JP2005171033A - Spherical composite cured melamine resin particle and its production method - Google Patents
Spherical composite cured melamine resin particle and its production method Download PDFInfo
- Publication number
- JP2005171033A JP2005171033A JP2003411129A JP2003411129A JP2005171033A JP 2005171033 A JP2005171033 A JP 2005171033A JP 2003411129 A JP2003411129 A JP 2003411129A JP 2003411129 A JP2003411129 A JP 2003411129A JP 2005171033 A JP2005171033 A JP 2005171033A
- Authority
- JP
- Japan
- Prior art keywords
- melamine resin
- core
- shell
- melamine
- colloidal silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 139
- 239000002245 particle Substances 0.000 title claims abstract description 133
- 239000004640 Melamine resin Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000008119 colloidal silica Substances 0.000 claims abstract description 44
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011258 core-shell material Substances 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- -1 melamine compound Chemical class 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 239000012736 aqueous medium Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 4
- 238000000149 argon plasma sintering Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 30
- 238000000034 method Methods 0.000 description 16
- 239000012798 spherical particle Substances 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000007850 fluorescent dye Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JADVWWSKYZXRGX-UHFFFAOYSA-M thioflavine T Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C1=[N+](C)C2=CC=C(C)C=C2S1 JADVWWSKYZXRGX-UHFFFAOYSA-M 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XKTMIJODWOEBKO-UHFFFAOYSA-M Guinee green B Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC=CC=2)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 XKTMIJODWOEBKO-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- BGLGAKMTYHWWKW-UHFFFAOYSA-N acridine yellow Chemical compound [H+].[Cl-].CC1=C(N)C=C2N=C(C=C(C(C)=C3)N)C3=CC2=C1 BGLGAKMTYHWWKW-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QTMKCINNZVKHJT-UHFFFAOYSA-N azane;3-[[ethyl-[4-[[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]-(2-sulfophenyl)methylidene]cyclohexa-2,5-dien-1-ylidene]azaniumyl]methyl]benzenesulfonate Chemical compound N.C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S(O)(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 QTMKCINNZVKHJT-UHFFFAOYSA-N 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000012745 brilliant blue FCF Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- WSALIDVQXCHFEG-UHFFFAOYSA-L disodium;4,8-diamino-1,5-dihydroxy-9,10-dioxoanthracene-2,6-disulfonate Chemical compound [Na+].[Na+].O=C1C2=C(N)C=C(S([O-])(=O)=O)C(O)=C2C(=O)C2=C1C(O)=C(S([O-])(=O)=O)C=C2N WSALIDVQXCHFEG-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 235000012738 indigotine Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002866 paraformaldehyde Polymers 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
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
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- TXVWTOBHDDIASC-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)=C(N)C1=CC=CC=C1 TXVWTOBHDDIASC-UHFFFAOYSA-N 0.000 description 1
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
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- VVZRKVYGKNFTRR-UHFFFAOYSA-N 12h-benzo[a]xanthene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4OC3=CC=C21 VVZRKVYGKNFTRR-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
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- BUJNIHFICKTDHT-UHFFFAOYSA-M sodium;4-[4-[acetyl(methyl)amino]anilino]-1-amino-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].C1=CC(N(C(C)=O)C)=CC=C1NC1=CC(S([O-])(=O)=O)=C(N)C2=C1C(=O)C1=CC=CC=C1C2=O BUJNIHFICKTDHT-UHFFFAOYSA-M 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
本発明は、コア−シェル型の球状複合硬化メラミン樹脂粒子およびその製造方法に関するものである。 The present invention relates to a core-shell type spherical composite cured melamine resin particle and a method for producing the same.
本発明のコア−シェル型の球状複合硬化メラミン樹脂粒子は、特に可視光に対する光散乱特性や光反射特性を改良でき、さらに耐水性、耐溶剤性、耐熱性も良好で、粒子径分布が狭いという特徴を有し、塗料、インキ、各種研磨剤、各種分析試薬、診断試薬、印刷材料、トナーおよびトナー用外添剤、艶消し剤、樹脂フィラー、樹脂フィルムの滑り性向上剤、クロマト充填剤、耐磨耗剤、液晶ディスプレイ用スペーサー、光拡散シートの光拡散剤、デジタルペーパーなどの電気泳動表示装置用顔料、タッチパネル用ハードコート剤、光学材料、磁性材料、導電材料、難燃剤、製紙材料、繊維処理材料などとして好適に利用される。 The core-shell type spherical composite cured melamine resin particles of the present invention can improve light scattering characteristics and light reflection characteristics especially for visible light, and also have good water resistance, solvent resistance, heat resistance, and narrow particle size distribution. Paints, inks, various abrasives, various analytical reagents, diagnostic reagents, printing materials, toners and external additives for toners, matting agents, resin fillers, resin film slipperiness improvers, chromatographic fillers , Anti-wear agent, liquid crystal display spacer, light diffusion sheet light diffusion agent, pigment for electrophoretic display devices such as digital paper, hard coat agent for touch panel, optical material, magnetic material, conductive material, flame retardant, papermaking material It is preferably used as a fiber processing material.
従来より、光散乱、隠蔽性、光反射防止などの光特性や耐熱性などを改良するために、コア−シェル型粒子が提案されている。メラミン系樹脂をコアとしたコア−シェル型粒子の製造方法としては、水性媒体中で塩基性触媒とフッ化カルシウム、フッ化マグネシウム及びフッ化ストロンチウムからなる群より選ばれた少なくとも１種の実質的に水に不溶性の無機塩類の懸濁下でメラミンとアルデヒド化合物を反応させる方法が開示されている。（特許文献１参照。）この方法では粒子表面が実質的に水に不溶な無機塩類で被覆された硬化メラミン樹脂粒子が得られるが、無機塩類の層厚みについての記載はない。 Conventionally, core-shell type particles have been proposed in order to improve light characteristics such as light scattering, concealability, and light reflection prevention and heat resistance. As a method for producing core-shell type particles having a melamine resin core, at least one substance selected from the group consisting of a basic catalyst, calcium fluoride, magnesium fluoride and strontium fluoride in an aqueous medium is used. Discloses a method of reacting melamine with an aldehyde compound in a suspension of inorganic salts insoluble in water. (See Patent Document 1.) In this method, cured melamine resin particles whose particle surfaces are coated with inorganic salts that are substantially insoluble in water are obtained, but there is no description about the layer thickness of the inorganic salts.
また５〜７０ｎｍの平均粒子径を有するコロイダルシリカの懸濁下でメラミン化合物とアルデヒド化合物の初期縮合物の水溶液を生成させ、この水溶液に酸触媒を加えて球状複合硬化メラミン樹脂粒子を析出させる方法が開示されている。（特許文献２参照）この方法で得られる球状複合硬化メラミン樹脂粒子は、コロイダルシリカが粒子表面付近のメラミン系硬化樹脂内に埋め込まれているか、又は粒子表面上に固着した状態で存在しており、シェル層に相当するメラミン樹脂−シリカ複合層の厚みは５０ｎｍ以下であった。シェルの層厚みが５０ｎｍ以下であると可視光はシェル層を通過してしまうので、光特性においてシェル層の存在は無関係であった。 Also, a method of forming an aqueous solution of an initial condensate of a melamine compound and an aldehyde compound under a suspension of colloidal silica having an average particle diameter of 5 to 70 nm and adding an acid catalyst to the aqueous solution to precipitate spherical composite cured melamine resin particles Is disclosed. (See Patent Document 2) The spherical composite cured melamine resin particles obtained by this method are present in a state where colloidal silica is embedded in the melamine cured resin near the particle surface or fixed on the particle surface. The thickness of the melamine resin-silica composite layer corresponding to the shell layer was 50 nm or less. Since visible light passes through the shell layer when the thickness of the shell layer is 50 nm or less, the presence of the shell layer is irrelevant in optical characteristics.
特に可視光に対する粒子の光散乱特性や光反射特性を改良するために、従来のものよりシェルの層厚みを厚くしたコア−シェル型の球状複合硬化メラミン樹脂粒子を製造する方法の開発が望まれている。
上述のように、従来のメラミン系樹脂をコアとしたコア−シェル型粒子は、シェルの層厚みが５０ｎｍ以下であるので特に可視光に対する粒子の光散乱特性や光反射特性を改良することにおいて課題がある。 As described above, the core-shell type particles having the conventional melamine resin as the core have a shell layer thickness of 50 nm or less, and thus there is a problem in improving the light scattering characteristics and light reflection characteristics of the particles particularly for visible light. There is.
従って、本発明の目的は、従来よりシェルの層厚みを厚くした、具体的にはコアがメラミン系樹脂からなり、シェルが５〜７０ｎｍの平均粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなる、該シェルの層厚みが８０〜４００ｎｍであるコア−シェル型の球状複合硬化メラミン樹脂粒子を提供する。そして、コア−シェル型の球状複合硬化メラミン樹脂粒子の製造方法を提供する。 Accordingly, an object of the present invention is to increase the shell thickness of the shell, more specifically, a melamine in which the core is made of a melamine resin and the shell is closely packed with colloidal silica having an average particle diameter of 5 to 70 nm. Provided is a core-shell type spherical composite cured melamine resin particle having a shell layer thickness of 80 to 400 nm, comprising a resin-silica composite layer. And the manufacturing method of a core-shell type spherical composite hardening melamine resin particle is provided.
本発明の目的は、以下の手段によって達成される。 The object of the present invention is achieved by the following means.
本発明の第一観点は、コアがメラミン系樹脂からなり、シェルが５〜７０ｎｍの平均粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなる、８０〜４００ｎｍの該シェルの層厚みを有する、コア−シェル型の球状複合硬化メラミン樹脂粒子である。 The first aspect of the present invention is that the core is made of a melamine-based resin, and the shell is made of a melamine-based resin-silica composite layer in which colloidal silica having an average particle diameter of 5 to 70 nm is densely packed. These are core-shell type spherical composite cured melamine resin particles having a shell layer thickness.
次に本発明の第二観点は、下記の工程（ａ）及び（ｂ）を含む、コアがメラミン系樹脂からなり、シェルが５〜７０ｎｍの平均粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなる、８０〜４００ｎｍの該シェルの層厚みを有する、コア−シェル型の球状複合硬化メラミン樹脂粒子の製造方法である。 Next, the second aspect of the present invention includes the following steps (a) and (b), wherein the core is made of a melamine resin, and the shell is densely filled with colloidal silica having an average particle diameter of 5 to 70 nm. This is a method for producing core-shell type spherical composite cured melamine resin particles having a shell thickness of 80 to 400 nm, comprising a melamine resin-silica composite layer.
（ａ）：無機酸のアルカリ金属塩を溶解した水性媒体中、５〜７０ｎｍの平均粒子径を有するコロイダルシリカの懸濁下で、メラミン化合物とアルデヒド化合物を塩基性条件下で反応させて、水に可溶なメラミン系樹脂の初期縮合物の水溶液を生成させる工程、及び
（ｂ）：（ａ）工程で得られた水溶液に酸触媒を加えて、球状複合硬化メラミン樹脂粒子を析出させる工程。
(A): A melamine compound and an aldehyde compound are reacted under basic conditions in a suspension of colloidal silica having an average particle diameter of 5 to 70 nm in an aqueous medium in which an alkali metal salt of an inorganic acid is dissolved, and water A step of forming an aqueous solution of an initial condensate of melamine-based resin that is soluble in the solution, and (b): a step of adding an acid catalyst to the aqueous solution obtained in the step (a) to precipitate spherical composite cured melamine resin particles.
その好ましい態様は、以下の通りである。 The preferable aspect is as follows.
（ａ）工程において、無機酸のアルカリ金属塩の添加量が、メラミン化合物１００質量部に対して０．１〜２０質量部であること。 (A) In process, the addition amount of the alkali metal salt of an inorganic acid is 0.1-20 mass parts with respect to 100 mass parts of melamine compounds.
（ａ）工程において、コロイダルシリカの添加量が、メラミン化合物１００質量部に対して３．０〜１００質量部であること。 (A) In process, the addition amount of colloidal silica is 3.0-100 mass parts with respect to 100 mass parts of melamine compounds.
コロイダルシリカが水性シリカゾルであること。 Colloidal silica is an aqueous silica sol.
特に可視光に対する粒子の光散乱特性や光反射特性を改良するために、コアがメラミン系樹脂からなり、シェルが５〜７０ｎｍの平均粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなる、該シェルの層厚みが８０〜４００ｎｍであるコア−シェル型の球状複合硬化メラミン樹脂粒子の製造方法を確立し、該粒子を提供することを可能にした。 In particular, in order to improve light scattering characteristics and light reflection characteristics of particles with respect to visible light, a melamine resin in which a core is made of a melamine resin and a shell is closely packed with colloidal silica having an average particle diameter of 5 to 70 nm. The manufacturing method of the core-shell type spherical composite cured melamine resin particles having a shell layer thickness of 80 to 400 nm composed of a silica composite layer has been established, and the particles can be provided.
まず（ａ）工程について具体的に説明する。（ａ）工程で使用されるメラミン化合物としては、メラミン、メラミンのアミノ基の水素をアルキル基、アルケニル基、フェニル基で置換した置換メラミン化合物［米国特許第５，９９８，５７３号明細書（対応日本特許：特開平９−１４３２３８号公報）に記載されている。］、そしてメラミンのアミノ基の水素をヒドロキシアルキル基、ヒドロキシアルキル（オキサアルキル）ｎ基、アミノアルキル基で置換した置換メラミン化合物［米国特許第５，３２２，９１５号明細書（対応日本特許：特開平５−２０２１５７号公報）に記載されている。］などが使用できる。この中では安価なメラミンが最も好ましい。 First, the step (a) will be specifically described. As the melamine compound used in the step (a), melamine, a substituted melamine compound in which the hydrogen of the amino group of melamine is substituted with an alkyl group, an alkenyl group, or a phenyl group [US Pat. No. 5,998,573 (corresponding) (Japanese Patent: JP-A-9-143238). And a substituted melamine compound in which the hydrogen of the amino group of melamine is substituted with a hydroxyalkyl group, a hydroxyalkyl (oxaalkyl) n group or an aminoalkyl group [US Pat. No. 5,322,915 (corresponding Japanese Patent: Special (Kaihei 5-202157). ] Can be used. Of these, inexpensive melamine is most preferred.
またメラミン化合物とメラミン化合物の一部を尿素、チオ尿素、エチレン尿素などの尿素類、ベンゾグアナミン、アセトグアナミンなどのグアナミン類、フェノール、クレゾール、アルキルフェノール、レゾルシン、ハイドロキノン、ピロガロールなどのフェノール類、アニリンで置き換えて混合物として使用することもできる。 Also, melamine compounds and some of the melamine compounds are replaced with ureas such as urea, thiourea and ethylene urea, guanamines such as benzoguanamine and acetoguanamine, phenols such as phenol, cresol, alkylphenol, resorcin, hydroquinone and pyrogallol, and aniline. Can also be used as a mixture.
アルデヒド化合物としては、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、フルフラールなどが挙げられるが、安価でメラミン化合物との反応性が良いホルムアルデヒドやパラホルムアルデヒドが好ましい。アルデヒド化合物はメラミン化合物１モルに対して有効アルデヒド基当たり１．１〜６．０モル、特に１．２〜４．０モルをとなるアルデヒド化合物を使用することが好ましい。 Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, furfural and the like, but formaldehyde and paraformaldehyde which are inexpensive and have good reactivity with the melamine compound are preferable. As the aldehyde compound, it is preferable to use an aldehyde compound having an amount of 1.1 to 6.0 mol, particularly 1.2 to 4.0 mol, per effective aldehyde group with respect to 1 mol of the melamine compound.
本発明の（ａ）工程で使用する媒体としては水が最も好ましい。また水の一部を、水に可溶する有機溶媒に置き換えた混合溶液も使用でき、この場合メラミン樹脂の初期縮合物や無機酸のアルカリ金属塩を溶解することが可能な有機溶媒を選択すると良い。好ましい有機溶媒としては、メタノール、エタノール、イソプロパノール、プロパノールなどのアルコール類、ジオキサン、テトラヒドロフラン、１，２−ジメトキシエタンなどのエーテル類、ジメチルホルムアミド、ジメチルスルオキシドなどの極性溶媒が挙げられる。 Water is most preferable as the medium used in the step (a) of the present invention. In addition, a mixed solution in which a part of water is replaced with an organic solvent soluble in water can be used. In this case, if an organic solvent capable of dissolving an initial condensate of melamine resin or an alkali metal salt of an inorganic acid is selected. good. Preferable organic solvents include alcohols such as methanol, ethanol, isopropanol and propanol, ethers such as dioxane, tetrahydrofuran and 1,2-dimethoxyethane, and polar solvents such as dimethylformamide and dimethyl sulfoxide.
無機酸のアルカリ金属塩は、水溶性のものが使用できる。具体例として、塩酸、硫酸、硝酸、リン酸などのリチウム塩、ナトリウム塩、カリウム塩が挙げられる。無機酸のアルカリ金属塩の添加量は、メラミン化合物１００質量部に対して０．１〜２０質量部存在させることが好ましい。０．１質量部未満ではメラミン系樹脂−シリカ複合層からなるシェルの層厚みが８０ｎｍ未満になり好ましくない。 A water-soluble alkali metal salt of an inorganic acid can be used. Specific examples include lithium salts such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, sodium salts, and potassium salts. The addition amount of the alkali metal salt of the inorganic acid is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the melamine compound. If it is less than 0.1 part by mass, the thickness of the shell composed of the melamine resin-silica composite layer is less than 80 nm, which is not preferable.
コロイダルシリカは、５〜７０ｎｍの平均粒子径を有するものが使用される。 Colloidal silica having an average particle diameter of 5 to 70 nm is used.
ここでコロイダルシリカの平均粒子径は、窒素吸着法（ＢＥＴ法）により測定して得られる比表面積径である。平均粒子径（比表面積径）（Ｄｎｍ）は、窒素吸着法で測定して、比表面積Ｓｍ２／ｇから、Ｄ＝２７２０／Ｓの式によって与えられる。沈降性シリカパウダー、気相法シリカパウダーなどのパウダー状のコロイダルシリカを使用することもできるが、好ましくは媒体中で一次粒子レベルまで安定分散させたコロイダルシリカのゾルを使用すると良い。コロイダルシリカのゾルとしては水性シリカゾルとオルガノシリカゾルがありどちらも適用可能であるが、メラミン樹脂の製造に水性媒体を用いるため、コロイダルシリカのゾルの分散安定性の面から水性シリカゾルを使用することが最も好ましい。コロイダルシリカのゾル中のシリカ濃度（Ｓｉ０2濃度）は５〜５０質量％のものが一般に市販されており、容易に入手できて好ましい。 Here, the average particle diameter of colloidal silica is a specific surface area diameter obtained by measurement by a nitrogen adsorption method (BET method). The average particle diameter (specific surface area diameter) (Dnm) is given by the formula D = 2720 / S from the specific surface area Sm 2 / g as measured by the nitrogen adsorption method. Although powdered colloidal silica such as precipitated silica powder and vapor phase method silica powder can be used, it is preferable to use a colloidal silica sol stably dispersed to the primary particle level in a medium. There are two types of colloidal silica sols: aqueous silica sol and organosilica sol, both of which can be used. However, since an aqueous medium is used for the production of melamine resin, aqueous silica sol can be used from the viewpoint of dispersion stability of colloidal silica sol. Most preferred. Silica concentration in the sol of colloidal silica (Si0 2 concentration) are generally commercially available include the 5 to 50 mass%, preferably with readily available.
コロイダルシリカの平均粒子径が７０ｎｍを超える場合は、後の（ｂ）工程で析出する複合硬化メラミン樹脂は球状粒子になり難くなる。球状複合硬化メラミン樹脂粒子の平均粒子径は、一般的にメラミン系樹脂濃度が低いほど、またコロイダルシリカの平均粒子径が小さいほど小さくなる傾向にある。 When the average particle diameter of colloidal silica exceeds 70 nm, the composite cured melamine resin that precipitates in the subsequent step (b) is difficult to become spherical particles. In general, the average particle diameter of the spherical composite cured melamine resin particles tends to be smaller as the melamine resin concentration is lower and the average particle diameter of the colloidal silica is smaller.
コロイダルシリカの添加量は、メラミン化合物１００質量部に対して３．０〜１００質量部、特に５．０〜５０質量部存在させることが好ましい。３．０質量部未満ではシェルの層厚みが８０〜４００ｎｍである、コア−シェル型の球状複合硬化メラミン樹脂粒子を得ることが困難になり、シェルの層厚みが８０ｎｍ未満になりやすい。また１００質量部を超えてもコア−シェル型の球状複合硬化メラミン樹脂粒子が得られるが、球状ではなく、球状複合硬化メラミン樹脂粒子に比べ微小な凝集粒子が副生するので好ましくない。 The amount of colloidal silica added is preferably 3.0 to 100 parts by mass, more preferably 5.0 to 50 parts by mass with respect to 100 parts by mass of the melamine compound. If it is less than 3.0 parts by mass, it becomes difficult to obtain core-shell type spherical composite cured melamine resin particles having a shell layer thickness of 80 to 400 nm, and the shell layer thickness tends to be less than 80 nm. If the amount exceeds 100 parts by mass, the core-shell type spherical composite cured melamine resin particles can be obtained, but it is not preferable because it is not spherical, and fine aggregated particles are by-produced compared to the spherical composite cured melamine resin particles.
本発明の（ａ）工程において、メラミン化合物とアルデヒド化合物の反応は塩基性条件下で行われる。一般的なメラミン樹脂に使用される塩基性触媒を使用し、反応液のｐＨを７〜１０に調整して反応を行うことが好ましい。塩基性触媒としては、例えば水酸化ナトリウム、水酸化カリウム、アンモニア水などが好適に使用できる。反応は、通常５０〜８０℃で行えばよく、分子量２００〜７００程度の水に可溶なメラミン樹脂の初期縮合物の水溶液が調製される。 In the step (a) of the present invention, the reaction between the melamine compound and the aldehyde compound is performed under basic conditions. It is preferable to carry out the reaction by using a basic catalyst used for a general melamine resin and adjusting the pH of the reaction solution to 7 to 10. As the basic catalyst, for example, sodium hydroxide, potassium hydroxide, aqueous ammonia and the like can be suitably used. The reaction may be usually performed at 50 to 80 ° C., and an aqueous solution of an initial condensate of melamine resin soluble in water having a molecular weight of about 200 to 700 is prepared.
次に（ｂ）工程について説明する。（ｂ）工程の硬化反応で使用する酸触媒としては特に制限はなく、塩酸、硫酸、硝酸、リン酸や、メタンスルホン酸、ベンゼンスルホン酸、パラトルエンスルホン酸、アルキルベンゼンスルホン酸、スルファミン酸などのスルホン酸類、ギ酸、シュウ酸、安息香酸、フタル酸などの有機酸などが挙げられる。 Next, step (b) will be described. (B) There is no restriction | limiting in particular as an acid catalyst used by hardening reaction of a process, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid, alkylbenzenesulfonic acid, sulfamic acid, etc. Examples include sulfonic acids, formic acid, oxalic acid, benzoic acid, and organic acids such as phthalic acid.
（ｂ）工程において、（ａ）工程で得られた初期縮合物の水溶液に酸触媒を加えて硬化反応を行うが、通常は酸触媒添加後、数分でコア−シェル型の硬化メラミン樹脂粒子が析出する。硬化反応は、反応液のｐＨを酸触媒により３〜７に調整して、７０〜１００℃で行うことが好ましい。 In the step (b), an acid catalyst is added to the aqueous solution of the initial condensate obtained in the step (a) to perform a curing reaction. Usually, the core-shell type cured melamine resin particles are added within a few minutes after the addition of the acid catalyst. Precipitates. The curing reaction is preferably performed at 70 to 100 ° C. by adjusting the pH of the reaction solution to 3 to 7 with an acid catalyst.
また本発明において、（ａ）工程および／または（ｂ）工程で、蛍光染料や水溶性染料を添加することにより、コアがメラミン系樹脂からなり、シェルが５〜７０ｎｍの平均粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなる、シェルの層厚みが８０〜４００ｎｍである、着色されたコア−シェル型の球状複合硬化メラミン樹脂粒子を製造することができる。 Further, in the present invention, a colloidal having a core made of melamine resin and a shell having an average particle diameter of 5 to 70 nm by adding a fluorescent dye or a water-soluble dye in step (a) and / or (b). Colored core-shell type spherical composite cured melamine resin particles having a shell layer thickness of 80 to 400 nm, which is composed of a melamine-based resin-silica composite layer densely filled with silica, can be produced.
蛍光染料としては、公知の蛍光染料や蛍光増白染料を使用できる。メラミン樹脂の製造に水性媒体を使用するため、水溶性の蛍光染料を使用することが好ましく、酸性染料でも塩基性染料でもどちらでも使用できる。また蛍光染料と蛍光を有さない通常の染料を組み合わせて使用することもできる。蛍光染料としては、キサンテン系、ベンゾキサンテン系、ベンゾチオキサンテン系、クマリン系、ペリレン系、ナフタルイミド系、アクリジン系、チオフラビン系、ジアミノスチルベン系、イミダゾール系、チアゾール系、オキサゾール系、ピラゾリン系などがあり、具体的には、ウラニン（Ｃ．Ｉ．４５３５０）、ベーシックイエロー１（Ｃ．Ｉ．４９００５）、アクリジンイエロー（Ｃ．Ｉ．４６０２５）、エオシンＹ（Ｃ．Ｉ．４５３８０）、エオシンＢ（Ｃ．Ｉ．４５４００）、ローダミンＢ（Ｃ．Ｉ．４５１７０）、ローダミン６Ｇ（Ｃ．Ｉ．４５１６０）、ブリリアントブルーＦＣＦ（Ｃ．Ｉ．４２０９０）、ブリリアントブルー６Ｂ（Ｃ．Ｉ．２４４１０）、アシッドブルー９２（Ｃ．Ｉ．１３３９０）、ナフトールグリーンＢ（Ｃ．Ｉ．１００２０）、ブリリアントグリーン（Ｃ．Ｉ．４２０４０）、アリザリングリーン（Ｃ．Ｉ．４２１００）などが挙げられる。 Known fluorescent dyes and fluorescent whitening dyes can be used as the fluorescent dye. Since an aqueous medium is used for the production of the melamine resin, it is preferable to use a water-soluble fluorescent dye, and either an acid dye or a basic dye can be used. Moreover, it can also be used combining the fluorescent dye and the normal dye which does not have fluorescence. Fluorescent dyes include xanthene, benzoxanthene, benzothioxanthene, coumarin, perylene, naphthalimide, acridine, thioflavine, diaminostilbene, imidazole, thiazole, oxazole, pyrazoline, etc. Specifically, uranin (C.I. 45350), basic yellow 1 (C.I. 49005), acridine yellow (C.I. 46025), eosin Y (C.I. 45380), eosin B ( CI. 45400), Rhodamine B (C.I. 45170), Rhodamine 6G (C.I. 45160), Brilliant Blue FCF (C.I. 42090), Brilliant Blue 6B (C.I. 24410), Acid Blue 92 (C.I. 13390), naphthol green (C.I.10020), brilliant green (C.I.42040), alizarin green (C.I.42100) and the like.
水溶性染料としては、公知の酸性染料や塩基性染料を使用できる。例えば、ベンゾキノン系、ナフトキノン系、アントラキノン系、アゾ系、フタロシアニン系、インジゴイド系、フェニルメタン系、ニトロ系、ニトロソ系、アジン系、キノリン系、メチン系などが挙げられ、具体的には、タートラジン（Ｃ．Ｉ．１９１４０）、メタニルイエロー（Ｃ．Ｉ．１３０６５）、ニューコクシン（Ｃ．Ｉ．１６２５５）、ファストレッドＳ（Ｃ．Ｉ．１５６２０）、アシッドブルー４１（Ｃ．Ｉ．６２１３０）、アシッドブルー４５（Ｃ．Ｉ．６３０１０）、インジゴカルミン（Ｃ．Ｉ．７３０１５）、アルファズリンＦＧ（Ｃ．Ｉ．４２０９０）、アシッドグリーン３（Ｃ．Ｉ．４２０８５）、アシッドグリーン５（Ｃ．Ｉ．４２０９５）、ファストグリーンＦＣＦ（Ｃ．Ｉ．４２０５３）、ナフトールブルーブラック（Ｃ．Ｉ．２０４７０）などが挙げられる。
蛍光染料や水溶性染料の添加は、（ａ）工程でも（ｂ）工程でもどちらでもよく、また（ａ）工程と（ｂ）工程でそれぞれ分割して添加してもよい。（ｂ）工程で加える場合は、コア−シェル型の硬化メラミン樹脂粒子が析出した後に加えてもよいが、通常析出後３０分以内に加えることが好ましい。コア−シェル型の硬化メラミン樹脂粒子の析出後３０分以上経過してから加えると、着色の程度が不十分になりやすい。
As the water-soluble dye, known acid dyes and basic dyes can be used. Examples include benzoquinone, naphthoquinone, anthraquinone, azo, phthalocyanine, indigoid, phenylmethane, nitro, nitroso, azine, quinoline, methine, and the like. Specifically, tartrazine ( CI 19140), Methanil Yellow (C.I. 13065), New Coxin (C.I. 16255), Fast Red S (C.I. 15620), Acid Blue 41 (C.I. 62130) Acid Blue 45 (C.I. 63010), Indigo Carmine (C.I. 73015), Alphazurin FG (C.I. 42090), Acid Green 3 (C.I. 42085), Acid Green 5 (C I.42095), Fast Green FCF (C.I.42053), Naphthol Blue Click (C.I.20470) and the like.
The fluorescent dye or water-soluble dye may be added in either step (a) or step (b), or may be added separately in steps (a) and (b). When adding in the step (b), it may be added after the core-shell type cured melamine resin particles are precipitated, but it is usually preferable to add within 30 minutes after the precipitation. If added after 30 minutes or more after the deposition of the core-shell type cured melamine resin particles, the degree of coloring tends to be insufficient.
蛍光染料や水溶性染料の添加量は、メラミン化合物１００質量部に対して０．０１〜２０質量部、特に０．０５〜１０質量部存在させることが好ましい。０．０１質量部未満では着色の程度が不十分であり、２０質量部を超えると（ｂ）工程で塊状ゲル化を起こしやすくなり、安定的に着色されたコア−シェル型の球状複合硬化メラミン樹脂粒子を得ることが困難になる。 The addition amount of the fluorescent dye or the water-soluble dye is preferably 0.01 to 20 parts by mass, particularly 0.05 to 10 parts by mass with respect to 100 parts by mass of the melamine compound. If the amount is less than 0.01 parts by weight, the degree of coloring is insufficient, and if it exceeds 20 parts by weight, it becomes easy to cause massive gelation in the step (b), and the core-shell type spherical composite cured melamine is colored stably. It becomes difficult to obtain resin particles.
本発明ではさらに紫外線吸収剤を添加することができる。紫外線吸収剤としては、ヒドロキシベンゾフェノン系、ベンゾトリアゾール系、サリチレート系、ヒンダードアミン系などの公知の紫外線吸収剤を使用できる。メラミン樹脂の製造に水性媒体を使用するため、水溶性の紫外線吸収剤を使用することが好ましい。 In the present invention, an ultraviolet absorber can be further added. As the ultraviolet absorber, known ultraviolet absorbers such as hydroxybenzophenone, benzotriazole, salicylate, and hindered amine can be used. Since an aqueous medium is used for production of the melamine resin, it is preferable to use a water-soluble ultraviolet absorber.
紫外線吸収剤の添加は、（ａ）工程でも（ｂ）工程でもどちらでもよく、また（ａ）工程と（ｂ）工程でそれぞれ分割して添加してもよい。（ｂ）工程で加える場合は、硬化メラミン樹脂粒子が析出した後に加えてもよいが、通常析出後３０分以内に加えることが好ましい。 The ultraviolet absorber may be added in either step (a) or step (b), or may be added separately in steps (a) and (b). In the case of adding in the step (b), it may be added after the cured melamine resin particles are precipitated, but it is usually preferably added within 30 minutes after the precipitation.
紫外線吸収剤の添加量は、メラミン化合物１００質量部に対して０．０１〜２０質量部、特に０．０５〜１０質量部存在させることが好ましい。２０質量部を超えると（ｂ）工程で塊状ゲル化を起こしやすくなり、安定的に着色されたコア−シェル型の球状複合硬化メラミン樹脂粒子を得ることが困難になる。 The addition amount of the ultraviolet absorber is preferably 0.01 to 20 parts by mass, particularly 0.05 to 10 parts by mass with respect to 100 parts by mass of the melamine compound. When it exceeds 20 parts by mass, it becomes easy to cause bulk gelation in the step (b), and it becomes difficult to obtain core-shell type spherical composite cured melamine resin particles that are stably colored.
本発明で得られるコア−シェル型の球状複合硬化メラミン樹脂粒子は、一般的な濾過又は遠心分離した固形分を乾燥するか、又は樹脂粒子の水分散スラリーを直接噴霧乾燥することにより、粉末状の粒子として得ることができる。乾燥条件は、温度が５０℃から２５０℃、時間は０．０１時間から５０時間行うことが好ましい。乾燥された粉末状の粒子が粒子間凝集している場合は、ホモミキサー、ヘンシェルミキサー、レーディゲミキサーなどの剪断力を有する混合機や、ピンディスクミル、パルベライザー、イノマイザー、カウンタージェットミルなどの粉砕機で適切に処理すれば、球状粒子を破壊することなく粒子間凝集をほぐすことができる。 The core-shell type spherical composite cured melamine resin particles obtained in the present invention are in a powder form by drying a solid content obtained by general filtration or centrifugation, or by directly spray-drying an aqueous dispersion slurry of resin particles. It can be obtained as particles. The drying conditions are preferably a temperature of 50 ° C. to 250 ° C. and a time of 0.01 hours to 50 hours. If the dried powder particles are aggregated between particles, use a mixer with shearing force such as a homomixer, Henschel mixer, or Laedige mixer, or a pin disc mill, pulverizer, inomizer, counter jet mill, etc. When appropriately treated with a pulverizer, interparticle aggregation can be loosened without destroying the spherical particles.
本発明で得られるコア−シェル型の球状複合硬化メラミン樹脂粒子は、平均粒子径が０．５〜１００μｍである。ここでコア−シェル型の球状複合硬化メラミン樹脂粒子の平均粒子径（μｍ）は、Ｍｉｅ理論に基づくレーザー回折・散乱法により測定して得られる５０％体積径（メジアン径）である。 The core-shell type spherical composite cured melamine resin particles obtained in the present invention have an average particle size of 0.5 to 100 μm. The average particle diameter (μm) of the core-shell type spherical composite cured melamine resin particles is a 50% volume diameter (median diameter) obtained by measurement by a laser diffraction / scattering method based on the Mie theory.
本発明のコア−シェル型の球状複合硬化メラミン樹脂粒子の製造において、コロイダルシリカの作用機構は明らかではないが、おそらくメラミン系樹脂中のアミノ基とコロイダルシリカ粒子表面に存在するシラノール基が水素結合的に作用するために、メラミン系硬化樹脂粒子の析出時にコロイダルシリカが界面活性剤としての役割を果たしていると考えられる。
さらに無機酸のアルカリ金属塩は、コロイダルシリカの粒子表面特性に影響を与え、コア−シェル型の球状複合硬化メラミン樹脂粒子の表面でコロイダルシリカが数層から数十層に積層させる役目を果たしていると考えられる。そのため、通常コロイダルシリカをメラミン化合物に対して所定量より多く添加した場合は、球状ではなく球状複合硬化メラミン樹脂粒子に比べ微小な凝集粒子が副生する傾向にあるが、無機酸のアルカリ金属塩を使用した場合はメラミン化合物に対してコロイダルシリカを所定量より多く添加しても微小な凝集粒子が副生し難く、結果としてコロイダルシリカを多く添加することができ、シリカからなるシェル層を厚くすることが可能になると考えられる。
In the production of the core-shell type spherical composite cured melamine resin particles of the present invention, the mechanism of action of the colloidal silica is not clear, but the amino groups in the melamine resin and the silanol groups present on the surface of the colloidal silica particles are probably hydrogen bonds. Therefore, it is considered that colloidal silica plays a role as a surfactant during precipitation of melamine-based cured resin particles.
Furthermore, the alkali metal salt of an inorganic acid affects the particle surface properties of colloidal silica, and plays a role in laminating colloidal silica into several to several tens of layers on the surface of core-shell type spherical composite cured melamine resin particles. it is conceivable that. Therefore, usually when colloidal silica is added in a larger amount than the predetermined amount with respect to the melamine compound, there is a tendency that fine agglomerated particles are produced as a by-product as compared to spherical composite cured melamine resin particles instead of spherical particles. When a larger amount of colloidal silica is added to the melamine compound than a predetermined amount, fine agglomerated particles are hardly produced as a by-product, and as a result, a large amount of colloidal silica can be added, resulting in a thicker silica shell layer. It will be possible to do this.
本発明で得られるコアがメラミン系樹脂、シェルが５〜７０ｎｍの平均粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなり、該シェルの層厚みが８０〜４００ｎｍである、コア−シェル型球状複合硬化メラミン樹脂粒子とは、一次粒子が球状で独立しており、空孔は有しておらず、シェル層はコロイダルシリカがメラミン系硬化樹脂内で密に充填された状態で存在していることを意味している。コロイダルシリカは粒子表面付近のメラミン系硬化樹脂内に埋め込まれていたり、粒子表面上に固着した状態で存在する。このような形態は、コア−シェル型の球状複合硬化メラミン樹脂粒子のスライス片を、電子顕微鏡を用いた撮影写真などによって容易に観察することができる。 The core obtained in the present invention is composed of a melamine-based resin, a shell is a melamine-based resin-silica composite layer in which colloidal silica having an average particle diameter of 5 to 70 nm is closely packed, and the shell has a layer thickness of 80 to 400 nm. Some core-shell type spherical composite cured melamine resin particles have primary particles that are spherical and independent, do not have pores, and the shell layer is closely packed with colloidal silica in the melamine-based cured resin. It means that it exists in the state. Colloidal silica is embedded in a melamine-based cured resin near the particle surface or is fixed on the particle surface. In such a form, a slice of core-shell type spherical composite cured melamine resin particles can be easily observed by a photograph taken using an electron microscope.
本発明で得られるコアがメラミン系樹脂からなり、シェルが５〜７０ｎｍの平均粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなる、該シェルの層厚みが８０〜４００ｎｍである、コア−シェル型球状複合硬化メラミン樹脂粒子は、メラミン樹脂の屈折率（ｎＤ）が約１．６５で、コロイダルシリカの屈折率（ｎＤ）が約１．４６であり、コアとシェル間で屈折率差を有するため、可視光が照射されると粒子の最表面とコア−シェル界面の両方で反射するので、光散乱特性や光反射特性を改良することができる。 The core obtained in the present invention is composed of a melamine-based resin, and the shell is composed of a melamine-based resin-silica composite layer in which colloidal silica having an average particle diameter of 5 to 70 nm is closely packed. The core-shell type spherical composite cured melamine resin particle having a thickness of 400 nm has a refractive index (n D ) of melamine resin of about 1.65 and a refractive index (n D ) of colloidal silica of about 1.46. Therefore, when the visible light is irradiated, the light is reflected at both the outermost surface of the particle and the core-shell interface, so that the light scattering characteristics and the light reflection characteristics can be improved.
以下に実施例、比較例をもって本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
シェルの層厚みの測定は以下のようにして行った。 The thickness of the shell layer was measured as follows.
包埋用ボードに包埋用エポキシ樹脂と本発明の粒子と硬化剤を入れて十分に混ぜ、温度６０℃のオーブン中で一晩硬化させた。硬化物をミクロトーム［ＵＬＴＲＡＣＵＴ Ｎ（商品名）Ｒｅｉｃｈｅｒｔ−Ｎｉｓｓｅｎ製］で薄片化して、粒子のスライス片を透過型電子顕微鏡（ＴＥＭ）にて撮影した。ＴＥＭ写真よりシェルの層厚みを実測した。 The embedding board was filled with the embedding epoxy resin, the particles of the present invention and the curing agent, and was cured in an oven at a temperature of 60 ° C. overnight. The cured product was sliced with a microtome [ULTRACUT N (trade name) manufactured by Reichert-Nissen], and a slice of the particle was photographed with a transmission electron microscope (TEM). The thickness of the shell layer was measured from a TEM photograph.
実施例１
撹拌機、還流コンデンサー及び温度計を装備した２Ｌの反応フラスコに、メラミン８０．０ｇ、３７％ホルマリン１５４．４ｇ、水性シリカゾル［日産化学工業（株）製 スノーテックスＯ−４０（商品名）：Ｓｉ０2濃度４０．７質量％、ｐＨ２．４、平均粒子径２３．０ｎｍ］１６．８ｇ、硫酸ナトリウム１．０ｇ、水６８３ｇを仕込み、２５％アンモニア水にてｐＨを８．５に調整した。その後、上記混合物を撹拌しながら昇温して、温度を７０℃に保ち、３０分反応させてメラミン樹脂の初期縮合物の水溶液を調製した。この時点でのメラミン樹脂の分子量は、ＧＰＣ法（ポリスチレン換算）にて測定したところ２９０であった。次に温度を７０℃に維持したまま、得られた初期縮合物の水溶液にパラトルエンスルホン酸・一水和物の１０質量％水溶液を添加してｐＨを５．１に調整した。約５分後に反応系内が白濁して硬化メラミン樹脂粒子が析出した。その後、温度を９０℃まで昇温して３時間硬化反応を続けた。冷却後、得られた反応液を濾過、乾燥し、ピンディスクミルで粉砕することにより白色の硬化メラミン樹脂粒子を得た。平均粒子径はレーザー回折・散乱式粒度分布測定装置［マスターサイザー２０００（商品名）マルバーン社製］で測定したところ、４．５μｍであった。この硬化樹脂粒子をそのままの状態で走査型電子顕微鏡（ＳＥＭ）にて観察したところ、球状粒子のみが観察された。またこの球状粒子をスライス片の状態で透過型電子顕微鏡−エネルギー分散型Ｘ線分析（ＴＥＭ−ＥＤＸ）にて観察したところ、コアがメラミン樹脂、シェルが２３ｎｍの粒子径を有するコロイダルシリカが密に充填されたメラミン樹脂−シリカ複合層からなり、そのシェルの層厚みは１５０ｎｍであることが確認された。
Example 1
In a 2 L reaction flask equipped with a stirrer, a reflux condenser and a thermometer, melamine 80.0 g, 37% formalin 154.4 g, aqueous silica sol [Nissan Chemical Industry Co., Ltd. Snowtex O-40 (trade name): Si0 2 Concentration 40.7% by mass, pH 2.4, average particle diameter 23.0 nm] 16.8 g, sodium sulfate 1.0 g, and water 683 g were charged, and the pH was adjusted to 8.5 with 25% aqueous ammonia. Thereafter, the temperature of the mixture was increased while stirring, the temperature was maintained at 70 ° C., and the mixture was reacted for 30 minutes to prepare an aqueous solution of an initial condensate of melamine resin. The molecular weight of the melamine resin at this point was 290 as measured by GPC method (polystyrene conversion). Next, while maintaining the temperature at 70 ° C., a 10% by mass aqueous solution of paratoluenesulfonic acid monohydrate was added to the obtained aqueous solution of the initial condensate to adjust the pH to 5.1. About 5 minutes later, the reaction system became cloudy and cured melamine resin particles were precipitated. Thereafter, the temperature was raised to 90 ° C. and the curing reaction was continued for 3 hours. After cooling, the obtained reaction solution was filtered, dried, and pulverized with a pin disc mill to obtain white cured melamine resin particles. The average particle size was 4.5 μm as measured by a laser diffraction / scattering type particle size distribution analyzer [Mastersizer 2000 (trade name) manufactured by Malvern, Inc.]. When the cured resin particles were observed as they were with a scanning electron microscope (SEM), only spherical particles were observed. The spherical particles were observed in the form of slices by transmission electron microscope-energy dispersive X-ray analysis (TEM-EDX). The core was melamine resin and the shell was densely colloidal silica having a particle diameter of 23 nm. It was confirmed to be composed of a filled melamine resin-silica composite layer, and the layer thickness of the shell was 150 nm.
実施例２
撹拌機、還流コンデンサー及び温度計を装備した２Ｌの反応フラスコに、メラミン８０．０ｇ、３７％ホルマリン１５４．４ｇ、水性シリカゾル［日産化学工業（株）製 スノーテックスＯ−４０（商品名）：Ｓｉ０2濃度４０．７質量％、ｐＨ２．４、平均粒子径２３．０ｎｍ］１３．４ｇ、硫酸ナトリウム０．５ｇ、水６８３ｇを仕込み、２５％アンモニア水にてｐＨを８．５に調整した。その後、上記混合物を撹拌しながら昇温し、温度を７０℃に保ち、３０分反応させてメラミン樹脂の初期縮合物の水溶液を調製した。この時点でのメラミン樹脂の分子量は、ＧＰＣ法（ポリスチレン換算）にて測定したところ２８０であった。次に温度を７０℃に維持したまま、得られた初期縮合物の水溶液にパラトルエンスルホン酸・一水和物の１０質量％水溶液を添加してｐＨを５．０に調整した。約５分後に反応系内が白濁して硬化メラミン樹脂粒子が析出した。その後、温度を９０℃まで昇温して３時間硬化反応を続けた。冷却後、得られた反応液を濾過、乾燥し、ピンディスクミルで粉砕することにより白色の硬化メラミン樹脂粒子を得た。平均粒子径はレーザー回折・散乱式粒度分布測定装置［マスターサイザー２０００（商品名）マルバーン社製］で測定したところ、４．４μｍであった。この硬化樹脂粒子をそのままの状態で走査型電子顕微鏡（ＳＥＭ）にて観察したところ、球状粒子のみが観察された。またこの球状粒子をスライス片の状態で透過型電子顕微鏡−エネルギー分散型Ｘ線分析（ＴＥＭ−ＥＤＸ）にて観察したところ、コアがメラミン樹脂、シェルが２３ｎｍの粒子径を有するコロイダルシリカが密に充填されたメラミン樹脂−シリカ複合層からなり、そのシェルの層厚みは９０ｎｍであることが確認された。
Example 2
In a 2 L reaction flask equipped with a stirrer, a reflux condenser and a thermometer, melamine 80.0 g, 37% formalin 154.4 g, aqueous silica sol [Nissan Chemical Industry Co., Ltd. Snowtex O-40 (trade name): Si0 2 concentration 40.7 mass%, pH 2.4, average particle diameter 23.0 nm] 13.4 g, sodium sulfate 0.5 g, and water 683 g were charged, and the pH was adjusted to 8.5 with 25% aqueous ammonia. Thereafter, the temperature of the mixture was increased while stirring, the temperature was kept at 70 ° C., and the mixture was reacted for 30 minutes to prepare an aqueous solution of an initial condensate of melamine resin. The molecular weight of the melamine resin at this time was 280 as measured by GPC method (polystyrene conversion). Next, while maintaining the temperature at 70 ° C., a 10% by mass aqueous solution of paratoluenesulfonic acid monohydrate was added to the obtained aqueous solution of the initial condensate to adjust the pH to 5.0. About 5 minutes later, the reaction system became cloudy and cured melamine resin particles were precipitated. Thereafter, the temperature was raised to 90 ° C. and the curing reaction was continued for 3 hours. After cooling, the obtained reaction solution was filtered, dried, and pulverized with a pin disc mill to obtain white cured melamine resin particles. The average particle size was 4.4 μm as measured by a laser diffraction / scattering type particle size distribution analyzer [Mastersizer 2000 (trade name) manufactured by Malvern, Inc.]. When the cured resin particles were observed as they were with a scanning electron microscope (SEM), only spherical particles were observed. The spherical particles were observed in the form of slices by transmission electron microscope-energy dispersive X-ray analysis (TEM-EDX). The core was melamine resin and the shell was densely colloidal silica having a particle diameter of 23 nm. It consisted of the filled melamine resin-silica composite layer, and the layer thickness of the shell was confirmed to be 90 nm.
実施例３
撹拌機、還流コンデンサー及び温度計を装備した２Ｌの反応フラスコに、メラミン８０．０ｇ、３７％ホルマリン１５４．４ｇ、水性シリカゾル［日産化学工業（株）製 スノーテックスＯ−４０（商品名）：Ｓｉ０2濃度４０．７質量％、ｐＨ２．４、平均粒子径２３．０ｎｍ］１８．０ｇ、硫酸ナトリウム１．０ｇ、水６８３ｇを仕込み、２５％アンモニア水にてｐＨを８．５に調整した。その後、上記混合物を撹拌しながら昇温して、温度を７０℃に保ち、３０分反応させてメラミン樹脂の初期縮合物の水溶液を調製した。この時点でのメラミン樹脂の分子量は、ＧＰＣ法（ポリスチレン換算）にて測定したところ２９０であった。次に温度を７０℃に維持したまま、得られた初期縮合物の水溶液にパラトルエンスルホン酸・一水和物の１０質量％水溶液を添加してｐＨを５．１に調整した。約５分後に反応系内が白濁して硬化メラミン樹脂粒子が析出した。その後、温度を９０℃まで昇温して３時間硬化反応を続けた。冷却後、得られた反応液を濾過、乾燥し、ピンディスクミルで粉砕することにより白色の硬化メラミン樹脂粒子を得た。平均粒子径はレーザー回折・散乱式粒度分布測定装置［マスターサイザー２０００（商品名）マルバーン社製］で測定したところ、４．６μｍであった。この硬化樹脂粒子をそのままの状態で走査型電子顕微鏡（ＳＥＭ）にて観察したところ、球状粒子のみが観察された。またこの球状粒子をスライス片の状態で透過型電子顕微鏡−エネルギー分散型Ｘ線分析（ＴＥＭ−ＥＤＸ）にて観察したところ、コアがメラミン樹脂、シェルが２３ｎｍの粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなり、そのシェルの層厚みは２２０ｎｍであることが確認された。
Example 3
In a 2 L reaction flask equipped with a stirrer, a reflux condenser and a thermometer, melamine 80.0 g, 37% formalin 154.4 g, aqueous silica sol [Nissan Chemical Industry Co., Ltd. Snowtex O-40 (trade name): Si0 2 Concentration 40.7% by mass, pH 2.4, average particle size 23.0 nm] 18.0 g, sodium sulfate 1.0 g, and water 683 g were charged, and the pH was adjusted to 8.5 with 25% aqueous ammonia. Thereafter, the temperature of the mixture was increased while stirring, the temperature was maintained at 70 ° C., and the mixture was reacted for 30 minutes to prepare an aqueous solution of an initial condensate of melamine resin. The molecular weight of the melamine resin at this point was 290 as measured by GPC method (polystyrene conversion). Next, while maintaining the temperature at 70 ° C., a 10% by mass aqueous solution of paratoluenesulfonic acid monohydrate was added to the obtained aqueous solution of the initial condensate to adjust the pH to 5.1. About 5 minutes later, the reaction system became cloudy and cured melamine resin particles were precipitated. Thereafter, the temperature was raised to 90 ° C. and the curing reaction was continued for 3 hours. After cooling, the obtained reaction solution was filtered, dried, and pulverized with a pin disc mill to obtain white cured melamine resin particles. The average particle size was 4.6 μm as measured by a laser diffraction / scattering type particle size distribution analyzer [Mastersizer 2000 (trade name) manufactured by Malvern, Inc.]. When the cured resin particles were observed as they were with a scanning electron microscope (SEM), only spherical particles were observed. The spherical particles were observed in the form of slices by transmission electron microscope-energy dispersive X-ray analysis (TEM-EDX). The core was melamine resin and the shell was densely colloidal silica having a particle diameter of 23 nm. It was confirmed to be composed of a filled melamine-based resin-silica composite layer, and the layer thickness of the shell was 220 nm.
実施例４
撹拌機、還流コンデンサー及び温度計を装備した２Ｌの反応フラスコに、メラミン８０．０ｇ、３７％ホルマリン１５４．４ｇ、水性シリカゾル［日産化学工業（株）製 スノーテックスＯ−４０（商品名）：Ｓｉ０2濃度４０．７質量％、ｐＨ２．４、平均粒子径２３．０ｎｍ］１８．０ｇ、塩化ナトリウム１．０ｇ、水６８３ｇを仕込み、２５％アンモニア水にてｐＨを８．５に調整した。その後、上記混合物を撹拌しながら昇温して、温度を７０℃に保ち、３０分反応させてメラミン樹脂の初期縮合物の水溶液を調製した。この時点でのメラミン樹脂の分子量は、ＧＰＣ法（ポリスチレン換算）にて測定したところ２８０であった。次に温度を７０℃に維持したまま、得られた初期縮合物の水溶液にパラトルエンスルホン酸・一水和物の１０質量％水溶液を添加してｐＨを５．１に調整した。約４分後に反応系内が白濁して硬化メラミン樹脂粒子が析出した。その後、温度を９０℃まで昇温して３時間硬化反応を続けた。冷却後、得られた反応液を濾過、乾燥し、ピンディスクミルで粉砕することにより白色の硬化メラミン樹脂粒子を得た。平均粒子径はレーザー回折・散乱式粒度分布測定装置［マスターサイザー２０００（商品名）マルバーン社製］で測定したところ、３．６μｍであった。この硬化樹脂粒子をそのままの状態で走査型電子顕微鏡（ＳＥＭ）にて観察したところ、球状粒子のみが観察された。またこの球状粒子をスライス片の状態で透過型電子顕微鏡−エネルギー分散型Ｘ線分析（ＴＥＭ−ＥＤＸ）にて観察したところ、コアがメラミン樹脂、シェルが２３ｎｍの粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなり、そのシェルの層厚みは１２０ｎｍであることが確認された。
Example 4
In a 2 L reaction flask equipped with a stirrer, a reflux condenser and a thermometer, melamine 80.0 g, 37% formalin 154.4 g, aqueous silica sol [Nissan Chemical Industry Co., Ltd. Snowtex O-40 (trade name): Si0 2 Concentration 40.7% by mass, pH 2.4, average particle diameter 23.0 nm] 18.0 g, sodium chloride 1.0 g, and water 683 g were charged, and the pH was adjusted to 8.5 with 25% aqueous ammonia. Thereafter, the temperature of the mixture was increased while stirring, the temperature was maintained at 70 ° C., and the mixture was reacted for 30 minutes to prepare an aqueous solution of an initial condensate of melamine resin. The molecular weight of the melamine resin at this time was 280 as measured by GPC method (polystyrene conversion). Next, while maintaining the temperature at 70 ° C., a 10% by mass aqueous solution of paratoluenesulfonic acid monohydrate was added to the obtained aqueous solution of the initial condensate to adjust the pH to 5.1. After about 4 minutes, the reaction system was clouded and cured melamine resin particles were precipitated. Thereafter, the temperature was raised to 90 ° C. and the curing reaction was continued for 3 hours. After cooling, the obtained reaction solution was filtered, dried, and pulverized with a pin disc mill to obtain white cured melamine resin particles. The average particle size was 3.6 μm as measured by a laser diffraction / scattering type particle size distribution analyzer [Mastersizer 2000 (trade name), manufactured by Malvern, Inc.]. When the cured resin particles were observed as they were with a scanning electron microscope (SEM), only spherical particles were observed. The spherical particles were observed in the form of slices by transmission electron microscope-energy dispersive X-ray analysis (TEM-EDX). The core was melamine resin and the shell was densely colloidal silica having a particle diameter of 23 nm. It consisted of the filled melamine resin-silica composite layer, and it was confirmed that the layer thickness of the shell was 120 nm.
比較例１
硫酸ナトリウムを使用しなかったほかは、実施例１と同様に行った。得られた反応液を濾過、乾燥し、ピンディスクミルで粉砕することにより白色の硬化メラミン樹脂粒子を得た。平均粒子径はレーザー回折・散乱式粒度分布測定装置［マスターサイザー２０００（商品名）マルバーン社製］で測定したところ、４．０μｍであった。この硬化樹脂粒子をそのままの状態で走査型電子顕微鏡（ＳＥＭ）にて観察したところ、球状粒子以外に球状でない微小な凝集粒子が副生していた。またこの球状粒子をスライス片の状態で透過型電子顕微鏡−エネルギー分散型Ｘ線分析（ＴＥＭ−ＥＤＸ）にて観察したところ、コアがメラミン樹脂、シェルが２３ｎｍの粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなり、そのシェルの層厚みは４０ｎｍであった。
Comparative Example 1
The same procedure as in Example 1 was performed except that sodium sulfate was not used. The obtained reaction solution was filtered, dried, and pulverized with a pin disc mill to obtain white cured melamine resin particles. The average particle size was 4.0 μm as measured by a laser diffraction / scattering type particle size distribution analyzer [Mastersizer 2000 (trade name) manufactured by Malvern, Inc.]. When the cured resin particles were observed as they were with a scanning electron microscope (SEM), fine non-spherical aggregated particles other than spherical particles were by-produced. The spherical particles were observed in the form of slices by transmission electron microscope-energy dispersive X-ray analysis (TEM-EDX). The core was melamine resin and the shell was densely colloidal silica having a particle diameter of 23 nm. It was composed of a filled melamine-based resin-silica composite layer, and the shell layer thickness was 40 nm.
比較例２
硫酸ナトリウムを使用せず、水性シリカゾル［日産化学工業（株）製 スノーテックスＯ−４０（商品名）：Ｓｉ０2濃度４０．７質量％、ｐＨ２．４、平均粒子径２３．０ｎｍ］を１０．３ｇに減らしたほかは、実施例１と同様に行った。得られた反応液を濾過、乾燥し、ピンディスクミルで粉砕することにより白色の硬化メラミン樹脂粒子を得た。平均粒子径はレーザー回折・散乱式粒度分布測定装置［マスターサイザー２０００（商品名）マルバーン社製］で測定したところ、４．５μｍであった。この硬化樹脂粒子をそのままの状態で走査型電子顕微鏡（ＳＥＭ）にて観察したところ、球状粒子のみが観察された。またこの球状粒子をスライス片の状態で透過型電子顕微鏡−エネルギー分散型Ｘ線分析（ＴＥＭ−ＥＤＸ）にて観察したところ、コアがメラミン樹脂、シェルが２３ｎｍの粒子径を有するコロイダルシリカが密に充填されたメラミン系樹脂−シリカ複合層からなり、そのシェルの層厚みは４０ｎｍであった。
Comparative Example 2
Sodium sulfate is not used, and an aqueous silica sol [Snowtex O-40 (trade name) manufactured by Nissan Chemical Industries, Ltd .: SiO 2 concentration 40.7 mass%, pH 2.4, average particle size 23.0 nm] is used. The procedure was the same as Example 1 except that the amount was reduced to 3 g. The obtained reaction solution was filtered, dried, and pulverized with a pin disc mill to obtain white cured melamine resin particles. The average particle size was 4.5 μm as measured by a laser diffraction / scattering type particle size distribution analyzer [Mastersizer 2000 (trade name) manufactured by Malvern, Inc.]. When the cured resin particles were observed as they were with a scanning electron microscope (SEM), only spherical particles were observed. The spherical particles were observed in the form of slices by transmission electron microscope-energy dispersive X-ray analysis (TEM-EDX). The core was melamine resin and the shell was densely colloidal silica having a particle diameter of 23 nm. It was composed of a filled melamine-based resin-silica composite layer, and the shell layer thickness was 40 nm.
Claims (5)
（ａ）：無機酸のアルカリ金属塩を溶解した水性媒体中、５〜７０ｎｍの平均粒子径を有するコロイダルシリカの懸濁下で、メラミン化合物とアルデヒド化合物を塩基性条件下で反応させて、水に可溶なメラミン系樹脂の初期縮合物の水溶液を生成させる工程、及び
（ｂ）：（ａ）工程で得られた水溶液に酸触媒を加えて、球状複合硬化メラミン樹脂粒子を析出させる工程。 Including the following steps (a) and (b), the core is composed of a melamine resin, and the shell is composed of a melamine resin-silica composite layer in which colloidal silica having an average particle diameter of 5 to 70 nm is closely packed, A method for producing core-shell type spherical composite cured melamine resin particles having a shell layer thickness of 80 to 400 nm.
(A): A melamine compound and an aldehyde compound are reacted under basic conditions in a suspension of colloidal silica having an average particle diameter of 5 to 70 nm in an aqueous medium in which an alkali metal salt of an inorganic acid is dissolved, and water A step of forming an aqueous solution of an initial condensate of melamine-based resin that is soluble in the solution, and (b): a step of adding an acid catalyst to the aqueous solution obtained in the step (a) to precipitate spherical composite cured melamine resin particles.
The method for producing core-shell type spherical composite cured melamine resin particles according to claim 2, 3 or 4, wherein the colloidal silica is an aqueous silica sol.
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