JP6180317B2 - Method for producing fluorescent dye-containing resin beads, fluorescent dye-containing resin beads obtained by the method, and fluorescent article using the same - Google Patents
Method for producing fluorescent dye-containing resin beads, fluorescent dye-containing resin beads obtained by the method, and fluorescent article using the same Download PDFInfo
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- JP6180317B2 JP6180317B2 JP2013264991A JP2013264991A JP6180317B2 JP 6180317 B2 JP6180317 B2 JP 6180317B2 JP 2013264991 A JP2013264991 A JP 2013264991A JP 2013264991 A JP2013264991 A JP 2013264991A JP 6180317 B2 JP6180317 B2 JP 6180317B2
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- 239000007850 fluorescent dye Substances 0.000 title claims description 117
- 239000012508 resin bead Substances 0.000 title claims description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 238000000034 method Methods 0.000 title description 8
- 239000000178 monomer Substances 0.000 claims description 95
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 40
- 125000000524 functional group Chemical group 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 11
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkylene diol Chemical class 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000956 coumarin Drugs 0.000 claims description 2
- 235000001671 coumarin Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 43
- 229940048053 acrylate Drugs 0.000 description 29
- 238000013508 migration Methods 0.000 description 15
- 230000005012 migration Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- RLUCXJBHKHIDSP-UHFFFAOYSA-N propane-1,2-diol;propanoic acid Chemical compound CCC(O)=O.CC(O)CO RLUCXJBHKHIDSP-UHFFFAOYSA-N 0.000 description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、色移行に対する耐性に優れた蛍光性染料含有樹脂ビーズの製造方法、該方法によって得られた蛍光性染料含有樹脂ビーズ、並びにこれを用いた蛍光性を有する物品に関する。 The present invention relates to a method for producing a fluorescent dye-containing resin bead excellent in resistance to color transfer, a fluorescent dye-containing resin bead obtained by the method, and a fluorescent article using the same.
蛍光性染料は良好な蛍光特性を有するため、従来より、成形体、フィルム、印刷物、塗膜、塗料、分散体及び分散液などの様々な用途に使用されている。中でもペリレン系蛍光性染料は、非常に堅牢な耐候性や耐熱性を持つ蛍光性染料として知られており、有用である。しかし、ペリレン系蛍光性染料には、下記に挙げるように、色移行の面での問題があった。具体的には、樹脂中で使用した際にはマイグレーション耐性に劣り、蛍光性染料が樹脂に色移行する場合があった。また、塗料として使用した場合には、ブリード耐性が劣ることから、重ね塗りした塗膜に色移行するといった現象が起こりやすかった。このため、その使用に際しては、これらの色移行の問題を解決しなければならなかった。 Since fluorescent dyes have good fluorescent properties, they have been used in various applications such as molded bodies, films, printed materials, coating films, paints, dispersions and dispersions. Among them, perylene fluorescent dyes are known and useful as fluorescent dyes having extremely strong weather resistance and heat resistance. However, the perylene-based fluorescent dye has a problem in terms of color transfer as described below. Specifically, when used in a resin, the migration resistance is inferior, and the fluorescent dye may migrate to the resin. Further, when used as a paint, the bleed resistance is inferior, so that a phenomenon such as color transfer to the overcoated film tends to occur. For this reason, in the use thereof, it has been necessary to solve these color shift problems.
上記したような色移行の問題を解決するため、これまでに様々な工夫が施されてきた。例えば、特許文献１では、架橋ポリメタアクリレートまたはポリアクリレートである重合体マトリックスと、ペリレン系列等の非極性の蛍光性染料を実質的に含んでなる蛍光顔料を提案している。 In order to solve the problem of color shift as described above, various ideas have been made so far. For example, Patent Document 1 proposes a fluorescent pigment that substantially includes a polymer matrix that is a crosslinked polymethacrylate or polyacrylate and a nonpolar fluorescent dye such as a perylene series.
しかしながら、本発明者らの検討によれば、上記した従来技術では、前記した蛍光性染料の色移行に対する十分な効果が達成されておらず、使用した蛍光性染料がより良好な色移行に対する耐性を示すものとなる蛍光性染料の使用技術の開発が望まれる。 However, according to the study by the present inventors, in the above-described prior art, a sufficient effect on the color transfer of the fluorescent dye described above has not been achieved, and the used fluorescent dye has better resistance to color transfer. It is desired to develop a technique for using a fluorescent dye that exhibits
従って本発明の目的は、蛍光性染料が良好な蛍光特性を維持しつつ、色移行に対する十分な耐性を持つ、蛍光性染料含有樹脂ビーズの製造方法、該方法によって得られた蛍光性染料含有樹脂ビーズ、及びこれを用いた製品を提供することである。 Accordingly, an object of the present invention is to provide a method for producing fluorescent dye-containing resin beads, in which the fluorescent dye has sufficient resistance to color migration while maintaining good fluorescent properties, and the fluorescent dye-containing resin obtained by the method. It is to provide beads and products using the same.
本発明者らは、従来技術を解決すべく鋭意検討した結果、蛍光性染料、特に色移行に対する耐性について課題があったペリレン系蛍光性染料を使用した場合でも、良好な蛍光特性を維持しつつ、色移行に対する十分な耐性が付与された製品の提供が可能になる、極めて有用な蛍光性染料含有樹脂ビーズを提供し得る技術を見出して、本発明に到達したものである。 As a result of intensive studies to solve the prior art, the present inventors have maintained good fluorescence characteristics even when using fluorescent dyes, particularly perylene fluorescent dyes that have problems with respect to resistance to color migration. The present invention has been achieved by finding a technique capable of providing a very useful fluorescent dye-containing resin bead capable of providing a product with sufficient resistance to color transfer.
前記した従来技術の課題は、下記の本発明によって達成される。すなわち、本発明は、蛍光性染料含有樹脂ビーズの製造方法であって、共重合可能な官能基を２以上有するモノマーを、使用する全モノマーに対して３０質量％を超える量で含むモノマー混合液に、蛍光性染料をモノマー混合液に対して３質量％以下となる量で溶解し、これに重合開始剤を加えて重合性モノマー液を調製した後、該重合性モノマー液を水相に加えて撹拌して懸濁液を調製し、懸濁重合することにより、樹脂ビーズを得ることを特徴とする蛍光性染料含有樹脂ビーズの製造方法を提供する。 The problems of the prior art described above are achieved by the present invention described below. That is, the present invention is a method for producing a fluorescent dye-containing resin bead, which is a monomer mixed solution containing a monomer having two or more copolymerizable functional groups in an amount exceeding 30% by mass based on the total monomers used. In addition, after dissolving the fluorescent dye in an amount of 3% by mass or less with respect to the monomer mixture, a polymerization initiator is added thereto to prepare a polymerizable monomer solution, and then the polymerizable monomer solution is added to the aqueous phase. A method for producing a fluorescent dye-containing resin bead is provided, wherein the resin bead is obtained by stirring and preparing a suspension, followed by suspension polymerization.
上記した本発明の好ましい形態としては、下記のものが挙げられる。前記共重合可能な官能基を２以上有するモノマーが、（メタ）アクリレート骨格を有するモノマーであること；前記共重合可能な官能基を２以上有するモノマーが、アルキレンジオールジ（メタ）アクリレート、アルキレングリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート及びそれらの誘導体の群から選択された少なくとも１種であること；前記蛍光性染料が、ペリレン系蛍光性染料であること；前記蛍光性染料の使用量が、前記モノマー混合液に対して２質量％以下となる量であることが挙げられる。 The following are mentioned as a preferable form of this invention mentioned above. The monomer having two or more copolymerizable functional groups is a monomer having a (meth) acrylate skeleton; the monomer having two or more copolymerizable functional groups is an alkylene diol di (meth) acrylate or alkylene glycol It is at least one selected from the group of di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and derivatives thereof; the fluorescent dye is a perylene fluorescent dye The amount of the fluorescent dye used is 2% by mass or less based on the monomer mixture.
また、本発明は、別の実施形態として、上記した製造方法により製造されたことを特徴とする蛍光性染料含有樹脂ビーズを提供する。 Moreover, this invention provides the fluorescent dye containing resin bead characterized by being manufactured by the above-mentioned manufacturing method as another embodiment.
更に、本発明は、別の実施形態として、上記蛍光性染料含有樹脂ビーズを含むことを特徴とする蛍光性を有する物品であって、該物品が、蛍光性を有する、成形体、フィルム、印刷物、塗膜、塗料、分散体及び分散液のいずれかであることを特徴とする物品を提供する。 Furthermore, as another embodiment, the present invention is a fluorescent article characterized by comprising the above-mentioned fluorescent dye-containing resin beads, wherein the article has fluorescent properties, a molded article, a film, and a printed matter. An article characterized by being any one of a coating film, a paint, a dispersion and a dispersion.
本発明によれば、蛍光性染料が良好な蛍光特性を維持しつつ、色移行に対する十分な耐性を持つ、蛍光性染料含有樹脂ビーズの製造方法、該方法によって得られた蛍光性染料含有樹脂ビーズ、及びこれを用いた製品が提供される。 INDUSTRIAL APPLICABILITY According to the present invention, a method for producing a fluorescent dye-containing resin bead having a fluorescent dye having sufficient resistance to color migration while maintaining good fluorescent properties, and a fluorescent dye-containing resin bead obtained by the method , And products using the same.
以下に、本発明を実施するための最良の形態を挙げて本発明について詳述する。なお、本発明の特許請求の範囲及び明細書における「（メタ）アクリル」という用語は、「アクリル」及び「メタクリル」の双方を意味し、「（メタ）アクリレート」という用語は、「アクリレート」及び「メタクリレート」の双方を意味する。 The present invention will be described in detail below with reference to the best mode for carrying out the present invention. In addition, the term “(meth) acryl” in the claims and specification of the present invention means both “acryl” and “methacryl”, and the term “(meth) acrylate” It means both “methacrylate”.
本発明者らは、蛍光性染料、特にペリレン系蛍光性染料の良好な蛍光特性を維持しつつ、色移行に対する十分な耐性を示す蛍光性染料含有樹脂ビーズの製造する手段について種々検討したところ、共重合可能な官能基を２以上有するモノマーを含むモノマーを用い、これらを懸濁重合することによって、蛍光性染料を使用した場合の解決課題であった前記した色移行に対する耐性を持つ効果を付与できることを見出し、上記課題がみごとに解決されることを確認し、本発明に至ったものである。 The inventors of the present invention have studied various means for producing fluorescent dye-containing resin beads that exhibit sufficient resistance to color migration while maintaining good fluorescent properties of fluorescent dyes, particularly perylene fluorescent dyes. By using monomers containing monomers having two or more copolymerizable functional groups and suspension polymerizing them, the effect of having the above-mentioned resistance to color migration, which was a problem to be solved when using fluorescent dyes, is given. The present inventors have found that the above problems can be solved brilliantly, and have reached the present invention.
すなわち、本発明は、蛍光性染料含有樹脂ビーズの製造方法において、共重合可能な官能基を２以上有するモノマーを、使用する全モノマーに対して３０質量％を超える量で含むモノマー混合液に、蛍光性染料をモノマー混合液に対して３質量％以下となる量で溶解し、これに重合開始剤を加えて重合性モノマー液を調製した後、該重合性モノマー液を水相に加えて撹拌して懸濁液を調製し、懸濁重合することにより樹脂ビーズを得ることを特徴とする。本発明で使用する共重合可能な官能基を２以上有するモノマーとしては、共重合可能な、後述するような、多官能性モノマーや架橋作用性モノマーが挙げられる。以下、本発明の各構成について、それぞれ説明する。 That is, the present invention provides a monomer mixed solution containing a monomer having two or more copolymerizable functional groups in an amount exceeding 30% by mass based on the total amount of monomers used in the method for producing a fluorescent dye-containing resin bead. A fluorescent dye is dissolved in an amount of 3% by mass or less with respect to the monomer mixture, and after adding a polymerization initiator to prepare a polymerizable monomer solution, the polymerizable monomer solution is added to the aqueous phase and stirred. Then, a suspension is prepared, and resin beads are obtained by suspension polymerization. Examples of the monomer having two or more copolymerizable functional groups used in the present invention include copolymerizable monomers such as polyfunctional monomers and crosslinking functional monomers as described later. Hereinafter, each configuration of the present invention will be described.
［モノマー］
すなわち、本発明の製造方法では、モノマー成分として、共重合可能な官能基を２以上有するモノマー成分を、全体のモノマーに対して特定の量以上で使用して、この重合性モノマー液中に蛍光性染料を加え、該モノマー液を使用して懸濁重合することで樹脂ビーズを製造する。本発明の製造方法は、共重合可能な官能基を２以上有するモノマー成分を、使用する全モノマーに対して３０質量％を超える量で使用することを特徴とする。本発明者らの検討によれば、共重合可能な官能基を２以上有するモノマー成分が、懸濁重合に使用する全モノマーに対して３０質量％以下と少ないと、樹脂中の架橋ネットワークが粗くなり、樹脂中での蛍光性染料の移動（色移行）を許容し易くなる。懸濁重合に使用する全モノマー中における共重合可能な官能基を２以上有するモノマーの配合割合は、好ましくは４０質量％以上であり、更に好ましくは５０質量％以上である。
[monomer]
That is, in the production method of the present invention, a monomer component having two or more copolymerizable functional groups is used as a monomer component in a specific amount or more with respect to the entire monomer, and this polymerizable monomer solution is fluorescent. Resin beads are produced by adding a reactive dye and subjecting the monomer solution to suspension polymerization. The production method of the present invention is characterized in that a monomer component having two or more copolymerizable functional groups is used in an amount exceeding 30% by mass with respect to all monomers used. According to the study by the present inventors, when the monomer component having two or more copolymerizable functional groups is as small as 30% by mass or less based on the total monomers used for suspension polymerization, the crosslinked network in the resin is coarse. It becomes easy to allow movement (color shift) of the fluorescent dye in the resin. The blending ratio of the monomer having two or more copolymerizable functional groups in all monomers used for suspension polymerization is preferably 40% by mass or more, and more preferably 50% by mass or more.
本発明者らの検討によれば、例えば、本発明に好適なペリレン系蛍光性染料は、油溶性の蛍光性染料であるが、このような染料を用いて本発明の製造方法を実施して蛍光性染料含有樹脂ビーズを得る場合に、本発明で目的とする良好な蛍光特性を維持しつつ、色移行に対する十分な耐性を高いレベルで実現させるためには、使用するモノマー類の構成のバランスが重要になることが分かった。すなわち、例えば、上記したような油溶性の蛍光性染料を用いた場合に、水親和性が低過ぎるモノマー類が多いと、蛍光性染料が樹脂ビーズの表面のシェル層を容易に越えて移動し易くなり、改良の効果が低くなる傾向がある。反対に、使用するモノマー類の構成のバランスが、水親和性が高過ぎるモノマー類が多いと、懸濁重合が難しくなったり、懸濁重合の際に乳化重合が併発して収率が低下するなどの不具合を生じる傾向が高まるため、本発明の製造方法で使用する共重合性モノマー等を選択する際には、使用するモノマー類の構成の水親和性バランスを検討することが重要になる。 According to the study by the present inventors, for example, the perylene fluorescent dye suitable for the present invention is an oil-soluble fluorescent dye, and the production method of the present invention is carried out using such a dye. When obtaining fluorescent dye-containing resin beads, in order to achieve a high level of sufficient resistance to color migration while maintaining the desired fluorescent properties of the present invention, the balance of the composition of the monomers used is balanced. Was found to be important. That is, for example, when an oil-soluble fluorescent dye as described above is used, if there are many monomers having low water affinity, the fluorescent dye easily moves beyond the shell layer on the surface of the resin beads. It becomes easy and the effect of improvement tends to be low. On the other hand, if the balance of the composition of the monomers used is too high in water affinity, suspension polymerization becomes difficult or emulsion polymerization occurs simultaneously with suspension polymerization, resulting in a decrease in yield. Therefore, when selecting a copolymerizable monomer or the like to be used in the production method of the present invention, it is important to study the water affinity balance of the monomers used.
本発明者らは、上記した知見の下、本発明で使用するモノマーについて鋭意検討した結果、本発明で用いる共重合可能な官能基を２以上有するモノマー（以下、共重合性モノマーとも呼ぶ）の好適なものとしては、例えば、（メタ）アクリレート骨格を有するモノマーが挙げられ、中でも、アクリレート骨格を有するモノマーを使用することがより好ましいことを見出した。そして、この（メタ）アクリレート骨格を有するモノマーにおける効果の違いは、アクリレート系のモノマーは、メタクリレート系のモノマーに比べて水親和性が高く、このことが原因して本発明のより顕著な効果が得られたものと考えられる。すなわち、このような水親和性が適度に高い傾向にあるアクリレート系のモノマーを使用し、水相中で懸濁重合すると、得られる樹脂ビーズの表面（シェル層）が水親和性となるため、形成された蛍光性染料含有樹脂ビーズは、蛍光性染料の移動を妨げる効果において、より高い効果をもたらすものとなったと考えられる。先にも述べたように、本発明に好適なペリレン系蛍光性染料などは、油溶性の蛍光性染料であることから、樹脂中での移動をより効果的に防止するためには、上記したように、水親和性が適度に高い樹脂をシェル層とすることが好ましい。 As a result of intensive studies on the monomers used in the present invention under the above knowledge, the present inventors have found that the monomers having two or more copolymerizable functional groups used in the present invention (hereinafter also referred to as copolymerizable monomers). As a suitable thing, the monomer which has a (meth) acrylate skeleton is mentioned, for example, It discovered that it was more preferable to use the monomer which has an acrylate skeleton among these. The difference in the effect of the monomer having the (meth) acrylate skeleton is that the acrylate monomer has a higher water affinity than the methacrylate monomer, and this causes a more remarkable effect of the present invention. It is thought that it was obtained. That is, when using such an acrylate monomer that has a moderately high water affinity and suspension polymerization in the aqueous phase, the surface of the resulting resin beads (shell layer) becomes water compatible. The formed fluorescent dye-containing resin beads are considered to have a higher effect in preventing the movement of the fluorescent dye. As described above, since the perylene fluorescent dye suitable for the present invention is an oil-soluble fluorescent dye, the above-mentioned is used in order to more effectively prevent migration in the resin. As described above, it is preferable to use a resin having a moderately high water affinity as the shell layer.
本発明で用いる共重合可能な官能基を２以上有するモノマーとして好ましいものとしては、下記のものが挙げられる。具体的には、（メタ）アクリレート骨格を有するモノマーである、アルキレンジオールジ（メタ）アクリレート、アルキレングリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート及びそれらの誘導体が挙げられる。前記したように、本発明において、より顕著な効果を得るためには、これらの中でも、アクリレート骨格を有するモノマーを用いることがより好ましい。 Preferred examples of the monomer having two or more copolymerizable functional groups used in the present invention include the following. Specifically, monomers having a (meth) acrylate skeleton, alkylene diol di (meth) acrylate, alkylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like And derivatives thereof. As described above, in the present invention, in order to obtain a more remarkable effect, it is more preferable to use a monomer having an acrylate skeleton among these.
本発明の製造方法で使用する共重合可能な官能基を２以上有するモノマーとしては、一般的な、共重合の能力がある二重結合を含む架橋作用性の官能基を持つ共重合性モノマーを用いることができる。このような本発明に好適な架橋に適したモノマーとしては、以下のものが挙げられる。例えば、２官能（メタ）アクリレートである、エチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、変性ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレートなどを使用することができる。また、３官能（メタ）アクリレートである、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエトキシトリ（メタ）アクリレート、グリセリンプロポキシトリ（メタ）アクリレートなどを使用することができる。 As a monomer having two or more copolymerizable functional groups used in the production method of the present invention, a general copolymerizable monomer having a crosslinkable functional group containing a double bond capable of copolymerization is used. Can be used. Examples of such monomers suitable for crosslinking suitable for the present invention include the following. For example, bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, butanediol di ( (Meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, modified bisphenol A di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate Etc. can be used. Use trifunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, glycerin propoxytri (meth) acrylate, etc. Can do.
また、４官能（メタ）アクリレートである、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールエトキシテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレートなどを使用することができる。更に、６官能（メタ）アクリレートである、ジペンタエリスリトールヘキサ（メタ）アクリレートなどを使用することもできる。本発明では、更に、上記に列挙した多官能（メタ）アクリレートの誘導体も使用することができる。本発明において、上記した多官能（メタ）アクリレート及びこれらの誘導体は、単独で又は２種類以上を組み合わせて使用してもよい。 Further, tetraerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like, which are tetrafunctional (meth) acrylates, can be used. Furthermore, dipentaerythritol hexa (meth) acrylate etc. which are hexafunctional (meth) acrylates can also be used. In the present invention, derivatives of the polyfunctional (meth) acrylates listed above can also be used. In the present invention, the above-described polyfunctional (meth) acrylates and derivatives thereof may be used alone or in combination of two or more.
［蛍光性染料］
本発明の製造方法で使用する蛍光性染料としては、公知のものがいずれも使用できる。特に耐候性及び耐熱性に優れるペリレン系蛍光性染料を用いることが好ましく、市販のペリレン系蛍光性染料がいずれも好適に使用できる。例えば、ＬｕｍｏｇｅｎＦ Ｖｉｏｌｅｔ５７０（ＢＡＳＦ）、ＬｕｍｏｇｅｎＦ Ｙｅｌｌｏｗ０８３（ＢＡＳＦ）、ＬｕｍｏｇｅｎＦ Ｏｒａｎｇｅ２４０（ＢＡＳＦ）、ＬｕｍｏｇｅｎＦ Ｒｅｄ３０５（ＢＡＳＦ）などが挙げられる。
[Fluorescent dye]
Any known fluorescent dye can be used in the production method of the present invention. In particular, it is preferable to use a perylene fluorescent dye excellent in weather resistance and heat resistance, and any commercially available perylene fluorescent dye can be suitably used. Examples include LumogenF Violet 570 (BASF), LumogenF Yellow083 (BASF), LumogenF Orange240 (BASF), and LumogenF Red305 (BASF).
本発明の製造方法で形成した蛍光性染料含有樹脂ビーズは、該ビーズ中に含まれる蛍光性染料の濃度が３質量％以下となるようにすることを要す。すなわち、本発明者らの検討によれば、樹脂ビーズ中の染料濃度が３質量％よりも高いと濃度消光が生じて添加量に見合う蛍光強度を発しない。このため、本発明の製造方法では、上記したような共重合可能な官能基を２以上有するモノマーを、全モノマーに対して３０質量％を超える量で含むモノマー混合液に、上記に挙げたような蛍光性染料を３質量％以下となる量で溶解し、重合性モノマー液を調製した後、これを懸濁重合して製造することを要する。より好ましい蛍光性染料濃度は２質量％以下であり、更に好ましくは１質量％以下である。 The fluorescent dye-containing resin beads formed by the production method of the present invention require that the concentration of the fluorescent dye contained in the beads be 3% by mass or less. That is, according to the study by the present inventors, if the dye concentration in the resin beads is higher than 3% by mass, concentration quenching occurs and the fluorescence intensity corresponding to the added amount is not emitted. For this reason, in the production method of the present invention, as described above, the monomer mixture containing the monomer having two or more copolymerizable functional groups as described above in an amount exceeding 30% by mass with respect to the total monomers. It is necessary to prepare a polymerizable monomer solution by dissolving a fluorescent dye in an amount of 3% by mass or less and then subjecting it to suspension polymerization. A more preferable fluorescent dye concentration is 2% by mass or less, and further preferably 1% by mass or less.
本発明の製造方法で得られる蛍光性染料含有樹脂ビーズの大きさは特に限定されないが、例えば、その体積平均粒子径が２０μｍ以下の微粒子を容易に得ることができる。そして、このような大きさのものは、多様な用途に好適に使用でき、使用した場合に、良好な蛍光性を有する多様な製品とできる。すなわち、本発明者らの検討によれば、製造した蛍光性染料含有樹脂ビーズの体積平均粒子径が２０μｍよりも大きいと、このような樹脂ビーズを用いて、成形体、フィルム、印刷物、塗膜、塗料、分散体及び分散液等の物品とした場合に、その使用形態にもよるが、見かけの蛍光強度が低下して見えてしまう傾向が生じる場合もある。本発明の製造方法によれば、例えば、より微量な、体積平均粒子径が１５μｍ以下のものや、更には１０μｍ以下のものであって、しかも粒度の揃ったものを得ることができるので、用途に合致したより好適な粒子径のものを適宜に設計すればよい。 The size of the fluorescent dye-containing resin beads obtained by the production method of the present invention is not particularly limited. For example, fine particles having a volume average particle diameter of 20 μm or less can be easily obtained. A product having such a size can be suitably used for various applications, and when used, can be various products having good fluorescence. That is, according to the study by the present inventors, when the volume average particle diameter of the produced fluorescent dye-containing resin beads is larger than 20 μm, using such resin beads, a molded body, a film, a printed matter, and a coating film are used. In the case of articles such as paints, dispersions, and dispersions, the apparent fluorescence intensity may tend to decrease and appear depending on the form of use. According to the production method of the present invention, for example, it is possible to obtain a finer one having a volume average particle diameter of 15 μm or less, or even 10 μm or less, and having a uniform particle size. A particle having a more suitable particle size that matches the above may be designed as appropriate.
［懸濁重合の方法］
本発明の蛍光性染料含有樹脂ビーズの製造方法で行う懸濁重合は、従来公知の方法で行う。具体的には、上述した組成のモノマー混合液に、蛍光性染料を３質量％以下となる量で溶解し、これに重合開始剤を加えて重合性モノマー液を調製した後、該重合性モノマー液を水相に加えて撹拌して懸濁液を調製し、懸濁重合する。重合性モノマー液を調製する時に、モノマーの粘度調整や溶解性向上のために、例えばプロピレングリコールモノメチルアセテートのような公知の溶剤を添加してもよい。重合性モノマー液を調製する際には、十分に撹拌して蛍光性染料をモノマー類に溶解した後、例えば、公知の油溶性重合開始剤を溶解したモノマーまたは溶剤を添加して重合性モノマー液を調製すればよい。このようにすることで、モノマー混合液に、蛍光性染料と重合開始剤とを均一に溶解することができる。
[Method of suspension polymerization]
The suspension polymerization performed by the method for producing the fluorescent dye-containing resin beads of the present invention is performed by a conventionally known method. Specifically, after the fluorescent dye is dissolved in an amount of 3% by mass or less in the monomer mixed solution having the above-described composition, a polymerization initiator solution is added thereto to prepare a polymerizable monomer solution, and then the polymerizable monomer is added. The liquid is added to the aqueous phase and stirred to prepare a suspension, which is subjected to suspension polymerization. When preparing the polymerizable monomer solution, a known solvent such as propylene glycol monomethyl acetate may be added to adjust the viscosity of the monomer and improve solubility. When preparing the polymerizable monomer liquid, after sufficiently stirring and dissolving the fluorescent dye in the monomers, for example, a monomer or solvent in which a known oil-soluble polymerization initiator is dissolved is added to the polymerizable monomer liquid. May be prepared. By doing so, the fluorescent dye and the polymerization initiator can be uniformly dissolved in the monomer mixture.
本発明の製造方法では、上記のようにして得た重合性モノマー液を水相に加えて撹拌して懸濁液を調製し、懸濁重合する。この際に使用する水相としては、例えば、脱イオン水に分散安定剤（保護コロイド）を溶解した水媒体を調整して使用することが好ましい。本発明の製造方法では、このような水相に、上記した重合性モノマー液を加えて撹拌し、懸濁液を調製する。上記撹拌には、必要であれば、ホモジナイザーなどの乳化装置を用いて、重合性モノマー液の懸濁液滴径を調整する。ホモジナイザーなどの乳化装置は、回転数を変えてせん断力を調整することによって、容易に重合性モノマー液を所望の懸濁液滴径に調整できる。 In the production method of the present invention, the polymerizable monomer liquid obtained as described above is added to an aqueous phase and stirred to prepare a suspension, which is subjected to suspension polymerization. As the aqueous phase used at this time, for example, it is preferable to use an aqueous medium prepared by dissolving a dispersion stabilizer (protective colloid) in deionized water. In the production method of the present invention, the above polymerizable monomer liquid is added to such an aqueous phase and stirred to prepare a suspension. For the stirring, if necessary, the suspension droplet diameter of the polymerizable monomer liquid is adjusted using an emulsifying device such as a homogenizer. An emulsifying apparatus such as a homogenizer can easily adjust the polymerizable monomer liquid to a desired suspension droplet diameter by changing the number of rotations and adjusting the shearing force.
上記の分散安定剤（保護コロイド）を用いて調製する水相は、ホモジナイザーなどの乳化装置により作成された懸濁液滴が、液滴調整中や重合装置への移送中や重合過程中に液滴の破壊や合一など不具合が発生しないように、使用する分散安定剤の種類、濃度を適宜に設定することが好ましい。この際に使用することが可能な分散安定剤としては、メチルセルロース、ポリビニルアルコール（ＰＶＡ）、アクリル酸ソーダなどの水溶性高分子、ハイドロキシアパタイト、第３リン酸カルシウム、炭酸カルシウムなどの無機塩類が挙げられる。 In the aqueous phase prepared using the above dispersion stabilizer (protective colloid), suspension droplets created by an emulsifying device such as a homogenizer can be used during liquid adjustment or transfer to the polymerization device or during the polymerization process. It is preferable to appropriately set the type and concentration of the dispersion stabilizer used so as not to cause problems such as droplet breakage and coalescence. Examples of the dispersion stabilizer that can be used in this case include water-soluble polymers such as methyl cellulose, polyvinyl alcohol (PVA), and sodium acrylate, and inorganic salts such as hydroxyapatite, tricalcium phosphate, and calcium carbonate.
上記のようにして得られた懸濁液は、例えば、温度６０〜８０℃にて３〜１０時間加熱し、懸濁重合を行うことにより、蛍光性染料を含有してなる樹脂ビーズが得られる。更に、必要に応じて、洗浄工程にて分散安定剤を除去した後、脱イオン水に邂逅して分散し、再度洗浄工程にて溶解物を除去し、必要があれば洗浄を繰り返した後、乾燥する。乾燥後に凝集した状態で得られた粒子は、解砕することにより、粉状の樹脂ビーズとすることができる。 The suspension obtained as described above is heated at a temperature of 60 to 80 ° C. for 3 to 10 hours, for example, and suspension polymerization is performed to obtain resin beads containing a fluorescent dye. . Furthermore, if necessary, after removing the dispersion stabilizer in the washing step, dispersed in deionized water and dispersed again in the washing step, if necessary, repeated washing, dry. Particles obtained in an aggregated state after drying can be made into powdery resin beads by crushing.
本発明の蛍光性染料含有樹脂ビーズは、上記したようにして行う本発明の製造方法で得られるが、共重合可能な官能基を２以上有するモノマーを３０質量％を超える量で含み、且つ、蛍光性染料を３質量％以下となる量で含むモノマー混合液を用い、これを懸濁重合することで、蛍光性染料を、得られる樹脂ビーズ内に良好に固定化できる。この結果、蛍光性染料が良好な蛍光特性を維持しつつ、色移行に対する十分な耐性を有するものとなる。さらに、本発明の製造方法により得られた蛍光性染料含有樹脂ビーズを使用することで、これまで、色移行に対する十分な耐性が実現されていなかったために、蛍光性染料の使用が難しかった、成形体、フィルム、印刷物、塗膜、塗料、分散体及び分散液にも、蛍光性を付与することが可能となる。 The fluorescent dye-containing resin beads of the present invention are obtained by the production method of the present invention performed as described above, and contain a monomer having two or more copolymerizable functional groups in an amount exceeding 30% by mass, and By using a monomer mixture containing the fluorescent dye in an amount of 3% by mass or less and subjecting it to suspension polymerization, the fluorescent dye can be favorably immobilized in the resin beads to be obtained. As a result, the fluorescent dye has sufficient resistance to color migration while maintaining good fluorescence characteristics. Furthermore, by using the fluorescent dye-containing resin beads obtained by the production method of the present invention, until now sufficient resistance to color migration has not been realized, the use of fluorescent dyes has been difficult, molding It becomes possible to impart fluorescence to the body, film, printed matter, coating film, paint, dispersion and dispersion.
以下、実施例及び比較例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例により限定されるものではない。なお、文中「部」または「％」とあるのは質量基準である。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited by these Examples. In the text, “part” or “%” is based on mass.
下記に説明する実施例及び比較例では、特に記載がない限り、以下の部分ケン化ポリビニルアルコール及び重合開始剤を用いた。部分ケン化ポリビニルアルコールとしては、クラレ（株）製のポバール２０５（商品名、以下ＰＶＡと略す）を使用し、重合開始剤としては、油溶性の、大塚化学（株）製の２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ（商品名）、以下ＡＩＢＮと略す）を使用した。 In the examples and comparative examples described below, the following partially saponified polyvinyl alcohol and polymerization initiator were used unless otherwise specified. As the partially saponified polyvinyl alcohol, POVAL 205 (trade name, hereinafter abbreviated as PVA) manufactured by Kuraray Co., Ltd. is used, and as the polymerization initiator, oil-soluble 2,2 ′ manufactured by Otsuka Chemical Co., Ltd. -Azobisisobutyronitrile (AIBN (trade name), hereinafter abbreviated as AIBN) was used.
＜実施例１＞
容器に、エチレングリコールジメタクリレート１００部（新中村化学工業（株）製、ＮＫエステル１Ｇ）及びラウリルメタクリレート４０部（花王（株）製、エキセパールＬ−ＭＡ）のモノマー混合液に、ルモゲン蛍光性染料２部（ＢＡＳＦ製、ＬｕｍｏｇｅｎＦ Ｒｅｄ３０５）を加えて溶解し、蛍光性染料溶解液を得た。次に、予め、ＡＩＢＮ２部をエチレングリコールジメタクリレート６０部に溶解した溶液を、上記で得た蛍光性染料溶解液に加えて、均一に撹拌混合し、重合性モノマー液を調製した。別の容器に、イオン交換水６００部、ＰＶＡ６０部を混合溶解した水相を調製した後、その中に上記重合性モノマー液を加えて混合し、ディゾルバーにて２５００ｒｐｍで５分間撹拌して均一な懸濁液を得た。
<Example 1>
In a container, a lumogenic fluorescent dye is added to a monomer mixture of 100 parts of ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester 1G) and 40 parts of lauryl methacrylate (manufactured by Kao Corporation, Exepar L-MA). 2 parts (manufactured by BASF, Lumogen F Red305) was added and dissolved to obtain a fluorescent dye solution. Next, a solution prepared by dissolving 2 parts of AIBN in 60 parts of ethylene glycol dimethacrylate in advance was added to the fluorescent dye solution obtained above, and stirred and mixed uniformly to prepare a polymerizable monomer solution. In a separate container, an aqueous phase in which 600 parts of ion exchange water and 60 parts of PVA are mixed and dissolved is prepared, and the polymerizable monomer solution is added and mixed therein. The mixture is stirred at 2500 rpm for 5 minutes in a dissolver to make it uniform. A suspension was obtained.
次に、撹拌機、窒素ガス導入管を備え付けた重合装置の反応缶に、上記で得た懸濁液を仕込み、７０℃で６時間続けて重合反応を行った。冷却後、この懸濁液から生成した微粒子を濾過洗浄した。得られた樹脂ビーズをイオン交換水に再邂逅した後、懸濁液から微粒子を、ろ過、洗浄、乾燥、解砕処理を行って、本発明の実施例の蛍光性染料含有樹脂ビーズを得た。 Next, the suspension obtained above was charged in a reactor of a polymerization apparatus equipped with a stirrer and a nitrogen gas introduction tube, and a polymerization reaction was continued at 70 ° C. for 6 hours. After cooling, the fine particles produced from this suspension were filtered and washed. After the obtained resin beads were reconstituted in ion-exchanged water, the fine particles from the suspension were filtered, washed, dried, and crushed to obtain the fluorescent dye-containing resin beads of the examples of the present invention. .
＜実施例２＞
容器に、変性ビスフェノールジアクリレート１００部（ダイセルサイテック製、ＥＢ１５０）及びヘキサンジオールジアクリレート１００部（ダイセルサイテック（株）製、ＨＤＤＡ）に、ルモゲン蛍光性染料２部（ＢＡＳＦ製、ＬｕｍｏｇｅｎＦ Ｒｅｄ３０５）を溶解し、蛍光性染料溶解液を得た。次に、予め、ＡＩＢＮ２部を溶剤であるプロピレングリコールモノメチルアセテート２０部に溶解した溶液を、上記で得た蛍光性染料溶解液に加えて、均一に撹拌混合し、重合性モノマー液を調製した。その後は、実施例１と同様に操作し、本発明の実施例の蛍光性染料含有樹脂ビーズを得た。
<Example 2>
In a container, 100 parts of modified bisphenol diacrylate (manufactured by Daicel Cytec, EB150) and 100 parts of hexanediol diacrylate (manufactured by Daicel Cytec Co., Ltd., HDDA) are dissolved 2 parts of lumogen fluorescent dye (manufactured by BASF, Lumogen F Red305). As a result, a fluorescent dye solution was obtained. Next, a solution obtained by dissolving 2 parts of AIBN in 20 parts of propylene glycol monomethyl acetate as a solvent in advance was added to the fluorescent dye solution obtained above, and stirred and mixed uniformly to prepare a polymerizable monomer solution. Thereafter, the same operation as in Example 1 was performed to obtain a fluorescent dye-containing resin bead of Example of the present invention.
＜実施例３＞
容器に、ジペンタエリスリトールヘキサアクリレート１００部（ダイセルサイッテック製、ＤＰＨＡ）及びトリプロピレングリコールジアクリレート１００部（ダイセルサイッテック（株）製、ＴＰＧＤＡ）に、ルモゲン蛍光性染料１部（ＢＡＳＦ製、ＬｕｍｏｇｅｎＦ Ｒｅｄ３０５）を溶解し、蛍光性染料溶解液を得た。次に、予め、ＡＩＢＮ２部をプロピレングリコールモノメチルアセテート２０部に溶解した溶液を、上記蛍光性染料溶解液に加えて、均一に撹拌混合し、重合性モノマー液を調製した。その後は、実施例１と同様に操作し、本発明の実施例の蛍光性染料含有樹脂ビーズを得た。
<Example 3>
In a container, 100 parts of dipentaerythritol hexaacrylate (manufactured by Daicel Cytec, DPHA) and 100 parts of tripropylene glycol diacrylate (manufactured by Daicel Cytec Co., Ltd., TPGDA), 1 part of lumogenic fluorescent dye (manufactured by BASF, Lumogen F) Red 305) was dissolved to obtain a fluorescent dye solution. Next, a solution prepared by dissolving 2 parts of AIBN in 20 parts of propylene glycol monomethyl acetate in advance was added to the fluorescent dye solution, and the mixture was uniformly stirred and mixed to prepare a polymerizable monomer solution. Thereafter, the same operation as in Example 1 was performed to obtain a fluorescent dye-containing resin bead of Example of the present invention.
＜実施例４＞
容器に、変性ビスフェノールジアクリレート５０部（ダイセルサイテック製、ＥＢ１５０）及びトリプロピレングリコールジアクリレート５０部（ダイセルサイッテック（株）製、ＴＰＧＤＡ）及びラウリルアクリレート１００部（大阪有機化学工業（株）製、ＬＡ）に、ルモゲン蛍光性染料２部（ＢＡＳＦ製、ＬｕｍｏｇｅｎＦ Ｖｉｏｌｅｔ５７０）を溶解し、蛍光性染料溶解液を得た。次に、予め、ＡＩＢＮ２部をプロピレングリコールモノメチルアセテート２０部に溶解した溶液を、上記で得た蛍光性染料溶解液に加えて、均一に撹拌混合し、重合性モノマー液を調製した。その後は、実施例１と同様に操作し、本発明の実施例の蛍光性染料含有樹脂ビーズを得た。
<Example 4>
In the container, 50 parts of modified bisphenol diacrylate (manufactured by Daicel Cytec, EB150) and 50 parts of tripropylene glycol diacrylate (manufactured by Daicel Cytec Co., Ltd., TPGDA) and 100 parts of lauryl acrylate (manufactured by Osaka Organic Chemical Industries, Ltd., In LA), 2 parts of lumogen fluorescent dye (BASF, LumogenF Violet 570) was dissolved to obtain a fluorescent dye solution. Next, a solution prepared by dissolving 2 parts of AIBN in 20 parts of propylene glycol monomethyl acetate in advance was added to the fluorescent dye solution obtained above, and stirred and mixed uniformly to prepare a polymerizable monomer solution. Thereafter, the same operation as in Example 1 was performed to obtain a fluorescent dye-containing resin bead of Example of the present invention.
＜実施例５＞
容器に、変性ビスフェノールジアクリレート１００部（ダイセルサイテック製、ＥＢ１５０）及びヘキサンジオールジアクリレート１００部（ダイセルサイテック（株）製、ＨＤＤＡ）に、クマリン蛍光性染料２部（エアブラウン（株）製、ポトマックイエロー）を溶解し、蛍光性染料溶解液を得た。次に、予め、ＡＩＢＮ２部をプロピレングリコールモノメチルアセテート２０部に溶解した溶液を、上記で得た蛍光性染料溶解液に加えて、均一に撹拌混合し、重合性モノマー液を調製した。その後は、実施例１と同様に操作し、本発明の実施例の蛍光性染料含有樹脂ビーズを得た。
<Example 5>
In a container, 100 parts of modified bisphenol diacrylate (manufactured by Daicel Cytec, EB150) and 100 parts of hexanediol diacrylate (manufactured by Daicel Cytec Co., Ltd., HDDA), 2 parts of coumarin fluorescent dye (manufactured by Air Brown Co., Ltd., Potomac) Yellow) was dissolved to obtain a fluorescent dye solution. Next, a solution prepared by dissolving 2 parts of AIBN in 20 parts of propylene glycol monomethyl acetate in advance was added to the fluorescent dye solution obtained above, and stirred and mixed uniformly to prepare a polymerizable monomer solution. Thereafter, the same operation as in Example 1 was performed to obtain a fluorescent dye-containing resin bead of Example of the present invention.
＜比較例１＞
容器に、エチレングリコールジメタクリレート２０部（新中村化学工業（株）製、ＮＫエステル１Ｇ）及びラウリルメタクリレート１００部（花王（株）製、エキセパールＬＭＡ）に、ルモゲン蛍光性染料２部（ＢＡＳＦ製、ＬｕｍｏｇｅｎＦ Ｒｅｄ３０５）を溶解し、蛍光性染料溶解液を得た。次に、予め、ＡＩＢＮ２部をラウリルメタクリレート８０部に溶解した溶液を、上記蛍光性染料溶解液に加えて均一に撹拌混合し、重合性モノマー液を調製した。その後は、実施例１と同様に操作し、比較例の蛍光性染料含有樹脂ビーズを得た。
<Comparative Example 1>
In a container, 20 parts of ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester 1G) and 100 parts of lauryl methacrylate (manufactured by Kao Corporation, Exepal LMA), 2 parts of lumogen fluorescent dye (manufactured by BASF, LumogenF Red305) was dissolved to obtain a fluorescent dye solution. Next, a solution prepared by dissolving 2 parts of AIBN in 80 parts of lauryl methacrylate in advance was added to the fluorescent dye solution and uniformly mixed by stirring to prepare a polymerizable monomer solution. Thereafter, the same operation as in Example 1 was performed to obtain a fluorescent dye-containing resin bead of Comparative Example.
＜比較例２＞
容器に、変性ビスフェノールジアクリレート２０部（ダイセルサイテック製、ＥＢ１５０）及びトリプロピレングリコールジアクリレート２０部（ダイセルサイッテック（株）製、ＴＰＧＤＡ）及びラウリルアクリレート１６０部（大阪有機化学工業（株）製、ＬＡ）に、ルモゲン蛍光性染料１０部（ＢＡＳＦ製、ＬｕｍｏｇｅｎＦ Ｒｅｄ３０５）を溶解し、蛍光性染料溶解液を得た。次に、予め、ＡＩＢＮ２部をプロピレングリコールモノメチルアセテート２０部に溶解した溶液を、上記蛍光性染料溶解液に加えて均一に撹拌混合し、重合性モノマー液を調製した。その後は、実施例２と同様に操作し、比較例の蛍光性染料含有樹脂ビーズを得た。
<Comparative example 2>
In a container, 20 parts of modified bisphenol diacrylate (manufactured by Daicel Cytec, EB150) and 20 parts of tripropylene glycol diacrylate (manufactured by Daicel Cytec Co., Ltd., TPGDA) and 160 parts of lauryl acrylate (manufactured by Osaka Organic Chemical Industries, Ltd., In LA), 10 parts of lumogen fluorescent dye (BASF, Lumogen F Red305) was dissolved to obtain a fluorescent dye solution. Next, a solution prepared by dissolving 2 parts of AIBN in 20 parts of propylene glycol monomethyl acetate in advance was added to the fluorescent dye solution and stirred and mixed to prepare a polymerizable monomer solution. Thereafter, the same operation as in Example 2 was performed to obtain a fluorescent dye-containing resin bead of Comparative Example.
＜比較例３：＞
容器に、エチレングリコールジメタクリレート６０部（新中村化学工業（株）製、ＮＫエステル１Ｇ）及びラウリルメタクリレート８０部（花王（株）製、エキセパールＬＭＡ）のモノマー混合液に、ルモゲン蛍光性染料２部（ＢＡＳＦ製、ＬｕｍｏｇｅｎＦ Ｒｅｄ３０５）を加えて溶解し、蛍光性染料溶解液を得た。次に、予め、ＡＩＢＮ２部をラウリルメタクリレート６０部に溶解した溶液を、上記で得た蛍光性染料溶解液に加えて、均一に撹拌混合し、重合性モノマー液を調製した。その後は、実施例１と同様に操作し、比較例の蛍光性染料含有樹脂ビーズを得た。
<Comparative Example 3:>
In a container, add 2 parts of lumogenic fluorescent dye to a monomer mixture of 60 parts of ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester 1G) and 80 parts of lauryl methacrylate (manufactured by Kao Corporation, Exepar LMA). (BASF, LumogenF Red305) was added and dissolved to obtain a fluorescent dye solution. Next, a solution prepared by dissolving 2 parts of AIBN in 60 parts of lauryl methacrylate in advance was added to the fluorescent dye solution obtained above, and stirred and mixed uniformly to prepare a polymerizable monomer solution. Thereafter, the same operation as in Example 1 was performed to obtain a fluorescent dye-containing resin bead of Comparative Example.
［評価］
（１．体積平均粒子径）
実施例及び比較例で得られた各樹脂ビーズの体積平均粒子径を、コールターカウンター（ベックマン・コールター社製）を用いて測定した。その結果を表１にまとめた。
[Evaluation]
(1. Volume average particle diameter)
The volume average particle diameter of each resin bead obtained in Examples and Comparative Examples was measured using a Coulter counter (manufactured by Beckman Coulter). The results are summarized in Table 1.
（２．マイグレーション耐性）
実施例及び比較例で得られた各樹脂ビーズのマイグレーション耐性を、以下のようにして評価した。まず、実施例及び比較例の各樹脂ビーズを用い、蛍光性染料濃度が２００ｐｐｍとなるよう調整した、評価用のＰＶＣシートを、それぞれ作製した。そして、各ＰＶＣシートを、蛍光性染料の入っていない白ＰＶＣシートで挟み、５００ｇ／ｃｍ2の荷重を掛け１０５℃で２時間加熱放置した。この試験後、白ＰＶＣシートへの蛍光性染料の色移りの有無を目視で確認し、◎○×で評価した。その結果を表１にまとめて示した。
(2. Migration resistance)
The migration resistance of each resin bead obtained in the examples and comparative examples was evaluated as follows. First, PVC sheets for evaluation were prepared using the resin beads of Examples and Comparative Examples, and adjusted so that the concentration of the fluorescent dye was 200 ppm. Each PVC sheet was sandwiched between white PVC sheets not containing a fluorescent dye, and was left to heat at 105 ° C. for 2 hours under a load of 500 g / cm 2 . After this test, the presence or absence of color transfer of the fluorescent dye to the white PVC sheet was visually confirmed, and evaluated by ◎. The results are summarized in Table 1.
（３．蛍光強度、ブリード耐性）
実施例及び比較例得られた各樹脂ビーズの蛍光強度及びブリード耐性を、以下のようにして評価した。まず、実施例及び比較例の各樹脂ビーズを用い、蛍光性染料濃度が８００ｐｐｍとなるように調整した、評価用の各アクリル塗料を作製した。そして、各アクリル塗料をアプリケーターで塗布し、常乾後、蛍光強度を目視で確認した。その後、常乾後の塗膜に、白アクリル塗料を上掛して再び常乾した後、白アクリル塗料への色移り（ブリード）が無いか目視で確認し、◎○×で評価した。た。その結果を表１にまとめて示した。
(3. Fluorescence intensity, bleed resistance)
Examples and Comparative Examples The fluorescence intensity and bleed resistance of each resin bead obtained were evaluated as follows. First, each acrylic paint for evaluation, which was adjusted so that the fluorescent dye concentration became 800 ppm, was prepared using each resin bead of the example and the comparative example. And each acrylic paint was apply | coated with the applicator, and after normal drying, the fluorescence intensity was confirmed visually. Thereafter, the white acrylic coating was applied to the coating after normal drying, and the coating was dried again, and then visually checked for color transfer (bleed) to the white acrylic coating, and evaluated with ◎. It was. The results are summarized in Table 1.
表１に示した通り、実施例の樹脂ビーズを用いた成形体及び塗料は、比較例の樹脂ビーズを使用した成形体及び塗料よりも、マイグレーション耐性やブリード耐性が高く、蛍光性染料の移行や蛍光特性の低下が効果的に抑制されていることが確認できた。 As shown in Table 1, the molded products and paints using the resin beads of Examples have higher migration resistance and bleed resistance than the molded products and paints using the resin beads of Comparative Examples, It was confirmed that the deterioration of the fluorescence characteristics was effectively suppressed.
本発明の蛍光性染料含有樹脂ビーズは、マイグレーション耐性やブリード耐性が高く、蛍光性染料の色移行や蛍光特性の低下を効果的に防止することが可能であり、これらの特性や機能を求める分野、例えば、これを用いた成形体、フィルム、印刷物、塗膜、塗料、分散体及び分散液への使用に最適である。 The fluorescent dye-containing resin beads of the present invention have high migration resistance and bleed resistance, and can effectively prevent color migration of fluorescent dyes and deterioration of fluorescence characteristics. For example, it is most suitable for use in a molded article, a film, a printed matter, a coating film, a paint, a dispersion and a dispersion using the same.
Claims (6)
前記蛍光性染料が、油溶性のペリレン系蛍光性染料又はクマリン系蛍光染料であり、
共重合可能な官能基を２以上有するモノマーを、使用する全モノマーに対して３０質量％を超える量で含むモノマー混合液に、前記蛍光性染料をモノマー混合液に対して３質量％以下となる量で溶解し、これに重合開始剤を加えて重合性モノマー液を調製した後、該重合性モノマー液を水相に加えて撹拌して懸濁液を調製し、懸濁重合することにより、樹脂ビーズを得ることを特徴とする蛍光性染料含有樹脂ビーズの製造方法。 A method for producing a fluorescent dye-containing resin bead,
The fluorescent dye is an oil-soluble perylene fluorescent dye or a coumarin fluorescent dye,
A monomer having a functional group copolymerizable 2 or more, the monomer mixture containing an amount of more than 30% by weight, based on the total monomer used, the 3% by mass or less with respect to the monomer mixture wherein the fluorescent dye After preparing a polymerizable monomer liquid by adding a polymerization initiator to this, the polymerization monomer liquid is added to the aqueous phase and stirred to prepare a suspension, and suspension polymerization is performed. A method for producing a resin bead containing a fluorescent dye, comprising obtaining a resin bead.
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