles, comprising mixing a silica colloidal particle dispersion having an average particle diameter in the range of 4 to 40 nm and surface-treated with an amino group-containing silane compound.
[2] a colloidal gold particle dispersion having an average particle size in the range of 5 to 100 nm;
A method for producing silica-coated gold colloidal particles comprising mixing a silica colloidal particle dispersion having an average particle diameter in the range of 4 to 40 nm and surface-treated with a mercapto group-containing silane compound and introduced with thiol groups (-SH groups) .
[3] The method for producing a silica-coated gold colloidal particle according to [1] or [2], wherein after mixing the dispersion, an acidic silicic acid solution is further added to coat the surface of the silica colloidal particle.
[4] The method for producing silica-coated gold colloidal particles according to [1] to [3], which is further dried and / or heat-treated.
[5] Silica colloidal particles having an average particle size in the range of 4 to 40 nm and an average particle size of 5 to 10
Silica-coated gold colloidal particles obtained by coating the surface of colloidal gold particles in the range of 0 nm.
[6] The silica-coated gold colloidal particles according to [5], further formed with a silica coating layer.
[7] The silica-coated gold colloidal particles according to [5] or [6], wherein the thickness of the silica layer (the total of the silica colloid particle layer and the silica coating layer formed as necessary) is in the range of 4 to 50 nm.
[8] The silica-coated gold colloidal particles exhibit a red color (wavelength: 520 to 550 nm) [5] to [7]
Silica-coated gold colloidal particles.
本発明によれば、金コロイド粒子の表面が全面にわたってシリカコロイド粒子で被覆されているために、高温にさらしても凝集したり変形することがなく、さらに変色することもなく鮮明な赤色を呈する金コロイド粒子の製造方法および該製造方法によって得られるシリカ被覆金コロイド粒子を提供することができる。 According to the present invention, since the surface of the gold colloid particles is entirely coated with the silica colloid particles, it does not agglomerate or deform even when exposed to a high temperature, and exhibits a clear red color without further discoloration. A method for producing gold colloidal particles and silica-coated gold colloidal particles obtained by the production method can be provided.
以下、本発明について、具体的に説明する
[シリカ被覆金コロイド粒子の製造方法]
本発明に係るシリカ被覆金コロイド粒子の第１の製造方法は、
平均粒子径が５〜１００nmの範囲にあり、カルボキシル基および／またはカルボキシレート基含有有機化合物で表面処理された金コロイド粒子（M-1）分散液と、
平均粒子径が４〜４０nmの範囲にあり、アミノ基含有シラン化合物で表面処理されたシリカコロイド粒子（A-1）分散液とを混合することを特徴としている。
Hereinafter, the present invention will be specifically described.
[Method for producing silica-coated gold colloidal particles]
The first production method of the silica-coated gold colloidal particles according to the present invention includes:
A colloidal gold colloidal particle (M-1) dispersion having an average particle size in the range of 5 to 100 nm and surface-treated with a carboxyl group and / or carboxylate group-containing organic compound;
The average particle diameter is in the range of 4 to 40 nm and is characterized by mixing with a silica colloidal particle (A-1) dispersion liquid surface-treated with an amino group-containing silane compound.
また、本発明に係るシリカ被覆金コロイド粒子の第２の製造方法は、
平均粒子径が５〜１００nmの範囲にある金コロイド粒子（M-2）分散液と、
平均粒子径が４〜４０nmの範囲にあり、メルカプトト基含有シラン化合物で表面処理された表面にチオール基（-SH基）を有するシリカコロイド粒子（A-2）分散液とを混合することを特徴としている。
Further, the second production method of the silica-coated gold colloidal particles according to the present invention includes:
A colloidal gold particle (M-2) dispersion having an average particle size in the range of 5 to 100 nm;
Mixing with a silica colloidal particle (A-2) dispersion having an average particle diameter in the range of 4 to 40 nm and having a thiol group (-SH group) on the surface treated with a mercaptoto group-containing silane compound. It is a feature.
金コロイド粒子
金コロイド粒子（M）は、従来公知の金コロイド粒子を用いることができる。
金コロイド粒子は平均粒子径（ＤM）が５〜１００nm、さらには１０〜５０nmの範囲に
あることが好ましい。
Colloidal gold particles As the gold colloid particles (M), conventionally known gold colloid particles can be used.
The colloidal gold particles preferably have an average particle diameter (D M ) of 5 to 100 nm, more preferably 10 to 50 nm.
金コロイド粒子の平均粒子径（ＤM）が５nm未満の場合は、赤色顔料として用いる場合
、赤色の色調が損なわれ、またシリカコロイド粒子による被覆が困難であり、金コロイド粒子の平均粒子径（ＤM）が１００nmを越えると、赤色顔料としては不向きである。
When the average particle diameter (D M ) of the colloidal gold particles is less than 5 nm, when used as a red pigment, the red color tone is impaired, and it is difficult to coat with the colloidal silica particles. If D M ) exceeds 100 nm, it is not suitable as a red pigment.
赤色顔料として用いる場合は平均粒子径が５０nm以下、特に４０nm以下であることが好ましい。
このような金コロイド粒子（Ｍ）は、従来公知の方法によって製造することができる。例えば、還元剤の存在下、塩化金酸水溶液を還元する周知の方法によって製造することができる。あるいは、塩化金酸水溶液に超音波を照射することによっても得ることができる。
When used as a red pigment, the average particle size is preferably 50 nm or less, particularly 40 nm or less.
Such gold colloidal particles (M) can be produced by a conventionally known method. For example, it can be produced by a known method of reducing an aqueous chloroauric acid solution in the presence of a reducing agent. Or it can obtain also by irradiating a chloroauric acid aqueous solution with an ultrasonic wave.
本発明の第１の製造方法に用いる金コロイド粒子（M-1）はカルボキシル基および／ま
たはカルボキシレート基含有有機化合物で表面処理されている。カルボキシル基またはカルボキシレート基を有する有機化合物としては、例えば、酢酸、蓚酸、蟻酸、酒石酸、リンゴ酸、コハク酸、グルコン酸、マレイン酸、フタル酸、アルギン酸、クエン酸等の他、これらの塩およびエステルが挙げられる。
The gold colloidal particles (M-1) used in the first production method of the present invention are surface-treated with a carboxyl group and / or carboxylate group-containing organic compound. Examples of the organic compound having a carboxyl group or a carboxylate group include, for example, acetic acid, succinic acid, formic acid, tartaric acid, malic acid, succinic acid, gluconic acid, maleic acid, phthalic acid, alginic acid, citric acid, and salts thereof. Examples include esters.
金コロイド粒子（Ｍ）の処理方法は前記有機化合物が金属コロイド粒子（Ｍ）の表面に吸着あるいは結合すれば特に制限はなく従来公知の方法を採用することができる。例えば金コロイド粒子（Ｍ）の分散液に前記有機化合物を金コロイド粒子（Ｍ）の表面に充分量吸着するに足る量を加えることによって処理することができる。 The method for treating the gold colloidal particles (M) is not particularly limited as long as the organic compound is adsorbed or bonded to the surface of the metal colloidal particles (M), and a conventionally known method can be adopted. For example, the treatment can be performed by adding a sufficient amount of the organic compound to the gold colloid particle (M) surface to the dispersion of the gold colloid particle (M).
あるいは、Frensの方法によっても調製することができ、具体的には前記カルボキシル
基またはカルボキシレート基を有する有機化合物溶液に塩化金酸を添加し、加熱、還流することによって表面にカルボキシル基またはカルボキシレート基を有する有機化合物を吸着した金コロイド粒子を調製することができる。
Alternatively, it can also be prepared by the method of Frens. Specifically, chloroauric acid is added to the organic compound solution having the carboxyl group or carboxylate group, and the mixture is heated and refluxed to give carboxyl group or carboxylate on the surface. Colloidal gold particles adsorbing an organic compound having a group can be prepared.
この時、有機化合物の使用量は、有機化合物のＣＭＣ（臨界ミセル生成濃度）の５〜５０％、好ましくは５〜３０％である。
表面処理した金コロイド粒子分散液の濃度は、特に制限はないが、通常、固形分として０．１〜２０重量％の範囲にあることが好ましい。
At this time, the amount of the organic compound used is 5 to 50%, preferably 5 to 30%, of the CMC (critical micelle formation concentration) of the organic compound.
The concentration of the surface-treated gold colloid particle dispersion is not particularly limited, but it is usually preferably in the range of 0.1 to 20% by weight as the solid content.
また、第２の製造方法に用いる金コロイド粒子(M-2)は表面処理することなく使用され
る。
シリカコロイド粒子
本発明に用いるシリカコロイド粒子(A)は平均粒子径が後述する範囲にあれば特に制限
はなく、従来公知のシリカコロイド粒子を用いることができる。
The gold colloidal particles (M-2) used in the second production method are used without surface treatment.
Silica colloid particles The silica colloid particles (A) used in the present invention are not particularly limited as long as the average particle diameter is within the range described below, and conventionally known silica colloid particles can be used.
シリカコロイド粒子は平均粒子径（ＤA）が４〜４０nm、さらには５〜３０nmの範囲に
あることが好ましい。（ＤA）が小さい場合は、得ること自体が困難であり、得られたと
してもシリカコロイド粒子の安定性が不充分で、さらに表面処理することも困難であり、使用が難しい。（ＤA）が大きいものは、光学的散乱が増すため色調が損なわれる傾向に
あり、また、金コロイド粒子の表面に形成されるシリカ被服層が厚くなり、赤色顔料として用いる場合に不鮮明となることがある。さらに、被覆するシリカコロイド粒子間隙が残り赤色の変色を抑制することができない場合がある。
The silica colloidal particles preferably have an average particle diameter (D A ) in the range of 4 to 40 nm, more preferably 5 to 30 nm. When (D A ) is small, it is difficult to obtain itself, and even if it is obtained, the stability of the silica colloidal particles is insufficient, and it is also difficult to treat the surface, making it difficult to use. When (D A ) is large, the color tone tends to be impaired due to an increase in optical scattering, and the silica coating layer formed on the surface of the gold colloidal particles becomes thick and becomes unclear when used as a red pigment. Sometimes. Furthermore, there are cases where the gap between the silica colloidal particles to be coated remains and red discoloration cannot be suppressed.
また、シリカコロイド粒子（Ａ）の平均粒子径（ＤA）は金コロイド粒子（Ｍ）の平均
粒子径（ＤM）より小さいことが好ましい。（ＤA）／（ＤM）が０．０４〜１、さらには
０．０５〜０．５の範囲にあることが好ましい。（ＤA）／（ＤM）が小さいと、金コロイド粒子に被覆する際にシリカコロイド粒子同士が凝集することがあり、また、シリカ被覆層の厚さが薄いために、加熱（過熱）した際に被覆層が収縮し、クラックが生じて変色を抑制することができない場合がある。（ＤA）／（ＤM）が大きすぎても、金コロイド粒子（Ｍ）の平均粒子径（ＤM）によっても異なるが、金コロイド粒子表面をシリカコロイド
粒子で緻密に被覆することができない場合があり、耐熱性が不充分となり、赤色の色調が損なわれることがある。
The average particle diameter (D A ) of the silica colloid particles (A) is preferably smaller than the average particle diameter (D M ) of the gold colloid particles (M). (D A ) / (D M ) is preferably in the range of 0.04 to 1, and more preferably 0.05 to 0.5. When (D A ) / (D M ) is small, the colloidal silica particles may agglomerate when they are coated on the gold colloidal particles, and the silica coating layer is thin, and thus heated (overheated). In some cases, the coating layer contracts and cracks occur, and discoloration cannot be suppressed. Even if (D A ) / (D M ) is too large, it depends on the average particle diameter (D M ) of the gold colloid particles (M), but the surface of the gold colloid particles cannot be densely coated with the silica colloid particles. In some cases, the heat resistance becomes insufficient, and the red color tone may be impaired.
本発明の第１の製造方法に用いるシリカコロイド粒子(A-1)はアミノ基含有シラン化合
物で表面処理されている。アミノ基を有するシラン化合物としては、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−（フェニル）γ−アミノプロピルトリメトキシシラン等が挙げられる。シリカコロイド粒子（A-1）の
処理方法は、従来公知のシランカップリング剤処理と同様に行うことができ、具体的にはシリカコロイド粒子水分散液にアミノ基を有するシラン化合物が必要量溶解したアルコール溶液を添加する。ここで、シラン化合物の必要量はシリカコロイド粒子の粒子径（粒子表面積）によっても異なるが少なくともシリカコロイド粒子の表面を充分に覆うに足る量であることが好ましい。
The silica colloidal particles (A-1) used in the first production method of the present invention are surface-treated with an amino group-containing silane compound. Examples of the silane compound having an amino group include γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- ( Phenyl) γ-aminopropyltrimethoxysilane and the like. The silica colloidal particles (A-1) can be treated in the same way as the conventionally known silane coupling agent treatment. Specifically, the required amount of silane compounds having amino groups is dissolved in an aqueous dispersion of silica colloid particles. Add the prepared alcohol solution. Here, the required amount of the silane compound varies depending on the particle diameter (particle surface area) of the silica colloid particles, but is preferably an amount sufficient to sufficiently cover at least the surface of the silica colloid particles.
本発明の第２の製造方法に用いるシリカコロイド粒子(A-2)はメルカプトト基含有シラ
ン化合物で表面処理されている。メルカプト基を有するシラン化合物としては、γ-メル
カプトプロピルトリメトキシシラン、γ−メルカプトエチルメチルジメトキシシラン、γ−メルカプトジメチルジメトキシシラン、γ−メルカプトプロピルエチルジエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシ
シラン等が挙げられる。なかでも３（γ）−メルカプトプロピルトリメトキシシランが望ましい。
The silica colloid particles (A-2) used in the second production method of the present invention are surface-treated with a mercaptoto group-containing silane compound. Examples of the silane compound having a mercapto group include γ-mercaptopropyltrimethoxysilane, γ-mercaptoethylmethyldimethoxysilane, γ-mercaptodimethyldimethoxysilane, γ-mercaptopropylethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Mercaptopropyltriethoxysilane and the like. Of these, 3 (γ) -mercaptopropyltrimethoxysilane is preferable.
シリカコロイド粒子（A-2）の処理方法は、従来公知のシランカップリング剤処理と同
様に行うことができ、具体的にはシリカコロイド粒子（A-2）水分散液にメルカプト基を
有するシラン化合物が必用量溶解したアルコール溶液を添加する。ここで、シラン化合物の必要量はシリカコロイド粒子（A-2）の粒子径（粒子表面積）によっても異なるが少な
くともシリカコロイド粒子（A-2）の表面を充分に覆うに足る量であることが好ましい。
シリカコロイド粒子（A-2）は、表面がチオール基（−ＳＨ）により修飾されている。
The silica colloidal particles (A-2) can be treated in the same manner as the conventionally known silane coupling agent treatment. Specifically, the silica colloidal particles (A-2) in the aqueous dispersion have a mercapto group. Add an alcohol solution containing the required amount of compound. Here, the required amount of the silane compound varies depending on the particle diameter (particle surface area) of the silica colloidal particles (A-2), but is sufficient to cover at least the surface of the silica colloidal particles (A-2). preferable.
The surface of the silica colloidal particles (A-2) is modified with thiol groups (—SH).
本発明で用いられるシリカコロイド粒子（Ａ）分散液の濃度は特に制限はないが、通常、固形分として０．１〜２０重量％の範囲にあることが好ましい。
混合工程
以上のような、表面処理されたシリカコロイド粒子（Ａ）分散液と、金コロイド粒子（Ｍ）分散液とを混合すると金コロイド粒子（Ｍ）の表面にシリカコロイド粒子（Ａ）が集合し、第１の製造方法ではアミノ基とカルボキシル基またはカルボキシレート基とが結合して自己組織化する。また第２の製造方法では、金コロイド粒子の表面にシリカコロイド粒子が集合し、チオール基（−ＳＨ）が金属コロイド表面に結合して自己組織化する。
The concentration of the silica colloidal particle (A) dispersion used in the present invention is not particularly limited, but it is usually preferably in the range of 0.1 to 20% by weight as the solid content.
When the surface-treated silica colloidal particle (A) dispersion and the gold colloidal particle (M) dispersion are mixed as described above, the silica colloidal particles (A) are collected on the surface of the gold colloidal particles (M). In the first production method, an amino group and a carboxyl group or a carboxylate group are bonded and self-assembled. In the second production method, colloidal silica particles gather on the surface of the gold colloid particles, and thiol groups (-SH) are bonded to the metal colloid surface and self-assemble.
混合比は各粒子の平均粒子径によっても異なるが金コロイド粒子（Ｍ）の表面にシリカコロイド粒子（Ａ）の全量が、図１に示されるように１層に層をなして結合する量に充分な量であることが好ましい。例えば、金コロイド粒子（Ｍ）の平均粒子径が４０nmでシリカコロイド粒子（Ａ）の平均粒子径が５nmの場合、４π×(４０nm)2÷４π×(５nm)2＝１６００、すなわち、金コロイド粒子（Ｍ）１個当たり、シリカコロイド粒子（Ａ）を１６００個以上使用することが好ましい。
シリカ被覆層形成
次に、必要に応じて、上記混合工程で得られた分散液に、酸性珪酸液を添加して、シリカコロイド粒子層の表面を、シリカ被覆してもよい。
Although the mixing ratio varies depending on the average particle diameter of each particle, the total amount of the silica colloidal particles (A) on the surface of the gold colloidal particles (M) is an amount that binds in one layer as shown in FIG. A sufficient amount is preferred. For example, when the average particle diameter of the gold colloid particles (M) is 40 nm and the average particle diameter of the silica colloid particles (A) is 5 nm, 4π × (40 nm) 2 ÷ 4π × (5 nm) 2 = 1600, that is, gold colloid It is preferable to use 1600 or more silica colloidal particles (A) per particle (M).
Silica-coated layer formed Next, if necessary, the dispersion obtained in the mixing step, by adding an acidic silicic acid solution, the surface of the colloidal silica particles layer may be silica-coated.
ここで、酸性珪酸液とはアルカリ金属珪酸塩水溶液、水ガラス等からイオン交換樹脂等によって脱アルカリイオン処理して得られる酸性の珪酸水溶液である。酸性珪酸液は、濃度がＳiＯ２として概ね０．１〜６重量％の範囲にあり、ｐＨが概ね０．１〜３．５の範
囲にあるものが好適である。
Here, the acidic silicic acid solution is an acidic silicic acid aqueous solution obtained by subjecting an alkali metal silicate aqueous solution, water glass or the like to dealkalizing ion treatment with an ion exchange resin or the like. The acidic silicic acid solution having a concentration of about 0.1 to 6% by weight as SiO 2 and a pH of about 0.1 to 3.5 is suitable.
酸性珪酸液の使用量は、前記シリカコロイド粒子（Ａ）により形成される被覆層のシリカ粒子間隙を埋めることができれば特に制限はないが、概ねシリカ被覆層を形成するシリカコロイド粒子（Ａ）の１重量％以上、シリカ被覆層の厚さが５０nmを越えない範囲（約５０重量％）である。 The amount of the acidic silicic acid solution is not particularly limited as long as it can fill the gap between the silica particles of the coating layer formed by the silica colloid particles (A), but the silica colloid particles (A) forming the silica coating layer are generally not limited. 1 wt% or more, and the thickness of the silica coating layer does not exceed 50 nm (about 50 wt%).
酸性珪酸液の使用量が少ないと、特にシリカコロイド粒子の平均粒子径が大きい場合には、シリカ被覆層を形成する効果が充分に得られず、すなわち、耐熱性が不充分となり製造時または使用時に鮮明な赤色を維持することができない場合がある。また、シリカ被覆層の厚さが大きくすぎると、光学的散乱の影響を受け易くなり、鮮明な赤色が得られない場合がある。 When the amount of the acidic silicic acid solution is small, particularly when the average particle size of the silica colloid particles is large, the effect of forming the silica coating layer cannot be obtained sufficiently, that is, the heat resistance is insufficient and the production or use is Sometimes a vivid red color cannot be maintained. Moreover, when the thickness of the silica coating layer is too large, the silica coating layer is easily affected by optical scattering, and a clear red color may not be obtained.
なお、珪酸液の添加速度は酸性珪酸液の使用量によっても異なるが、緻密にシリカ被覆するためにできるだけ時間をかけて添加することが好ましい。
乾燥および／または加熱処理
さらに、必要に応じて、得られた分散液を凍結乾燥あるいは加熱乾燥等によって乾燥することができる。乾燥することによって粉体顔料として好適に用いることができる。
In addition, although the addition rate of a silicic acid liquid changes also with the usage-amount of an acidic silicic acid liquid, in order to coat | cover silica finely, adding over as much time as possible is preferable.
Drying and / or heat treatment Further, if necessary, the obtained dispersion can be dried by freeze drying or heat drying. It can be suitably used as a powder pigment by drying.
加熱乾燥する際の温度は特に制限はないが５０〜２００℃、さらには６０〜１２０℃の範囲にあることが好ましい。このような温度で加熱乾燥すると、耐熱性が向上するとともに得られるシリカ被覆金コロイド粒子が凝集しにくくなり、分散性に優れたシリカ被覆金コロイド粒子が得られる。さらに加熱処理してもよい。加熱処理温度は特に制限はないが、２００〜６００℃、さらには２５０〜５００℃の範囲にあることが好ましい。加熱処理雰囲気は酸化雰囲気、不活性ガス雰囲気または還元ガス雰囲気あるいはこれらを前後して組み合わせて用いることができる。 The temperature for drying by heating is not particularly limited, but is preferably in the range of 50 to 200 ° C, more preferably 60 to 120 ° C. Heat drying at such a temperature improves the heat resistance and makes it difficult for the resulting silica-coated gold colloid particles to aggregate, resulting in silica-coated gold colloid particles having excellent dispersibility. Further, heat treatment may be performed. The heat treatment temperature is not particularly limited, but is preferably in the range of 200 to 600 ° C, more preferably 250 to 500 ° C. As the heat treatment atmosphere, an oxidizing atmosphere, an inert gas atmosphere, a reducing gas atmosphere, or a combination of these can be used.
上記温度範囲で加熱処理すると金コロイド粒子（Ｍ）とシリカコロイド粒子（Ａ）との結合（接合）が促進されるとともにシリカ被覆層が緻密になり、凝集しにくくなるとともに、高温で使用しても安定的に鮮明な赤色を呈する顔料を得ることができる。 Heat treatment in the above temperature range promotes bonding (bonding) between the colloidal gold particles (M) and the silica colloidal particles (A), and the silica coating layer becomes dense and hardly aggregates. In addition, it is possible to obtain a pigment exhibiting a stable and vivid red color.
このようにして得られたシリカ被覆金コロイド粒子は、シリカ被覆層の厚さが４〜５０nm、さらには５〜３０nmの範囲にあることが好ましい。また、シリカ被覆金コロイド粒子の平均粒子径は１３〜２００nm、好ましくは２０〜１１０nmの範囲にある。 The silica-coated gold colloidal particles thus obtained preferably have a silica coating layer thickness of 4 to 50 nm, more preferably 5 to 30 nm. The average particle diameter of the silica-coated gold colloidal particles is in the range of 13 to 200 nm, preferably 20 to 110 nm.
また、このようにして得られたシリカ被覆金コロイド粒子は赤色（波長：５２０〜５５０nm）を呈することから赤色顔料として好適に用いることができる。
[シリカ被覆金コロイド粒子]
本発明に係るシリカ被覆金コロイド粒子は、平均粒子径が４〜４０nmの範囲にあるシリカコロイド粒子（Ａ）で平均粒子径が５〜１００nmの範囲にある金コロイド粒子（Ｍ）の表面が被覆されてなる。かかる粒子は例えば上記した製造方法で得ることができる。
The silica-coated gold colloidal particles thus obtained can be suitably used as a red pigment because they exhibit a red color (wavelength: 520 to 550 nm).
[Silica-coated gold colloidal particles]
The silica-coated gold colloidal particles according to the present invention are coated on the surface of the colloidal gold particles (A) having an average particle diameter in the range of 4 to 40 nm and the gold colloidal particles (M) having an average particle diameter in the range of 5 to 100 nm. Being done. Such particles can be obtained, for example, by the production method described above.
本発明のシリカ被覆金コロイド粒子の１態様の概略図を図１に示す。
シリカコロイド粒子（Ａ）
シリカコロイド粒子は平均粒子径が後述する範囲にあれば特に制限はなく、前記と同様、従来公知のシリカコロイド粒子を用いることができる。
A schematic view of one embodiment of the silica-coated gold colloidal particles of the present invention is shown in FIG.
Silica colloidal particles (A)
The silica colloidal particles are not particularly limited as long as the average particle diameter is in the range described below, and conventionally known silica colloidal particles can be used as described above.
本発明のシリカ被覆金コロイド粒子を構成するシリカコロイド粒子（Ａ）は、アミノ基含有シラン化合物またはメルカプト基含有シラン化合物で表面処理されている。アミノ基を有するシラン化合物およびメルカプト基含有シラン化合物としては前記した通りである。 The silica colloidal particles (A) constituting the silica-coated gold colloidal particles of the present invention are surface-treated with an amino group-containing silane compound or a mercapto group-containing silane compound. The silane compound having an amino group and the mercapto group-containing silane compound are as described above.
アミノ基含有シラン化合物で表面処理されたシリカコロイド粒子（A-1）、メルカプト
基含有シラン化合物で表面処理されたシリカコロイド粒子（A-2）としては前記と同様の
粒子を用いることができる。
As silica colloid particles (A-1) surface-treated with an amino group-containing silane compound and silica colloid particles (A-2) surface-treated with a mercapto group-containing silane compound, the same particles as described above can be used.
金コロイド粒子（Ｍ）
金コロイド粒子（Ｍ）は平均粒子径が後述する範囲にあれば特に制限はなく、前記と同様、従来公知の金コロイド粒子を用いることができる。
Gold colloidal particles (M)
The gold colloidal particles (M) are not particularly limited as long as the average particle diameter is in the range described later, and conventionally known gold colloidal particles can be used as described above.
なお、前記シリカコロイド粒子が、アミノ基含有シラン化合物で表面処理されたシリカコロイド粒子（A-1）の場合、金コロイド粒子（Ｍ）はカルボキシル基および／またはカ
ルボキシレート基含有有機化合物で表面処理されていることが望ましい。カルボキシル基またはカルボキシレート基を有する有機化合物としては、前記したものが例示される。
When the silica colloid particles are silica colloid particles (A-1) surface-treated with an amino group-containing silane compound, the gold colloid particles (M) are surface-treated with a carboxyl group and / or carboxylate group-containing organic compound. It is desirable that Examples of the organic compound having a carboxyl group or a carboxylate group include those described above.
アミノ基含有シラン化合物で表面処理されたシリカコロイド粒子（A-1）は、カルボキ
シル基および／またはカルボキシレート基を有する有機化合物で表面処理された金コロイド粒子（M-1）の表面を被覆する。この粒子では、前記シリカコロイド粒子（A-1）と前記
金コロイド粒子（M-1）とが、シリカコロイド粒子（A-1）表面のアミノ基と金コロイド粒子（M-1）表面のカルボキシル基との結合によって結合している。
The silica colloidal particles (A-1) surface-treated with an amino group-containing silane compound coat the surface of the gold colloidal particles (M-1) surface-treated with an organic compound having a carboxyl group and / or a carboxylate group. . In this particle, the silica colloid particle (A-1) and the gold colloid particle (M-1) are composed of an amino group on the surface of the silica colloid particle (A-1) and a carboxyl on the surface of the gold colloid particle (M-1). It is connected by the bond with the group.
メルカプト基含有シラン化合物で表面処理されたシリカコロイド粒子（A-2）は、表面
処理されていない金コロイド粒子（M-2）の表面を被覆する。この粒子では、前記シリカ
コロイド粒子（A-2）と前記金コロイド粒子（M-2）とが、シリカコロイド粒子（A-2）表
面のチオール基（−ＳＨ）と金コロイド粒子（Ｍ）とが水素結合によって結合している。
The silica colloidal particles (A-2) surface-treated with the mercapto group-containing silane compound coat the surface of the gold colloidal particles (M-2) that are not surface-treated. In this particle, the silica colloid particle (A-2) and the gold colloid particle (M-2) are composed of a thiol group (-SH) and a gold colloid particle (M) on the surface of the silica colloid particle (A-2). Are bonded by hydrogen bonds.
前記したシリカコロイド粒子（Ａ）の平均粒子径（ＤA）は金コロイド粒子（Ｍ）の平
均粒子径（ＤM）より小さいことが好ましく、（ＤA）／（ＤM）が０．０１〜１、さらに
は０．０２〜０．５の範囲にあることが好ましい。
The average particle size (D A ) of the silica colloid particles (A) is preferably smaller than the average particle size (D M ) of the gold colloid particles (M), and (D A ) / (D M ) is 0.01. Is preferably in the range of ˜1, more preferably 0.02 to 0.5.
（ＤA）／（ＤM）が小さすぎると、シリカコロイド粒子同士が凝集してしまい、均一なシリカコロイド被覆層を形成できなかったり、また、シリカコロイド被覆層が薄いために加熱時に収縮し、クラックが生じて、変色してしまうことがある。（ＤA）／（ＤM）が大きすぎると、金コロイド粒子表面をシリカコロイド粒子で緻密に被覆することができない場合があり、耐熱性が不充分となり、赤色の色調が損なわれることがある。 If (D A ) / (D M ) is too small, the silica colloid particles aggregate together, and a uniform silica colloid coating layer cannot be formed. Also, since the silica colloid coating layer is thin, it shrinks during heating. Cracks may occur, causing discoloration. If (D A ) / (D M ) is too large, the surface of the gold colloid particles may not be densely coated with silica colloid particles, heat resistance may be insufficient, and red color tone may be impaired. .
つぎに、シリカ被覆金コロイド粒子は、シリカコロイド粒子被覆層が、さらにシリカで被覆されていることが好ましい。
シリカの被覆量は、前記シリカコロイド粒子（Ａ）により形成されるシリカコロイド被覆層のシリカコロイド粒子間隙を埋めることができれば特に制限はないが、概ねシリカコロイド被覆層を形成するシリカコロイド粒子（Ａ）の１重量％以上、シリカコロイド粒子被覆層の厚さが５０nmを越えない範囲であることが望ましい。かかるシリカ被覆層は、上記したように酸性珪酸液に由来する。
Next, in the silica-coated gold colloidal particles, the silica colloidal particle coating layer is preferably further coated with silica.
The silica coating amount is not particularly limited as long as it can fill the silica colloid particle gap of the silica colloid coating layer formed by the silica colloid particles (A), but the silica colloid particles (A It is desirable that the thickness of the silica colloidal particle coating layer not exceed 50 nm. Such a silica coating layer is derived from an acidic silicic acid solution as described above.
シリカ被覆層のシリカ量が少ないと、特にシリカコロイド粒子の平均粒子径が大きい場合は、シリカ被覆層を形成する効果が充分得られず、すなわち、すなわち、使用時に鮮明な赤色を維持することができない場合があり、シリカ被覆層の厚さが厚すぎると、鮮明な赤色が得られない場合がある。 When the amount of silica in the silica coating layer is small, particularly when the average particle size of the silica colloidal particles is large, the effect of forming the silica coating layer cannot be obtained sufficiently, that is, a vivid red color can be maintained during use. In some cases, when the silica coating layer is too thick, a clear red color may not be obtained.
シリカコロイド粒子（Ａ）被覆層、および必要に応じて形成されるシリカ被覆層とからなるシリカ層の厚みは４〜５０nm、さらには５〜３０nmの範囲にあることが好ましい。
シリカ層の厚みが薄すぎると、シリカ被覆金コロイド粒子を高温下で赤色顔料として用いる場合、鮮明な赤色を維持することができない場合がある。シリカ層の厚みが厚すぎると、鮮明な赤色が得られない場合がある。
The thickness of the silica layer comprising the silica colloidal particle (A) coating layer and the silica coating layer formed as necessary is preferably 4 to 50 nm, more preferably 5 to 30 nm.
When the silica layer is too thin, when the silica-coated gold colloidal particles are used as a red pigment at a high temperature, a clear red color may not be maintained. If the thickness of the silica layer is too thick, a clear red color may not be obtained.
本発明に係るシリカ被覆金コロイド粒子の平均粒子径は、用途に応じて適宜選択されるが、通常１３〜２００nm、好ましくは２０〜１１０nmの範囲にある。シリカ被覆金コロイド粒子の平均粒子径が小さいものでは、耐熱性にすぐれ、鮮明な赤色を呈する粒子が得られないことがある。シリカ被覆金コロイド粒子の平均粒子径が大きすぎるものでは鮮明な赤色を呈する粒子が得られないことがある。 The average particle diameter of the silica-coated gold colloidal particles according to the present invention is appropriately selected depending on the application, but is usually in the range of 13 to 200 nm, preferably 20 to 110 nm. When the silica-coated gold colloidal particles have a small average particle diameter, they may be excellent in heat resistance and may not be able to obtain vivid red particles. When the average particle diameter of the silica-coated gold colloidal particles is too large, particles exhibiting a bright red color may not be obtained.
本発明のシリカ被覆金コロイド粒子は赤色（波長：５２０〜５５０nm）を呈することから赤色顔料として好適に用いることができる。
このような、本発明にかかるシリカ被覆金コロイドは、従来金コロイド粒子の使用が困難であった高温環境下での用途、たとえばブラウン管（カラーフィルター）やセラミックスへの着色顔料などに用いても変色することもなく用いることが可能となる。
［実施例］
以下に実施例を示して本発明を具体的に説明するが、本発明はこれら実施例に限定する
ものではない。
［実施例1］
表面処理金コロイド粒子(Au-1)分散液の調製
金コロイド粒子分散液（BB International製：平均粒子径５０nm、Ａu濃度５重量％）
２００ｇを純水３００ｍＬに分散させ、これにクエン酸ナトリウム４ｇを添加して１時間撹拌した後、両イオン交換樹脂にてフリーのクエン酸ナトリウムを除去し、表面処理金属コロイド粒子(Au-1)分散液を調製した。
Since the silica-coated gold colloidal particles of the present invention exhibit a red color (wavelength: 520 to 550 nm), they can be suitably used as a red pigment.
Such a silica-coated gold colloid according to the present invention is discolored even when used in a high-temperature environment where it has been difficult to use colloidal gold particles, such as a color tube for a cathode ray tube (color filter) or ceramics. It becomes possible to use without doing.
[Example]
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[Example 1]
Preparation of surface-treated gold colloidal particle (Au-1) dispersion Gold colloidal particle dispersion (manufactured by BB International: average particle diameter 50 nm, Au concentration 5% by weight)
200 g is dispersed in 300 mL of pure water, 4 g of sodium citrate is added thereto and stirred for 1 hour, free sodium citrate is removed with both ion exchange resins, and surface-treated metal colloidal particles (Au-1) A dispersion was prepared.
表面処理シリカコロイド粒子(S-1)分散液の調製
シリカコロイド粒子分散液（触媒化成工業(株)製：カタロイドSI-30、平均粒子径１２nm、ＳiＯ2濃度３０重量％）４９ｇを水／エタノール（５０／５０）混合溶媒６８ｇに分散させた。この分散液にγ−アミノプロピルトリエトキシシラン０．２５ｇを添加し、１時間攪拌した後、オートクレーブにて８０℃で２時間撹拌処理してアミノ基含有シラン化合物で表面処理されたシリカコロイド粒子(S-1)分散液を調製した。
Preparation of surface-treated silica colloidal particle (S-1) dispersion Silica colloidal particle dispersion (catalyst chemical industry Co., Ltd .: Cataloid SI-30, average particle size 12 nm, SiO 2 concentration 30% by weight) 49 g of water / ethanol (50/50) The mixture was dispersed in 68 g of a mixed solvent. 0.25 g of γ-aminopropyltriethoxysilane was added to this dispersion, and the mixture was stirred for 1 hour, and then a silica colloid particle (surface-treated with an amino group-containing silane compound by stirring at 80 ° C. for 2 hours in an autoclave) S-1) A dispersion was prepared.
シリカ被覆金コロイド粒子(1)の調製
上記で調製したシリカコロイド粒子(S-1)分散液と表面処理金コロイド粒子(Au-1)分散
液とを混合し、１時間撹拌してシリカ被覆金コロイド粒子(1)分散液を調製した。
Preparation of silica-coated gold colloidal particles (1) The silica colloidal particle (S-1) dispersion prepared above and the surface-treated gold colloidal particle (Au-1) dispersion are mixed and stirred for 1 hour to produce silica-coated gold. A dispersion of colloidal particles (1) was prepared.
シリカ被覆金コロイド粒子(1)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４
００℃で２時間加熱処理してシリカ被覆金コロイド粒子(1)粉体を得た。
シリカ被覆金コロイド粒子(1)の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の
凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価した。結果を表１に示した。
The silica-coated gold colloidal particle (1) dispersion is evaporated to dryness at 120 ° C.
A silica-coated gold colloidal particle (1) powder was obtained by heat treatment at 00 ° C. for 2 hours.
The average particle diameter of the silica-coated gold colloidal particles (1), the observation of the aggregated particles after drying, the observation of the aggregated particles after heat treatment (heat resistance), and the red sharpness after the heat treatment were evaluated. The results are shown in Table 1.
凝集粒子の観察
１２０℃で蒸発乾燥した後の粉体の電子顕微鏡写真を観察し、以下の基準で評価した。
凝集粒子が殆ど認められない。 ： ○
凝集粒子が僅かに認められる。 ： △
凝集粒子が多く認められる。 ： ×
耐熱性
シリカ被覆金コロイド粒子(1)の電子顕微鏡写真を観察し、以下の基準で評価した。
Observation of Aggregated Particles An electron micrograph of the powder after evaporating and drying at 120 ° C. was observed and evaluated according to the following criteria.
Almost no agglomerated particles are observed. : ○
Slightly aggregated particles are observed. : △
Many agglomerated particles are observed. : ×
An electron micrograph of the heat-resistant silica-coated gold colloidal particles (1) was observed and evaluated according to the following criteria.
凝集粒子が殆ど認められない。 ： ○
凝集粒子が僅かに認められる。 ： △
凝集粒子が多く認められる。 ： ×
赤色鮮明度
シリカ被覆金コロイド粒子(1)の赤色度を目視観察し、以下の基準で評価した。
Almost no agglomerated particles are observed. : ○
Slightly aggregated particles are observed. : △
Many agglomerated particles are observed. : ×
The redness of the red- coated silica-coated gold colloidal particles (1) was visually observed and evaluated according to the following criteria.
鮮明な赤色を呈している。 ： ○
比較的鮮明な赤色を呈している。 ： △
赤色が認められない程度に変色している。： ×
［実施例２］
シリカ被覆金コロイド粒子(2)の調製
実施例１と同様にしてシリカ被覆金コロイド粒子(1)分散液を調製した。これを撹拌し
ながら酸性珪酸液（ＳiＯ２濃度３．０重量％、ｐＨ２）１３．１ｇを１時間で添加し、
ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(2)分散液を調製した。
It has a bright red color. : ○
It has a relatively bright red color. : △
Discolored to the extent that red is not recognized. : ×
[Example 2]
Preparation of silica-coated gold colloidal particles (2) A silica-coated gold colloidal particle (1) dispersion was prepared in the same manner as in Example 1. While stirring this, 13.1 g of acidic silicic acid solution (SiO 2 concentration 3.0 wt%, pH 2) was added in 1 hour,
Next, the mixture was aged at 80 ° C. for 1 hour to prepare a dispersion of silica-coated gold colloidal particles (2).
シリカ被覆金コロイド粒子(2)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４
００℃で２時間加熱処理してシリカ被覆金コロイド粒子(2)粉体を得た。
シリカ被覆金コロイド粒子(2)の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の
凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表１に示した。
［実施例３］
表面処理シリカコロイド粒子(S-3)分散液の調製
シリカコロイド粒子分散液（触媒化成工業(株)製：カタロイドSI-550、平均粒子径５nm、ＳiＯ2濃度２０重量％）３ｇを水／エタノール（５０／５０）混合溶媒２７ｇに分散させた。
The silica-coated gold colloidal particle (2) dispersion is evaporated to dryness at 120 ° C.
A silica-coated gold colloidal particle (2) powder was obtained by heat treatment at 00 ° C. for 2 hours.
The average particle diameter of the silica-coated gold colloidal particles (2), observation of the aggregated particles after drying, observation of the aggregated particles after heat treatment (heat resistance), and redness after the heat treatment were evaluated, and the results are shown in Table 1. Indicated.
[Example 3]
Preparation of surface-treated silica colloidal particle (S-3) dispersion 3 g of silica colloidal particle dispersion (catalyst chemical industry Co., Ltd .: Cataloid SI-550, average particle diameter 5 nm, SiO 2 concentration 20% by weight) was added to water / ethanol. (50/50) The mixture was dispersed in 27 g of a mixed solvent.
この分散液にγ−アミノプロピルトリエトキシシラン０．２５ｇを添加し、１時間攪拌した後、オートクレーブにて８０℃で２時間撹拌処理してアミノ基含有シラン化合物で表面処理されたシリカコロイド粒子(S-3)分散液を調製した。
シリカ被覆金コロイド粒子(3)の調製
シリカコロイド粒子(S-3)分散液と、実施例１と同様にして調製した表面処理金コロイ
ド粒子(Au-1)分散液とを混合し、１時間撹拌してシリカ被覆金コロイド粒子分散液を調製した。
0.25 g of γ-aminopropyltriethoxysilane was added to this dispersion, and the mixture was stirred for 1 hour, and then a silica colloid particle (surface-treated with an amino group-containing silane compound by stirring at 80 ° C. for 2 hours in an autoclave) S-3) A dispersion was prepared.
Preparation of silica-coated gold colloidal particles (3) A silica colloidal particle (S-3) dispersion and a surface-treated gold colloidal particle (Au-1) dispersion prepared in the same manner as in Example 1 were mixed for 1 hour. A silica-coated gold colloidal particle dispersion was prepared by stirring.
ついで、これを撹拌しながら酸性珪酸液（ＳiＯ2濃度３．０重量％、ｐＨ２）４．５ｇを３０分間で添加し、ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(3)分
散液を調製した。
Next, while stirring this, 4.5 g of acidic silicic acid solution (SiO 2 concentration 3.0 wt%, pH 2) was added over 30 minutes, and then aged at 80 ° C. for 1 hour to produce silica-coated gold colloidal particles (3) A dispersion was prepared.
シリカ被覆金コロイド粒子(3)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４
００℃で２時間加熱処理してシリカ被覆金コロイド粒子(3)粉体を得た。
シリカ被覆金コロイド粒子(3)の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の
凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表1に示した。
［実施例４］
表面処理シリカコロイド粒子(S-4)分散液の調製
シリカコロイド粒子分散液（触媒化成工業(株)製：カタロイドSI-50、平均粒子径２５nm、ＳiＯ2濃度４８重量％）６．３ｇを水／エタノール（５０／５０）混合溶媒１４６ｇに分散させた。この分散液にγ−アミノプロピルトリエトキシシラン０．２５ｇを添加し、１時間攪拌した後、オートクレーブにて８０℃で２時間撹拌処理してアミノ基含有シラン化合物で表面処理されたシリカコロイド粒子(S-4)分散液を調製した。
The silica-coated gold colloidal particle (3) dispersion is evaporated to dryness at 120 ° C.
A silica-coated gold colloidal particle (3) powder was obtained by heat treatment at 00 ° C. for 2 hours.
The average particle diameter of the silica-coated gold colloidal particles (3), observation of the aggregated particles after drying, observation of the aggregated particles after heat treatment (heat resistance), and the redness after heat treatment were evaluated, and the results are shown in Table 1. Indicated.
[Example 4]
Preparation of surface-treated silica colloidal particle (S-4) dispersion Silica colloidal particle dispersion (catalyst chemical industry, Cataloid SI-50, average particle diameter 25 nm, SiO 2 concentration 48 wt%) 6.3 g of water / Ethanol (50/50) was dispersed in 146 g of a mixed solvent. 0.25 g of γ-aminopropyltriethoxysilane was added to this dispersion, and the mixture was stirred for 1 hour, and then a silica colloid particle (surface-treated with an amino group-containing silane compound by stirring at 80 ° C. for 2 hours in an autoclave) S-4) A dispersion was prepared.
シリカ被覆金コロイド粒子(4)の調製
シリカコロイド粒子(S-4)分散液と、実施例１と同様にして調製した表面処理金コロイ
ド粒子(Au-1)分散液とを混合し、１時間撹拌してシリカ被覆金コロイド粒子分散液を調製した。
Preparation of silica-coated gold colloidal particles (4) A silica colloidal particle (S-4) dispersion and a surface-treated gold colloidal particle (Au-1) dispersion prepared in the same manner as in Example 1 were mixed for 1 hour. A silica-coated gold colloidal particle dispersion was prepared by stirring.
ついで、これを撹拌しながら酸性珪酸液（ＳiＯ2濃度３．０重量％、ｐＨ２）２７．３ｇを２時間で添加し、ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(4)分
散液を調製した。
Next, 27.3 g of acidic silicic acid solution (SiO 2 concentration 3.0 wt%, pH 2) was added over 2 hours with stirring, and then aged at 80 ° C. for 1 hour to produce silica-coated gold colloidal particles (4) A dispersion was prepared.
シリカ被覆金コロイド粒子(4)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４
００℃で２時間加熱処理してシリカ被覆金コロイド粒子(4)粉体を得た。
シリカ被覆金コロイド粒子(4)の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の
凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表１に示した。
［実施例５］
表面処理金コロイド粒子(Au-5)分散液の調製
金コロイド粒子分散液（BB International製：平均粒子径２０nm、Ａu濃度５重量％
）２００ｇを純水３００ｍＬに分散させ、これにクエン酸ナトリウム１８ｇを添加して１時間撹拌した後、両イオン交換樹脂にてフリーのクエン酸ナトリウムを除去し、表面処理金コロイド粒子(Au-5)分散液を調製した。
The silica-coated gold colloidal particle (4) dispersion is evaporated to dryness at 120 ° C.
A silica-coated gold colloidal particle (4) powder was obtained by heat treatment at 00 ° C. for 2 hours.
The average particle diameter of silica-coated gold colloidal particles (4), observation of aggregated particles after drying, observation of aggregated particles after heat treatment (heat resistance), and redness after heat treatment were evaluated, and the results are shown in Table 1. Indicated.
[Example 5]
Preparation of surface-treated gold colloidal particle (Au-5) dispersion Gold colloidal particle dispersion (manufactured by BB International: average particle diameter 20 nm, Au concentration 5% by weight
) 200 g was dispersed in 300 mL of pure water, 18 g of sodium citrate was added thereto, and the mixture was stirred for 1 hour. Then, free sodium citrate was removed with both ion exchange resins, and the surface-treated gold colloidal particles (Au-5 ) A dispersion was prepared.
シリカ被覆金コロイド粒子(5)の調製
実施例３と同様にして調製した表面処理シリカコロイド粒子(S-3)分散液と、表面処理
金コロイド粒子(Au-5)分散液とを混合し、１時間撹拌してシリカ被覆金コロイド粒子分散液を調製した。
Preparation of silica-coated gold colloidal particles (5) A surface-treated silica colloidal particle (S-3) dispersion prepared in the same manner as in Example 3 and a surface-treated gold colloidal particle (Au-5) dispersion were mixed. The mixture was stirred for 1 hour to prepare a silica-coated gold colloid particle dispersion.
ついで、これを撹拌しながら酸性珪酸液（ＳiＯ2濃度３．０重量％、ｐＨ２）１３．７ｇを１時間で添加し、ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(5)分
散液を調製した。
Next, 13.7 g of acidic silicic acid solution (SiO 2 concentration 3.0 wt%, pH 2) was added over 1 hour while stirring this, and then aged at 80 ° C. for 1 hour to produce silica-coated gold colloidal particles (5) A dispersion was prepared.
シリカ被覆金コロイド粒子(5)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４
００℃で２時間加熱処理してシリカ被覆金コロイド粒子(5)粉体を得た。
シリカ被覆金コロイド粒子(5)の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の
凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表に示した。
［実施例６］
表面処理金コロイド粒子(Au-6)分散液の調製
金コロイド粒子分散液（BB International製：平均粒子径８０nm、Ａu濃度５重量％）
２００ｇを純水３００ｍＬに分散させ、これにクエン酸４．４ｇを添加して１時間撹拌した後、両イオン交換樹脂にてフリーのクエン酸ナトリウムを除去し、表面処理金コロイド粒子(Au-6)分散液を調製した。
The silica-coated gold colloidal particle (5) dispersion was evaporated to dryness at 120 ° C.
A silica-coated gold colloidal particle (5) powder was obtained by heat treatment at 00 ° C. for 2 hours.
Evaluation of average particle size of silica-coated gold colloidal particles (5), observation of aggregated particles after drying, observation of aggregated particles after heat treatment (heat resistance), red sharpness after heat treatment, and the results are shown in the table It was.
[Example 6]
Preparation of surface-treated gold colloidal particle (Au-6) dispersion Gold colloidal particle dispersion (manufactured by BB International: average particle diameter 80 nm, Au concentration 5% by weight)
200 g was dispersed in 300 mL of pure water, 4.4 g of citric acid was added thereto and stirred for 1 hour, free sodium citrate was removed with both ion exchange resins, and surface treated gold colloidal particles (Au-6 ) A dispersion was prepared.
シリカ被覆金コロイド粒子(6)の調製
実施例４と同様にして調製した表面処理シリカコロイド粒子(S-4)分散液と、表面処理
金コロイド粒子(Au-6)分散液とを混合し、１時間撹拌してシリカ被覆金コロイド粒子分散液を調製した。
Preparation of silica-coated gold colloidal particles (6) A surface-treated silica colloidal particle (S-4) dispersion prepared in the same manner as in Example 4 and a surface-treated gold colloidal particle (Au-6) dispersion were mixed. The mixture was stirred for 1 hour to prepare a silica-coated gold colloid particle dispersion.
ついで、これを撹拌しながら酸性珪酸液（ＳiＯ2濃度３．０重量％、ｐＨ２）１７．１ｇを１．５時間で添加し、ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(6)分散液を調製した。 Next, while stirring this, 17.1 g of acidic silicate solution (SiO 2 concentration 3.0 wt%, pH 2) was added in 1.5 hours, and then aged at 80 ° C. for 1 hour to produce silica-coated gold colloidal particles ( 6) A dispersion was prepared.
シリカ被覆金コロイド粒子(6)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４
００℃で２時間加熱処理してシリカ被覆金コロイド粒子(6)粉体を得た。
シリカ被覆金コロイド粒子(6)の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の
凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表１に示した。
［実施例７］
表面処理シリカコロイド粒子(S-7)分散液の調製
シリカコロイド粒子分散液（触媒化成工業(株)製：カタロイドSI-30、平均粒子径１２nm、ＳiＯ2濃度３０重量％）４．９ｇを水／エタノール（５０／５０）混合溶媒６８ｇに分散させた。この分散液にγ-メルカプトプロピルトリメトキシシラン０．２５ｇを添加し、１時間攪拌した後、オートクレーブにて８０℃で２時間撹拌処理してメルカプトト基含有シラン化合物で表面処理し、表面にチオール基を有するシリカコロイド粒子(S-7)分散液を調製した。
The silica-coated gold colloidal particle (6) dispersion was evaporated to dryness at 120 ° C.
A silica-coated gold colloidal particle (6) powder was obtained by heat treatment at 00 ° C. for 2 hours.
The average particle diameter of the silica-coated gold colloidal particles (6), observation of the aggregated particles after drying, observation of the aggregated particles after heat treatment (heat resistance), and redness after the heat treatment were evaluated, and the results are shown in Table 1. Indicated.
[Example 7]
Preparation of surface treated silica colloidal particle (S-7) dispersion Silica colloidal particle dispersion (catalyst chemical industry, Cataloid SI-30, average particle size 12 nm, SiO 2 concentration 30 wt%) 4.9 g in water / Ethanol (50/50) was dispersed in 68 g of a mixed solvent. To this dispersion was added 0.25 g of γ-mercaptopropyltrimethoxysilane, and the mixture was stirred for 1 hour, then stirred at 80 ° C. for 2 hours in an autoclave, surface-treated with a mercaptoto group-containing silane compound, and thiol on the surface. A dispersion of colloidal silica particles (S-7) having groups was prepared.
金コロイド粒子(Au-7)分散液の調製
金コロイド粒子分散液（BBInternational製：平均粒子径５０nm、Ａu濃度５重量％）２００ｇを純水３００ｍＬに分散させて金コロイド粒子(Au-7)分散液を調製した。
Preparation of gold colloidal particle (Au-7) dispersion Gold colloidal particle dispersion (Au-7) was dispersed by dispersing 200 g of gold colloidal particle dispersion (BBInternational: average particle diameter 50 nm, Au concentration 5% by weight) in 300 mL of pure water. A liquid was prepared.
シリカ被覆金コロイド粒子(7)の調製
上記で調製したシリカコロイド粒子(S-7)分散液と金コロイド粒子(Au-7)分散液とを混
合し、１時間撹拌してシリカ被覆金コロイド粒子(7)分散液を調製した。
Preparation of silica-coated gold colloidal particles (7) The silica colloidal particle (S-7) dispersion prepared above and the gold colloidal particle (Au-7) dispersion are mixed and stirred for 1 hour to produce silica-coated gold colloidal particles. (7) A dispersion was prepared.
シリカ被覆金コロイド粒子(7)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４
００℃で２時間加熱処理してシリカ被覆金コロイド粒子(7)粉体を得た。
シリカ被覆金コロイド粒子(7)の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の
凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表に示した。
［実施例８］
シリカ被覆金コロイド粒子(8)の調製
実施例７と同様にしてシリカ被覆金コロイド粒子分散液を調製した。
The silica-coated gold colloidal particle (7) dispersion was evaporated to dryness at 120 ° C.
A silica-coated gold colloidal particle (7) powder was obtained by heat treatment at 00 ° C. for 2 hours.
Evaluation of average particle size of silica-coated gold colloidal particles (7), observation of aggregated particles after drying, observation of aggregated particles after heat treatment (heat resistance), redness after heat treatment, and results are shown in the table It was.
[Example 8]
Preparation of silica-coated gold colloidal particles (8) In the same manner as in Example 7, a silica-coated gold colloidal particle dispersion was prepared.
ついで、これを撹拌しながら酸性珪酸液（ＳiＯ２濃度３．０重量％、ｐＨ２）１３．
１ｇを１時間で添加し、ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(8)
分散液を調製した。
Next, an acidic silicic acid solution (SiO 2 concentration 3.0 wt%, pH 2) while stirring the solution 13.
1g was added in 1 hour, and then aged at 80 ° C for 1 hour to produce silica-coated gold colloidal particles (8)
A dispersion was prepared.
シリカ被覆金コロイド粒子(8)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４
００℃で２時間加熱処理してシリカ被覆金コロイド粒子(8)粉体を得た。
シリカ被覆金コロイド粒子(8)の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の
凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表１に示した。
［比較例１］
シリカ被覆金コロイド粒子(R1)の調製
実施例７と同様にして表面にカルボキシル基を持たない濃度１重量％の金コロイド粒子分散液を調製した。
The silica-coated gold colloidal particle (8) dispersion was evaporated to dryness at 120 ° C.
A silica-coated gold colloidal particle (8) powder was obtained by heat treatment at 00 ° C. for 2 hours.
The average particle diameter of the silica-coated gold colloidal particles (8), observation of the aggregated particles after drying, observation of the aggregated particles after heat treatment (heat resistance), and redness after the heat treatment were evaluated, and the results are shown in Table 1. Indicated.
[Comparative Example 1]
Preparation of silica-coated gold colloidal particles (R1) In the same manner as in Example 7, a gold colloidal particle dispersion having a concentration of 1% by weight having no carboxyl group on the surface was prepared.
ついで、これを撹拌しながら酸性珪酸液（ＳiＯ2濃度３．０重量％、ｐＨ２）６１．７ｇを５時間で添加し、ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(R1)分散液を調製した。 Next, 61.7 g of acidic silicic acid solution (SiO 2 concentration 3.0 wt%, pH 2) was added over 5 hours while stirring the mixture, and then aged at 80 ° C. for 1 hour to produce silica-coated gold colloidal particles (R1). A dispersion was prepared.
シリカ被覆金コロイド粒子(R1)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４００℃で２時間加熱処理してシリカ被覆金コロイド粒子(R1)粉体を得た。
シリカ被覆金コロイド粒子(R1) の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後
の凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表１に示した。［比較例２］
シリカ被覆金コロイド粒子(R2)の調製
実施例１と同様にして表面処理金コロイド粒子(Au-1)分散液を調製した。
The silica-coated gold colloidal particle (R1) dispersion was evaporated to dryness at 120 ° C. and heat-treated at 400 ° C. for 2 hours in a hydrogen gas atmosphere to obtain silica-coated gold colloidal particle (R1) powder.
Evaluation of average particle diameter of silica-coated gold colloidal particles (R1), observation of aggregated particles after drying, observation of aggregated particles after heat treatment (heat resistance), redness after heat treatment, and results are shown in Table 1. Indicated. [Comparative Example 2]
Preparation of silica-coated gold colloidal particles (R2) A surface-treated gold colloidal particle (Au-1) dispersion was prepared in the same manner as in Example 1.
ついで、これを撹拌しながら酸性珪酸液（ＳiＯ2濃度３．０重量％、ｐＨ２）６１．７ｇを５時間で添加し、ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(R2)分散液を調製した。 Next, 61.7 g of acidic silicic acid solution (SiO 2 concentration 3.0 wt%, pH 2) was added over 5 hours while stirring the mixture, and then aged at 80 ° C. for 1 hour to produce silica-coated gold colloidal particles (R2). A dispersion was prepared.
シリカ被覆金コロイド粒子(R2)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４００℃で２時間加熱処理してシリカ被覆金コロイド粒子(R2)粉体を得た。
シリカ被覆金コロイド粒子(R2) の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後
の凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表１に示した。［比較例３］
表面処理金コロイド粒子(RAu-3)分散液の調製
金コロイド粒子分散液（BB International製：平均粒子径１５０nm、Au濃度５重量％）２００ｇを純水３００ｍＬに分散させ、これにクエン酸２．４ｇを添加して１時間撹拌した後、両イオン交換樹脂にてフリーのクエン酸ナトリウムを除去し、表面処理金コロイド粒子(RAu-3)分散液を調製した。
The silica-coated gold colloidal particle (R2) dispersion was evaporated to dryness at 120 ° C. and heat-treated at 400 ° C. for 2 hours in a hydrogen gas atmosphere to obtain silica-coated gold colloidal particle (R2) powder.
Evaluation of average particle diameter of silica-coated gold colloidal particles (R2), observation of aggregated particles after drying, observation of aggregated particles after heat treatment (heat resistance), redness after heat treatment, and results are shown in Table 1. Indicated. [Comparative Example 3]
Preparation of surface-treated gold colloidal particle (RAu-3) dispersion 200 g of gold colloidal particle dispersion (manufactured by BB International: average particle diameter 150 nm, Au concentration 5% by weight) is dispersed in 300 mL of pure water. After adding 4 g and stirring for 1 hour, free sodium citrate was removed with both ion exchange resins to prepare a surface-treated gold colloidal particle (RAu-3) dispersion.
シリカ被覆金コロイド粒子(R3)の調製
実施例１と同様にして調製したシリカコロイド粒子(S-1)分散液と、表面処理金コロイ
ド粒子(RAu-3)分散液とを混合し、１時間撹拌してシリカ被覆金コロイド粒子分散液(R3)
を調製した。
Preparation of silica-coated gold colloidal particles (R3) A silica colloidal particle (S-1) dispersion prepared in the same manner as in Example 1 and a surface-treated gold colloidal particle (RAu-3) dispersion were mixed for 1 hour. Silica-coated gold colloidal particle dispersion (R3) with stirring
Was prepared.
シリカ被覆金コロイド粒子(R3)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４００℃で２時間加熱処理してシリカ被覆金コロイド粒子(R3)粉体を得た。シリカ被覆金コロイド粒子(R3) の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後の凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表1に示した。
［比較例４］
シリカ被覆金コロイド粒子(R4)の調製
実施例１と同様にして調製したシリカコロイド粒子(S-1)分散液と、比較例３と同様に
して調製した表面処理金コロイド粒子(RAu-3)分散液とを混合し、１時間撹拌してシリカ
被覆金コロイド粒子分散液を調製した。
The silica-coated gold colloidal particle (R3) dispersion was evaporated to dryness at 120 ° C. and heat-treated at 400 ° C. for 2 hours in a hydrogen gas atmosphere to obtain silica-coated gold colloidal particle (R3) powder. Evaluation of average particle diameter of silica-coated gold colloidal particles (R3), observation of aggregated particles after drying, observation of aggregated particles after heat treatment (heat resistance), redness after heat treatment, and results are shown in Table 1. Indicated.
[Comparative Example 4]
Preparation of silica-coated gold colloidal particles (R4) Silica colloidal particle (S-1) dispersion prepared in the same manner as in Example 1, and surface-treated gold colloidal particles (RAu-3) prepared in the same manner as in Comparative Example 3 The dispersion was mixed and stirred for 1 hour to prepare a silica-coated gold colloidal particle dispersion.
ついで、これを撹拌しながら酸性珪酸液（ＳiＯ2濃度３．０重量％、ｐＨ２）４．４ｇを３０分間で添加し、ついで、８０℃で１時間熟成してシリカ被覆金コロイド粒子(R4)分散液を調製した。 Next, 4.4 g of acidic silicic acid solution (SiO 2 concentration: 3.0 wt%, pH 2) was added over 30 minutes while stirring the mixture, and then aged at 80 ° C. for 1 hour to produce silica-coated gold colloidal particles (R4). A dispersion was prepared.
シリカ被覆金コロイド粒子(R4)分散液を１２０℃で蒸発乾燥し、水素ガス雰囲気下、４００℃で２時間加熱処理してシリカ被覆金コロイド粒子(R4)粉体を得た。
シリカ被覆金コロイド粒子(R4) の平均粒子径、乾燥後の凝集粒子の観察、加熱処理後
の凝集粒子の観察（耐熱性）、加熱処理後の赤色鮮明度を評価し、結果を表１に示した。
The silica-coated gold colloidal particle (R4) dispersion was evaporated to dryness at 120 ° C. and heat-treated at 400 ° C. for 2 hours in a hydrogen gas atmosphere to obtain silica-coated gold colloidal particle (R4) powder.
Evaluation of average particle diameter of silica-coated gold colloidal particles (R4), observation of aggregated particles after drying, observation of aggregated particles after heat treatment (heat resistance), redness after heat treatment, and results are shown in Table 1. Indicated.
Claims (9)
平均粒子径が４〜４０nmの範囲にあり、アミノ基含有シラン化合物で表面処理されたシリカコロイド粒子分散液とを混合することを特徴とするシリカ被覆金コロイド粒子の製造方法。 A gold colloidal particle dispersion having an average particle diameter in the range of 5 to 100 nm and surface-treated with a carboxyl group and / or carboxylate group-containing organic compound;
A method for producing silica-coated gold colloidal particles, comprising mixing a silica colloidal particle dispersion having an average particle diameter in the range of 4 to 40 nm and surface-treated with an amino group-containing silane compound.
平均粒子径が４〜４０nmの範囲にあり、メルカプト基含有シラン化合物で表面処理されてチオール基（−ＳＨ基）が導入されたシリカコロイド粒子分散液と
を混合することを特徴とするシリカ被覆金コロイド粒子の製造方法。 A colloidal gold particle dispersion having an average particle size in the range of 5 to 100 nm;
Silica-coated gold having an average particle diameter in the range of 4 to 40 nm and a silica colloidal particle dispersion liquid surface-treated with a mercapto group-containing silane compound and introduced with thiol groups (—SH groups) A method for producing colloidal particles.
(ii)平均粒子径が５〜１００nmの範囲にあり、カルボキシル基および／またはカルボキシレート基含有有機化合物で表面処理された金コロイド粒子の表面を、
被覆されてなることを特徴とするシリカ被覆金コロイド粒子。 (i) an average particle diameter of Ri range near the 4～40Nm, silica colloidal particles surface-treated with an amino group-containing silane compound,
(ii) an average particle diameter of Ri range near the 5 to 100 nm, the surface treated surface of the colloidal gold particles with carboxyl groups and / or carboxylate group-containing organic compound,
Silica-coated gold colloidal particles characterized by being coated.
(ii)平均粒子径が５〜１００nmの範囲にある金コロイド粒子の表面を、
被覆されてなることを特徴とするシリカ被覆金コロイド粒子。 (i) silica colloidal particles having an average particle diameter in the range of 4 to 40 nm and surface-treated with a mercapto group-containing silane compound to introduce thiol groups (-SH groups);
(ii) a surface of colloidal gold particles having an average particle diameter in the range of 5 to 100 nm,
Silica-coated gold colloidal particles characterized by being coated.
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