JP5696918B2 - Aggregated resin particles, method for producing the particles, and coating composition and coating film containing the particles - Google Patents
Aggregated resin particles, method for producing the particles, and coating composition and coating film containing the particles Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims description 187
- 229920005989 resin Polymers 0.000 title claims description 145
- 239000011347 resin Substances 0.000 title claims description 145
- 238000000576 coating method Methods 0.000 title claims description 51
- 239000011248 coating agent Substances 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000008199 coating composition Substances 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000002776 aggregation Effects 0.000 claims description 14
- 238000004220 aggregation Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 230000001788 irregular Effects 0.000 claims description 10
- 238000001878 scanning electron micrograph Methods 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000004931 aggregating effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 description 23
- 239000003973 paint Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000006224 matting agent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- MJGLWGBXQWRFCX-UHFFFAOYSA-N 2-[(1-imino-2-methyl-1-pyrrolidin-1-ylpropan-2-yl)diazenyl]-2-methyl-1-pyrrolidin-1-ylpropan-1-imine;dihydrochloride Chemical compound Cl.Cl.C1CCCN1C(=N)C(C)(C)N=NC(C)(C)C(=N)N1CCCC1 MJGLWGBXQWRFCX-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- -1 alkyl vinyl ethers Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 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
- ODKBBGGUUMCXFY-UHFFFAOYSA-N 2-(2-cyanopentan-2-yldiazenyl)-2-methylpentanenitrile Chemical compound CCCC(C)(C#N)N=NC(C)(C#N)CCC ODKBBGGUUMCXFY-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 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
本発明は凝集樹脂粒子及び該粒子の製造方法に関する。さらに、本発明は該粒子を含有する塗料組成物及び塗膜に関する。 The present invention relates to aggregated resin particles and a method for producing the particles. Furthermore, this invention relates to the coating composition and coating film containing this particle | grain.
従来、塗膜などの艶消し剤としては球状樹脂粒子が多く利用されてきた。樹脂である球状樹脂粒子は透明性が良く下地の色調を損なうことなく艶消し効果が得られるという利点があるが、得られる艶消し効果はそれほど高いものではなく、また、該粒子を添加した塗膜は塗膜を見る角度による艶消し効果に斑が大きいという問題点も有している。 Conventionally, spherical resin particles have been widely used as matting agents for coating films and the like. Spherical resin particles, which are resins, have the advantage that they have a good transparency and a matte effect without impairing the color tone of the base, but the matte effect obtained is not so high. The film also has a problem that the matte effect due to the viewing angle of the coating film is large.
かかる問題点に対して、特許文献１や特許文献２にはシリカ微粉末と樹脂粒子を併用することが提案されているが、シリカは透明性が悪いため、塗膜の白化現象を起こし下地の色調を阻害してしまう問題点がある。 In order to deal with such problems, Patent Document 1 and Patent Document 2 propose to use silica fine powder and resin particles in combination. There is a problem that disturbs the color tone.
また、特許文献３には、乳化重合により得られた架橋重合体エマルジョンを噴霧乾燥することによって得られる球状の凝集樹脂粒子からなる艶消し剤が開示されている。かかる艶消し剤は凝集樹脂粒子であるが全体として球状であるため、艶消し効果がそれほど高くならない。また、該凝集樹脂粒子は界面活性剤を含んだ状態で凝集しているため、界面活性剤が塗料や塗膜の特性を低下させたり、水系塗料に添加混合した場合には凝集状態を維持しにくくなって艶消し効果が低下したりする恐れがある。 Patent Document 3 discloses a matting agent comprising spherical aggregated resin particles obtained by spray drying a cross-linked polymer emulsion obtained by emulsion polymerization. Such a matting agent is agglomerated resin particles, but since it is spherical as a whole, the matting effect is not so high. In addition, since the aggregated resin particles are aggregated in a state containing a surfactant, the aggregated state is maintained when the surfactant deteriorates the properties of the paint or the coating film or is added to and mixed with the water-based paint. It may become difficult to reduce the matting effect.
以上のように、従来の艶消し剤は、見る角度によらず一定以上の艶消し効果を発現させることと透明性を両立することが難しい、あるいは、塗料や塗膜の特性を低下させる恐れのある添加物を含有するという問題点を有している。本発明は、かかる問題点を解消する凝集樹脂粒子および該粒子の製造方法を提供することを目的とする。さらに、本発明はかかる粒子を含有する塗料組成物および塗膜を提供することを目的とする。 As described above, it is difficult for conventional matting agents to exhibit both a certain level of matting effect and transparency regardless of the viewing angle, or to reduce the properties of paints and coatings. It has the problem of containing certain additives. An object of this invention is to provide the aggregated resin particle which eliminates this problem, and the manufacturing method of this particle | grain. Furthermore, this invention aims at providing the coating composition and coating film containing such particle | grains.
本発明者らは上記目的について検討を重ねた結果、不定形状でかつ特定範囲の嵩密度を有する凝集樹脂粒子が高い透明性と広範囲の角度にわたる優れた艶消し効果を発現することを見出し、本発明に到達した。すなわち、本発明の目的は、以下の手段により達成される。 As a result of repeated investigations on the above object, the present inventors have found that the agglomerated resin particles having an irregular shape and a specific range of bulk density exhibit high transparency and an excellent matting effect over a wide range of angles. The invention has been reached. That is, the object of the present invention is achieved by the following means.
［１］ 微小樹脂粒子が凝集した凝集樹脂粒子において、前記微小樹脂粒子が凝集前の形状を維持しており、前記微小樹脂粒子のＳＥＭ画像によって測定した平均粒子径が１００〜６００ｎｍであり、前記凝集樹脂粒子の形状が不定形であって、嵩密度が０．２０〜０．５０ｇ／ｃｍ３であり、かつ体積平均粒子径が５〜５０μｍであることを特徴とする凝集樹脂粒子。
［２］ 微小樹脂粒子が凝集した凝集樹脂粒子において、前記微小樹脂粒子が凝集前の形状を維持しており、前記微小樹脂粒子のＳＥＭ画像によって測定した平均粒子径が１００〜６００ｎｍであり、前記凝集樹脂粒子の形状が不定形であって、嵩密度が０．２０〜０．５０ｇ／ｃｍ ３ であり、かつ分散安定剤を含有しないことを特徴とする凝集樹脂粒子。
［３］ 凝集剤を含有しないことを特徴とする［１］または［２］に記載の凝集樹脂粒子。
［４］ ［１］〜［３］のいずれかに記載の凝集樹脂粒子を含有する塗料組成物。
［５］ ［１］〜［３］のいずれかに記載の凝集樹脂粒子を含有する塗膜。
［６］ 全単量体重量に対して、水に対する溶解性が３重量％未満であるビニル系単量体を９０重量％以上と水溶性重合開始剤を０．２５〜３重量％用いて、水中で重合することにより凝集樹脂粒子を形成させる凝集樹脂粒子の製造方法。
［７］ 凝集剤を添加しないことを特徴とする［６］に記載の凝集樹脂粒子の製造方法。
［８］ 分散安定剤を添加しないことを特徴とする［６］または［７］に記載の凝集樹脂粒子の製造方法。
[1] In the aggregated resin particles in which the fine resin particles are aggregated, the fine resin particles maintain a shape before aggregation, and an average particle diameter measured by an SEM image of the fine resin particles is 100 to 600 nm, Aggregated resin particles, wherein the aggregated resin particles have an irregular shape, a bulk density of 0.20 to 0.50 g / cm 3 , and a volume average particle diameter of 5 to 50 μm .
[2] In the aggregated resin particles in which the fine resin particles are aggregated, the fine resin particles maintain a shape before aggregation, and an average particle diameter measured by an SEM image of the fine resin particles is 100 to 600 nm, An aggregated resin particle characterized in that the aggregated resin particle has an irregular shape, a bulk density of 0.20 to 0.50 g / cm 3 , and no dispersion stabilizer.
[3] The agglomerated resin particles according to [1] or [2], which do not contain a flocculant.
[4] A coating composition containing the aggregated resin particles according to any one of [1] to [ 3 ].
[ 5 ] A coating film containing the aggregated resin particles according to any one of [1] to [ 3 ].
[ 6 ] Using 90% by weight or more of a vinyl monomer having a solubility in water of less than 3% by weight and 0.25 to 3% by weight of a water-soluble polymerization initiator based on the total monomer weight, The manufacturing method of the aggregated resin particle which forms an aggregated resin particle by superposing | polymerizing in water.
[ 7 ] The method for producing aggregated resin particles according to [ 6 ], wherein no flocculant is added.
[ 8 ] The method for producing aggregated resin particles according to [ 6 ] or [ 7 ], wherein a dispersion stabilizer is not added.
本発明の凝集樹脂粒子は樹脂であり、不定形で、かつ、一次粒子が球形であり、特定範囲の嵩密度を有するものである。かかる特性を有する本発明の凝集樹脂粒子を塗料組成物を添加することにより、高い透明性と広範囲の角度にわたる高い艶消し効果の両方を有する塗膜を得ることができる。また、本発明の凝集樹脂粒子の製造方法のよれば、かかる凝集樹脂粒子を簡便かつ効率的に製造することができる。 The agglomerated resin particles of the present invention are resins, are indefinite, have primary particles that are spherical, and have a bulk density in a specific range. By adding the coating composition to the agglomerated resin particles of the present invention having such properties, a coating film having both high transparency and a high matting effect over a wide range of angles can be obtained. Moreover, according to the manufacturing method of the aggregated resin particle of this invention, this aggregated resin particle can be manufactured simply and efficiently.
以下、本発明を詳述する。本発明の凝集樹脂粒子は、微小樹脂粒子が凝集してなるものである。かかる微小樹脂粒子は凝集樹脂粒子を形成している状態において、凝集前の形状を維持している。ここで「凝集前の形状を維持している」とは、凝集樹脂粒子をＳＥＭで観察した場合に、微小樹脂粒子同士が融着して凝集前の微小樹脂粒子の輪郭がはっきりしないような状態ではなく、一つ一つの微小樹脂粒子が区別できる程度に輪郭が維持されていることを言う。従って、例えば一部融着していているような状態でも、ＳＥＭ画像上で一つ一つの微小樹脂粒子を区別して見ることができる限り「凝集前の形状を維持している」状態である。 The present invention is described in detail below. The agglomerated resin particles of the present invention are formed by agglomerating fine resin particles. Such fine resin particles maintain the shape before aggregation in a state where aggregated resin particles are formed. Here, “maintaining the shape before aggregation” means that when the aggregated resin particles are observed with an SEM, the fine resin particles are fused together and the outline of the fine resin particles before aggregation is not clear. Rather, it means that the contour is maintained to such an extent that each fine resin particle can be distinguished. Therefore, for example, even in a partially fused state, as long as each fine resin particle can be distinguished and seen on the SEM image, it is in a state of “maintaining the shape before aggregation”.
このように微小樹脂粒子が「凝集前の形状を維持している」状態においては、微小樹脂粒子同士の融着がない、あるいは、融着している部分が小さいため、凝集樹脂粒子を粉砕工程により任意の粒子径に調整することが可能となる。また、凝集樹脂粒子の表面上にさまざまな角度の面が密に偏りなく存在することになるので、任意の方向からの入射光を斑なく散乱する効果が期待できる。 Thus, in the state in which the fine resin particles “maintain the shape before aggregation”, there is no fusion between the fine resin particles, or the fused portion is small, so the aggregation resin particles are pulverized. Thus, it is possible to adjust to an arbitrary particle size. Further, since the surfaces of various angles are present on the surface of the aggregated resin particles without being unevenly distributed, the effect of scattering incident light from an arbitrary direction can be expected.
かかる微小樹脂粒子のＳＥＭ画像によって測定した平均粒子径としては、上述の粒子径の調整や光散乱の効果の観点から、１００〜６００ｎｍ、好ましくは１５０〜４００ｎｍであることが望ましい。 The average particle size measured from the SEM image of such fine resin particles is preferably 100 to 600 nm, and preferably 150 to 400 nm, from the viewpoint of the adjustment of the particle size and the effect of light scattering.
また、本発明の凝集樹脂粒子の形状は不定形である。ここで、凝集樹脂粒子の形状とは凝集樹脂粒子の細部の形状ではなく、全体的な形状を対象とするものである。また、「不定形」とは、一つ一つの凝集樹脂粒子の形状がまちまちである状態のことである。かかる状態においては、多くの場合、大部分の粒子が球状とは言い難い形状を有しており、粒子を一方向から見た像、すなわち粒子投影像の周囲に凹凸を有している。 Moreover, the shape of the aggregated resin particles of the present invention is indefinite. Here, the shape of the aggregated resin particles is intended for the overall shape, not the detailed shape of the aggregated resin particles. Further, “indefinite shape” means a state in which the shape of each agglomerated resin particle varies. In such a state, in most cases, most of the particles have a shape that cannot be said to be spherical, and there are irregularities around the image of the particle viewed from one direction, that is, the particle projection image.
この不定形の度合いを表す尺度として、下記式によって定義される円形度を用いることができる。
粒子投影像の円形度＝（粒子投影面積と同じ面積の円の周長）／（粒子投影像の周長）
粒子投影像の円形度の平均値＝粒子の円形度
すなわち、円形度は真円の場合に１となり、不定形の度合いが増すにつれ、より小さい値となる。本発明の凝集樹脂粒子においては、上記の粒子の円形度として０．５０〜０．９４の範囲が好ましく、０．７０〜０．９０の範囲がより好ましい。なお、かかる円形度は、例えば、シスメックス株式会社製フロー式粒子像分析装置「ＦＰＩＡ−３０００Ｓ」を用いて測定することができる。
As a scale representing the degree of this irregular shape, the circularity defined by the following formula can be used.
Circularity of particle projection image = (circumference of a circle having the same area as the particle projection area) / (perimeter of particle projection image)
Average value of the circularity of the projected particle image = the circularity of the particle, that is, the circularity is 1 in the case of a perfect circle, and becomes a smaller value as the degree of the irregular shape increases. In the aggregated resin particles of the present invention, the circularity of the particles is preferably in the range of 0.50 to 0.94, and more preferably in the range of 0.70 to 0.90. The circularity can be measured using, for example, a flow type particle image analyzer “FPIA-3000S” manufactured by Sysmex Corporation.
このように凝集樹脂粒子が不定形を有している状態においては、入射光が不規則に散乱されるため、塗膜などに添加した場合、見る角度に依存せず、広範囲の角度にわたって高い艶消し効果を発現することが期待できる。 In such a state where the aggregated resin particles have an irregular shape, incident light is irregularly scattered. Therefore, when added to a coating film or the like, it does not depend on the viewing angle and has a high gloss over a wide range of angles. It can be expected to exert an erasing effect.
さらに、本発明の凝集樹脂粒子の嵩密度は０．２０〜０．５０ｇ／ｃｍ３であり、好ましくは０．２５〜０．４０ｇ／ｃｍ３であることが望ましい。この嵩密度は球状粒子においては０．７ｇ／ｃｍ３程度であるが、嵩密度が０．２０〜０．５０ｇ／ｃｍ３であれば、塗膜への粒子の添加重量を変えずに粒子数を増やし、塗膜表面の凹凸数を増やすことができるので、艶消し効果を高め、塗膜面に対して低角度から見た場合でも十分な艶消し効果が得られるようになる。 Furthermore, the bulk density of the aggregated resin particles of the present invention is 0.20 to 0.50 g / cm 3 , preferably 0.25 to 0.40 g / cm 3 . This bulk density is about 0.7 g / cm 3 in the case of spherical particles, but if the bulk density is 0.20 to 0.50 g / cm 3 , the number of particles without changing the weight of the particles added to the coating film The number of irregularities on the surface of the coating film can be increased, so that the matting effect is enhanced and a sufficient matting effect can be obtained even when viewed from a low angle with respect to the coating film surface.
かかる凝集樹脂粒子の体積平均粒子径としては、５〜５０μｍであることが好ましく、より好ましくは５〜３０μｍ、さらに好ましくは７〜２０μｍである。平均粒子径が５μｍ未満であると、塗膜の表面に凹凸が付き難くなって低角度から見た場合に十分な艶消し効果を発現できない恐れがある。一方、平均粒子径が５０μｍ範囲を越えると、塗膜への添加重量が同じであっても粒子数が減るため塗膜表面の凹凸数が減り、低角度から見た際の艶消し効果が不十分となる恐れがある。また、塗工時に斑が発生しやすくなり、塗膜表面にざらつきを与えるほか塗膜物性の低下を引き起こす可能性が高くなる。 The volume average particle diameter of the aggregated resin particles is preferably 5 to 50 μm, more preferably 5 to 30 μm, and further preferably 7 to 20 μm. If the average particle size is less than 5 μm, the surface of the coating film becomes difficult to be uneven, and there is a possibility that a sufficient matting effect cannot be exhibited when viewed from a low angle. On the other hand, if the average particle diameter exceeds 50 μm, the number of particles decreases even if the weight added to the coating is the same, so the number of irregularities on the coating surface decreases, and the matte effect when viewed from a low angle is not good. May be enough. Moreover, it becomes easy to generate | occur | produce a spot at the time of coating, and the possibility of causing the fall of a coating-film physical property besides giving a rough surface to a coating-film surface becomes high.
また、本発明の凝集樹脂粒子は分散安定剤および凝集剤のいずれも含有しないことが望ましい。ここで、分散安定剤とは、重合工程やその後に分散状態を安定化させるために添加される界面活性剤、乳化剤、懸濁安定剤などを指し、凝集剤とは一次粒子を凝集させるための高分子添加剤などを指す。これらの剤は凝集樹脂粒子を製造する工程において添加されることが多く、一般的な凝集樹脂粒子中にはこれらの剤が含有されている。しかし、これらの剤は、凝集樹脂粒子を塗料に添加混合した場合に凝集状態を解消させたり、塗料や塗膜の特性を低下させたりする恐れがある。 Moreover, it is desirable that the aggregated resin particles of the present invention contain neither a dispersion stabilizer nor an aggregating agent. Here, the dispersion stabilizer refers to a surfactant, an emulsifier, a suspension stabilizer, etc. added to stabilize the dispersion state after the polymerization step, and the aggregating agent is used to aggregate the primary particles. It refers to polymer additives. These agents are often added in the step of producing aggregated resin particles, and these agents are contained in general aggregated resin particles. However, these agents may cause the agglomerated state to be eliminated or the properties of the paint or coating film to be lowered when the agglomerated resin particles are added to and mixed with the paint.
本発明の凝集樹脂粒子の樹脂の種類、すなわち微小樹脂粒子の樹脂の種類としては特に限定されないが、凝集樹脂粒子が添加される塗料の樹脂との屈折率差ができるだけ小さくなる樹脂を凝集樹脂粒子の樹脂として選択することにより、得られる塗膜の内部ヘイズ値が低下し、透明性が向上する。具体的には凝集樹脂粒子と塗料樹脂の屈折率差が０〜０．０４、好ましくは０〜０．０３、より好ましくは０〜０．０２である場合に優れた透明性を有する塗膜を得ることができる。 The type of resin of the agglomerated resin particles of the present invention, that is, the type of resin of the fine resin particles is not particularly limited, but the resin having the smallest difference in refractive index from the resin of the paint to which the agglomerated resin particles are added is aggregated resin particles. By selecting as the resin, the internal haze value of the obtained coating film is lowered and the transparency is improved. Specifically, a coating film having excellent transparency when the difference in refractive index between the aggregated resin particles and the coating resin is 0 to 0.04, preferably 0 to 0.03, more preferably 0 to 0.02. Can be obtained.
この屈折率を調整するという観点から、凝集樹脂粒子の樹脂としては、利用できる単量体の種類が豊富なビニル系樹脂が好ましい。かかるビニル系樹脂を採用する場合に利用できるビニル系単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸２−エチルヘキシル、アクリル酸ラウリル、ジメチルアミノエチルアクリレート、ジエチルアミノエチルアクリレート等のアクリル酸エステル系単量体、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ラウリル、ジメチルアミノエチルメタクリレート等のメタクリル酸エステル系単量体、スチレン、ｐ−メチルスチレン等のスチレン系単量体、メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル、酢酸ビニル、酪酸ビニル等のビニルエステル系単量体、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド等のＮ−アルキル置換（メタ）アクリルアミド、アクリロニトリル、メタクリロニトリル等のニトリル系単量体、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート等の多官能単量体等が挙げられる。このような単量体は、単独で、または２種類以上を組合せて用いてもよい。 From the viewpoint of adjusting the refractive index, the resin of the aggregated resin particles is preferably a vinyl-based resin rich in the types of monomers that can be used. Examples of vinyl monomers that can be used when adopting such vinyl resins include acrylic acid esters such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl acrylate. Monomers, methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, lauryl methacrylate, dimethylaminoethyl methacrylate, styrene monomers such as styrene and p-methylstyrene, methyl vinyl ether, ethyl vinyl ether Vinyl ester monomers such as alkyl vinyl ethers such as vinyl acetate and vinyl butyrate, N-alkyl substituted (meth) acrylamides such as N-methyl acrylamide and N-ethyl acrylamide, acrylonitrile, Polyfunctional monomers such as nitrile monomers such as acrylonitrile, divinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Examples include the body. Such monomers may be used alone or in combination of two or more.
また、メタクリル酸メチルやエチレングリコールジメタクリレートなどの水に対する溶解性が３重量％未満であるビニル系単量体を用いる場合、後述する製造方法により、分散安定剤および凝集剤のいずれも含有しない凝集樹脂粒子を簡便に得ることができるという利点がある。 In addition, when a vinyl monomer having a water solubility of less than 3% by weight, such as methyl methacrylate or ethylene glycol dimethacrylate, is used, agglomeration containing neither a dispersion stabilizer nor a flocculant is produced by the production method described later. There is an advantage that resin particles can be easily obtained.
上述してきた本発明の凝集樹脂粒子は塗膜や樹脂成形品などの艶消し剤として利用した場合、艶消し効果が大きく、見る角度による艶消し効果の斑が小さいものを得ることができる。 When the above-described aggregated resin particles of the present invention are used as a matting agent such as a coating film or a resin molded product, it is possible to obtain particles having a large matting effect and small spots of the matting effect depending on the viewing angle.
塗膜の艶消し剤として利用する場合には、塗料組成物に本発明の凝集樹脂粒子を添加混合し、これを塗布すればよい。このとき、塗料樹脂に対して凝集樹脂粒子の添加量を３〜４０重量％とするのが好ましく、より好ましくは５〜３５重量％、さらに好ましくは８〜３０重量％である。添加量が３重量％未満であると艶消し効果を十分に付与することができず、一方、４０重量％を越えると塗膜の外観が損なわれたり、塗膜物性の低下を引き起こしたりする恐れがある。 When used as a matting agent for a coating film, the agglomerated resin particles of the present invention may be added to and mixed with the coating composition. At this time, the addition amount of the aggregated resin particles is preferably 3 to 40% by weight with respect to the coating resin, more preferably 5 to 35% by weight, and still more preferably 8 to 30% by weight. If the amount added is less than 3% by weight, the matte effect cannot be sufficiently imparted. On the other hand, if it exceeds 40% by weight, the appearance of the coating film may be impaired or the physical properties of the coating film may be deteriorated. There is.
また、上述したように、下地の色を損なわないようにしたいなど透明性が求められる場合には、凝集樹脂粒子と塗料樹脂との屈折率差ができるだけ小さくなるように樹脂の種類を選択することが望ましい。 In addition, as described above, when transparency is required, for example, in order not to impair the color of the ground, select the type of resin so that the refractive index difference between the aggregated resin particles and the coating resin is as small as possible. Is desirable.
塗料組成物に凝集樹脂粒子を添加混合する方法としては、従来公知の方法を採用することができるが、例えば市販の透明な水性トップコート塗料に対して純水と凝集樹脂粒子を加えて高速ディスパーやホモジナイザー、サンドミル等で攪拌し、このとき必要に応じて消泡剤、難燃剤、防腐剤、防カビ剤、粘度調整剤などの助剤を添加する方法などが挙げられる。また、凝集樹脂粒子を添加混合する際には該粒子を乾燥させておく必要はなく、水系塗料に添加する場合などには水分を含んだウェット状態で添加しても構わない。 As a method of adding and mixing the agglomerated resin particles to the coating composition, a conventionally known method can be adopted. For example, pure water and agglomerated resin particles are added to a commercially available transparent water-based topcoat paint to add a high-speed disperser. Or a homogenizer, a sand mill, or the like, and an auxiliary agent such as an antifoaming agent, a flame retardant, a preservative, a fungicide, or a viscosity modifier may be added as necessary. Further, when adding and mixing the aggregated resin particles, it is not necessary to dry the particles, and when adding to the water-based paint, it may be added in a wet state containing moisture.
かかる塗料組成物を塗布することにより、本発明の凝集樹脂粒子を含有する塗膜を形成することができる。かかる塗膜においては、従来に比べて高い艶消し効果の得られる角度が広範囲となり、特に、凝集樹脂粒子の体積平均粒子径が５〜５０μｍの範囲内である場合においては、２０°、６０°、８５°グロス値の全てを０〜３０％、さらには０〜２０％という低いレベルに抑制することも可能である。かかるグロス値を得るには、塗膜の厚さを凝集樹脂粒子の平均粒子径の３０〜２５０％、好ましくは４０〜２００％とすることが望ましい。また、上述したように凝集樹脂粒子と塗料樹脂の屈折率差を小さくすることにより塗膜の内部ヘイズ値を０〜８％という低いレベルに抑えることが可能である。すなわち、本発明の塗膜においては、２０°、６０°、８５°グロス値の全てが０〜２０％で、かつ内部ヘイズ値が０〜８％という従来困難であった特性の両立を実現することができ、高い透明性を維持しながら、あらゆる角度から見た際の高い艶消し性を有し、従来得られなかった高級感を有する塗膜外観を達成することができる。 By applying such a coating composition, a coating film containing the aggregated resin particles of the present invention can be formed. In such a coating film, the angle at which a high matting effect is obtained as compared with the conventional one is in a wide range, and in particular, when the volume average particle diameter of the aggregated resin particles is in the range of 5 to 50 μm, 20 °, 60 °. It is also possible to suppress all of the 85 ° gloss value to a low level of 0 to 30%, further 0 to 20%. In order to obtain such a gloss value, it is desirable that the thickness of the coating film is 30 to 250%, preferably 40 to 200% of the average particle diameter of the aggregated resin particles. Further, as described above, the internal haze value of the coating film can be suppressed to a low level of 0 to 8% by reducing the refractive index difference between the aggregated resin particles and the coating resin. That is, in the coating film of the present invention, all of the 20 °, 60 °, and 85 ° gloss values are 0 to 20% and the internal haze value is 0 to 8%, which achieves both of the conventionally difficult characteristics. In addition, while maintaining high transparency, it is possible to achieve a coating appearance that has high matteness when viewed from all angles and has a high-class feeling that has not been obtained conventionally.
以上に述べてきた本発明の凝集樹脂粒子の製造方法としては、目的の凝集樹脂粒子が得られる限り特に制限されない。ここでは、その一例として、重合開始剤の溶解した水中にビニル系単量体の液滴を分散させ、加熱・撹拌しながら重合することで凝集状の粒子を形成し、かかる粒子を必要に応じて粉砕・分級し、目的とする凝集樹脂粒子を得る方法について述べる。 The method for producing the aggregated resin particles of the present invention described above is not particularly limited as long as the desired aggregated resin particles are obtained. Here, as an example, droplets of vinyl monomer are dispersed in water in which a polymerization initiator is dissolved, and polymerized while heating and stirring to form aggregated particles. A method of pulverizing and classifying to obtain the desired aggregated resin particles will be described.
かかる方法において使用されるビニル系単量体としては、２０℃における水に対する溶解性が３重量％未満、好ましくは２重量％未満のビニル系単量体を用いることが望ましく、かかるビニル系単量体を全単量体重量に対して９０重量％以上、好ましくは９５重量％以上用いる。かかるビニル単量体の代表的な例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸２−エチルヘキシル、アクリル酸ラウリル等のアクリル酸エステル系単量体、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ラウリル等のメタクリル酸エステル系単量体、スチレン、ｐ−メチルスチレン等のスチレン系単量体、メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル、酢酸ビニル、酪酸ビニル等のビニルエステル系単量体、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレートなどを挙げることができる。かかる単量体が９０重量％未満の場合、微小樹脂粒子が凝集しなくなる場合がある。これは、水に対する溶解性が３重量％以上のビニル系単量体の使用量が多くなることで、かかる単量体が優先的に重合し、分散剤的な役割を果たすためと考えられる。また、全仕込み重量に対する全単量体重量の割合としては、５〜３５重量％であることが望ましい。 As the vinyl monomer used in such a method, it is desirable to use a vinyl monomer having a solubility in water at 20 ° C. of less than 3% by weight, preferably less than 2% by weight. The body is used in an amount of 90% by weight or more, preferably 95% by weight or more based on the total monomer weight. Representative examples of such vinyl monomers include acrylate monomers such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Methacrylic acid ester monomers such as lauryl, styrene monomers such as styrene and p-methylstyrene, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl ester monomers such as vinyl acetate and vinyl butyrate, divinyl Examples include benzene, ethylene glycol di (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate. That. When the monomer is less than 90% by weight, the fine resin particles may not aggregate. This is presumably because the amount of vinyl monomer having a solubility in water of 3% by weight or more increases the amount of such a monomer that preferentially polymerizes and acts as a dispersant. Moreover, as a ratio of the total monomer weight with respect to the total preparation weight, it is desirable that it is 5-35 weight%.
重合開始剤としては水溶性重合開始剤であれば、アゾ系、過硫酸塩系、過酸化物系、レドックス系などいずれの種類の開始剤でも採用でき、光開始剤でも、熱開始剤でもよい。代表的な例としては、2,2'-Azobis(2-methylpropionamidine)dihydrochloride、2,2'-Azobis(1-imino-1-pyrrolidino-2-methylpropane)dihydrochloride、t-Butyl
hydroperoxide、過硫酸アンモニウム、過硫酸カリウム、過酸化水素／鉄（ＩＩ）イオン系などを挙げることができる。
As the polymerization initiator, any type of initiator such as azo, persulfate, peroxide, redox, etc. can be adopted as long as it is a water-soluble polymerization initiator, and it may be a photoinitiator or a thermal initiator. . Typical examples include 2,2'-Azobis (2-methylpropionamidine) dihydrochloride, 2,2'-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, t-Butyl
Examples include hydroperoxide, ammonium persulfate, potassium persulfate, and hydrogen peroxide / iron (II) ion system.
かかる水溶性重合開始剤は、全単量体重量に対して０．２５〜３重量％、好ましくは０．２５〜２重量％用いることが望ましい。かかる範囲内とすることにより、微小樹脂粒子が凝集した状態であり、かつ、塊状化していない適度な大きさの粒子を得ることができる。 The water-soluble polymerization initiator is used in an amount of 0.25 to 3% by weight, preferably 0.25 to 2% by weight, based on the total monomer weight. By setting it within such a range, it is possible to obtain particles having a moderate size in which the fine resin particles are in an aggregated state and are not agglomerated.
以上のようにして、本発明の凝集樹脂粒子を得ることができるが、必要に応じて粉砕処理を施し、所望の粒子径に調整することも可能である。上述したようにかかる粒子は粉砕しやすい構造をとっているので、かかる粉砕処理においては特別な装置を必要とせず、ブレードミル、バンバリーミキサー、ニーダーミキサー、ロールなどの汎用の粉砕装置を用いることができる。また、粉砕処理に際しては、粒子を乾燥させておく必要はなく、重合終了後そのまま粉砕することも可能である。 As described above, the agglomerated resin particles of the present invention can be obtained, but it is also possible to adjust to a desired particle diameter by performing a pulverization treatment as necessary. As described above, since the particles have a structure that can be easily pulverized, a special apparatus is not required for the pulverization process, and a general-purpose pulverization apparatus such as a blade mill, a Banbury mixer, a kneader mixer, or a roll can be used. it can. In the pulverization treatment, it is not necessary to dry the particles, and the particles can be pulverized as they are after the polymerization.
また、上述したように本発明の凝集樹脂粒子の製造においては分散安定剤や凝集剤を用いないことが望ましい。上記に詳述した製造方法においては、これらの剤を使用せずに適度な凝集状態の凝集樹脂粒子を得ることが可能である。 Further, as described above, it is desirable not to use a dispersion stabilizer or a flocculant in the production of the aggregated resin particles of the present invention. In the production method described in detail above, it is possible to obtain agglomerated resin particles in an appropriate agglomerated state without using these agents.
以下、実施例および比較例により本発明の効果を説明するが、本発明の範囲はこれら実施例のみに限定されるものではない。なお、実施例における特性値の評価は以下の方法に従った。 Hereinafter, the effects of the present invention will be described with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples. In addition, evaluation of the characteristic value in an Example followed the following method.
（１）凝集樹脂粒子の円形度および体積平均粒子径
上述した定義による粒子の円形度および体積平均粒子径をフロー式粒子像分析装置（ＦＰＩＡ−３０００Ｓ：シスメックス(株)製）によって測定した。
(1) Circularity and volume average particle diameter of aggregated resin particles The circularity and volume average particle diameter of the particles as defined above were measured by a flow type particle image analyzer (FPIA-3000S: manufactured by Sysmex Corporation).
（２）微小樹脂粒子の平均粒子径
凝集樹脂粒子のＳＥＭ画像において、微小樹脂粒子を任意に２０個選び出して、それぞれの直径を測定し平均値を算出した。
(2) Average particle diameter of the fine resin particles In the SEM image of the aggregated resin particles, 20 fine resin particles were arbitrarily selected and the respective diameters were measured to calculate the average value.
（３）嵩密度
体積が既知の容器Ａ（ｃｍ３）に粒子を充填し、その重量Ｂ（ｇ）を測定して嵩密度を算出した。
嵩密度（ｇ／ｃｍ３）＝Ｂ（ｇ）／Ａ（ｃｍ３）
(3) A container A (cm 3 ) having a known bulk density volume was filled with particles, and its weight B (g) was measured to calculate the bulk density.
Bulk density (g / cm 3 ) = B (g) / A (cm 3 )
（４）屈折率差
試料をスライドガラスにセットして標準屈折液（カーギル標準屈折液）を滴下後、カバーガラスをセットして光学顕微鏡によってサンプルを観察した。サンプルが確認できなくなるまで標準屈折液を変更し、確認できなくなった標準液の屈折率をサンプルの屈折率とした。屈折率差は２つのサンプルの屈折率の差の絶対値である。なお、塗料樹脂については、該樹脂のみ硬化させたものを粉砕して得られた粉末を試料として用いた。
(4) The refractive index difference sample was set on a slide glass and a standard refractive liquid (Cargill standard refractive liquid) was dropped, then a cover glass was set and the sample was observed with an optical microscope. The standard refractive liquid was changed until the sample could not be confirmed, and the refractive index of the standard liquid that could not be confirmed was taken as the refractive index of the sample. The refractive index difference is the absolute value of the difference in refractive index between the two samples. In addition, about the coating resin, the powder obtained by grind | pulverizing what hardened only this resin was used as a sample.
（５）内部ヘイズ値
まず、塗膜サンプルの表面にセロファンテープを貼り付けて表面凹凸をなくした状態にして、ヘイズメーター（ＮＤＨ ２０００：日本電色（株）製）でヘイズ値を測定する（ヘイズＡ（％））。次にＰＥＴフィルム（コスモシャイン＃Ａ４３００（厚さ１００μｍ：東洋紡績（株）製）にセロファンテープを貼り付けたサンプルのヘイズ値を測定する（ヘイズＢ（％））。下記式より内部ヘイズ値（％）を算出した。
内部ヘイズ値［％］＝ヘイズＡ［％］−ヘイズＢ［％］
(5) Internal haze value First, cellophane tape is applied to the surface of the coating film sample to remove the surface irregularities, and the haze value is measured with a haze meter (NDH 2000: manufactured by Nippon Denshoku Co., Ltd.) ( Haze A (%)). Next, the haze value of a sample in which cellophane tape is pasted on a PET film (Cosmo Shine # A4300 (thickness 100 μm: manufactured by Toyobo Co., Ltd.)) is measured (haze B (%)). %) Was calculated.
Internal haze value [%] = Haze A [%] − Haze B [%]
（６）２０°、６０°、８５°グロス値
隠蔽率試験紙上に作成した塗膜サンプルを光沢度計（ＶＧ ２０００：日本電色（株）製）をによって測定した。
(6) 20 °, 60 °, 85 ° gloss value concealment rate The coating film sample prepared on the test paper was measured with a gloss meter (VG 2000: manufactured by Nippon Denshoku Co., Ltd.).
［実施例１］
反応槽に水３００重量部を仕込み、重合開始剤として2,2'-Azobis(1-imino-1-pyrrolidino-2-methylpropane)dihydrochloride０．６重量部を溶解させる。次いで単量体としてメタクリル酸メチル９９重量部とエチレングリコールメタクリレート１重量部を加えて、撹拌しながら４５℃で２時間反応させる。析出した凝集樹脂粒子を濾別、水洗、乾燥させた後、風力分級機で粉砕、分級し、実施例１の凝集樹脂粒子を得た。該凝集樹脂粒子の特性を測定した結果を表１に示す。また、該粒子のＳＥＭ画像を図１および図２に示す。
[Example 1]
300 parts by weight of water is charged into the reaction vessel, and 0.6 part by weight of 2,2′-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride is dissolved as a polymerization initiator. Next, 99 parts by weight of methyl methacrylate and 1 part by weight of ethylene glycol methacrylate are added as monomers and reacted at 45 ° C. for 2 hours with stirring. The precipitated aggregated resin particles were separated by filtration, washed with water and dried, and then pulverized and classified with an air classifier to obtain aggregated resin particles of Example 1. Table 1 shows the results of measuring the characteristics of the aggregated resin particles. In addition, SEM images of the particles are shown in FIGS.
上記で得られた凝集樹脂粒子３重量部と水５０重量部を水性トップコート塗料（水溶性つやだしニス（アクリル樹脂、樹脂濃度３０重量％）：和信ペイント（株）製）１００重量部に加え、ホモジナイザーで１０分間撹拌した。得られた塗料組成物をＰＥＴフィルム（コスモシャイン＃Ａ４３００（厚さ１００μｍ：東洋紡績（株）製）上にバーコーター＃２６で塗工し、その後５０℃の熱風乾燥機中で３０分乾燥した。かかる塗膜の評価結果を表１に示す。なお、塗膜の厚さは粒子による凹凸があるため直接測定できないが、粒子を添加しないこと以外は同様にして作成した塗膜の厚さをマイクロメータで測定したところ９μｍであった。 3 parts by weight of the agglomerated resin particles obtained above and 50 parts by weight of water are added to 100 parts by weight of an aqueous topcoat paint (water-soluble glossy varnish (acrylic resin, resin concentration 30% by weight): manufactured by Washin Paint Co., Ltd.). The mixture was stirred for 10 minutes with a homogenizer. The obtained coating composition was coated on a PET film (Cosmo Shine # A4300 (thickness 100 μm: manufactured by Toyobo Co., Ltd.) with a bar coater # 26, and then dried in a hot air dryer at 50 ° C. for 30 minutes. The evaluation results of the coating film are shown in Table 1. The thickness of the coating film cannot be directly measured because of irregularities due to the particles, but the thickness of the coating film prepared in the same manner except that no particles are added. It was 9 micrometers when measured with the micrometer.
［実施例２］
反応槽に水３００重量部を仕込み、重合開始剤として過硫酸カリウム０．６重量部を溶解させる。次いで単量体としてメタクリル酸メチル１００重量部を加えた後、ピロ亜硫酸ナトリウム０．４５重量部を加え、撹拌しながら４５℃で２時間反応させる。析出した凝集樹脂粒子を濾別、水洗、乾燥させた後、風力分級機で粉砕、分級し、実施例２の凝集樹脂粒子を得た。また、該粒子を用い、実施例１と同様にして、塗膜を作成した。これらの評価結果を表１に示す。
[Example 2]
300 parts by weight of water is charged into the reaction vessel, and 0.6 part by weight of potassium persulfate is dissolved as a polymerization initiator. Next, after adding 100 parts by weight of methyl methacrylate as a monomer, 0.45 part by weight of sodium pyrosulfite is added and reacted at 45 ° C. for 2 hours with stirring. The precipitated aggregated resin particles were separated by filtration, washed with water and dried, and then pulverized and classified with an air classifier to obtain aggregated resin particles of Example 2. Further, a coating film was prepared in the same manner as in Example 1 using the particles. These evaluation results are shown in Table 1.
［実施例３、４］
風力分級機での粉砕条件を変更すること以外は実施例１と同様にして、実施例３および４の凝集樹脂粒子および塗膜を得た。これらの評価結果を表１に示す。
[Examples 3 and 4]
Aggregated resin particles and coating films of Examples 3 and 4 were obtained in the same manner as in Example 1 except that the pulverization conditions in the air classifier were changed. These evaluation results are shown in Table 1.
［比較例１］
反応槽に水８３１重量部を仕込み、ポリビニルアルコール（ＰＶＡ２１７：（株）クラレ製）７部、硫酸ナトリウム１０重量部、硫酸銅・５水和物１重量部を溶解させる。次いで単量体としてメタアクリル酸メチル１３５重量部とエチレングリコールジメタクリレート１５重量部、開始剤として２，２’―アゾビス（２−メチルバレロニトリル）１重量部を溶解したものを加えて、攪拌しながら５０℃で５時間反応させることで球状粒子の水分散体を得た。該水分散体から粒子を濾別、水洗、乾燥させ、比較例１の粒子を得た。該粒子の特性を測定した結果を表１に示す。また、該粒子を用いること以外は実施例１と同様にして作成した塗膜の評価結果を表１に示す。
[Comparative Example 1]
The reaction vessel is charged with 831 parts by weight of water, and 7 parts of polyvinyl alcohol (PVA217: manufactured by Kuraray Co., Ltd.), 10 parts by weight of sodium sulfate, and 1 part by weight of copper sulfate pentahydrate are dissolved therein. Next, 135 parts by weight of methyl methacrylate and 15 parts by weight of ethylene glycol dimethacrylate as monomers and 1 part by weight of 2,2′-azobis (2-methylvaleronitrile) as an initiator were added and stirred. However, an aqueous dispersion of spherical particles was obtained by reacting at 50 ° C. for 5 hours. Particles were separated from the aqueous dispersion by filtration, washed with water, and dried to obtain Comparative Example 1 particles. The results of measuring the characteristics of the particles are shown in Table 1. Table 1 shows the evaluation results of the coating film prepared in the same manner as in Example 1 except that the particles were used.
［比較例２］
単量体としてメタクリル酸メチル８５重量部と２−ヒドロキシエチルメタクリレート１５重量部を用いること以外は実施例１と同様にして重合を行ったところ微小樹脂粒子の水分散体が得られた。かかる水分散体を噴霧乾燥し、球状の凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。また、該粒子を用いること以外は実施例１と同様にして作成した塗膜の評価結果を表１に示す。
[Comparative Example 2]
Polymerization was carried out in the same manner as in Example 1 except that 85 parts by weight of methyl methacrylate and 15 parts by weight of 2-hydroxyethyl methacrylate were used as monomers, and an aqueous dispersion of fine resin particles was obtained. The aqueous dispersion was spray-dried to obtain spherical aggregated resin particles. The results of measuring the characteristics of the particles are shown in Table 1. Table 1 shows the evaluation results of the coating film prepared in the same manner as in Example 1 except that the particles were used.
［比較例３］
過硫酸カリウムを５重量部、ピロ亜硫酸ナトリウムを３．７５重量部とを用いること以外は実施例２と同様にして反応を行ったが、析出した粒子が一体塊状化し、粉砕困難で、凝集樹脂粒子は得られなかった。
[Comparative Example 3]
The reaction was carried out in the same manner as in Example 2 except that 5 parts by weight of potassium persulfate and 3.75 parts by weight of sodium pyrosulfite were used. Particles were not obtained.
実施例１〜４では不定形の凝集樹脂粒子が得られ、これらの粒子を添加した塗膜は、広範囲にわたる角度において優れた艶消し効果を有しながら、高い透明性を併せ持つものである。一方、比較例１では単独の球形で凝集しておらず、嵩密度が高い粒子が得られ、該粒子を添加した塗膜の艶消し効果は高くない。これは、塗膜の表面状態が単調となり、相対的に凹凸数も少なくなるためと考えられる。比較例２では凝集しているが全体として球状の粒子が得られ、該粒子を添加した塗膜の艶消し効果は比較例１に対しては若干良いものの、不定形の凝集樹脂粒子に比べると劣るものである。 In Examples 1 to 4, irregular agglomerated resin particles are obtained, and the coating film to which these particles are added has high transparency while having an excellent matting effect in a wide range of angles. On the other hand, in Comparative Example 1, particles having a single spherical shape and not agglomerated and having a high bulk density are obtained, and the matte effect of the coating film to which the particles are added is not high. This is presumably because the surface state of the coating film becomes monotonous and the number of irregularities is relatively reduced. Although agglomerated in Comparative Example 2, spherical particles are obtained as a whole, and the matte effect of the coating film to which the particles are added is slightly better than that of Comparative Example 1, but compared with the irregular agglomerated resin particles. It is inferior.
本発明の凝集樹脂粒子を塗料組成物に添加し、これを塗布することで高い透明性と広範囲にわたる優れた艶消し性を両立する塗膜を得ることができるので、下地の色合い、柄、模様等をぼかすことなく、斑の小さい艶消し性を付与した高級感のある塗膜表面を提供することが可能である。かかる凝集樹脂粒子は塗料分野のみならず、樹脂成形品や人工皮革などの艶消し性の求められる分野に幅広く用いることができる。 By adding the agglomerated resin particles of the present invention to a coating composition and applying it, a coating film having both high transparency and a wide range of excellent matting properties can be obtained. Thus, it is possible to provide a high-quality coating surface having a matte property with small spots without blurring. Such agglomerated resin particles can be widely used not only in the paint field, but also in fields requiring matting properties such as resin molded products and artificial leather.
Claims (8)
The method for producing agglomerated resin particles according to claim 6 or 7 , wherein a dispersion stabilizer is not added.
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