JP4838448B2 - Acrylic plastisol for rotary screen printing - Google Patents
Acrylic plastisol for rotary screen printing Download PDFInfo
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- JP4838448B2 JP4838448B2 JP2001212221A JP2001212221A JP4838448B2 JP 4838448 B2 JP4838448 B2 JP 4838448B2 JP 2001212221 A JP2001212221 A JP 2001212221A JP 2001212221 A JP2001212221 A JP 2001212221A JP 4838448 B2 JP4838448 B2 JP 4838448B2
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- methacrylate
- fine particles
- weight
- phthalate
- acrylic
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- 229920001944 Plastisol Polymers 0.000 title claims abstract description 39
- 239000004999 plastisol Substances 0.000 title claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000010022 rotary screen printing Methods 0.000 title claims abstract description 12
- 239000010419 fine particle Substances 0.000 claims abstract description 30
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 23
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008029 phthalate plasticizer Substances 0.000 claims abstract description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims abstract description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims abstract description 3
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 claims abstract description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004014 plasticizer Substances 0.000 claims description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- -1 phthalate ester Chemical class 0.000 claims description 10
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N Diethylhexyl phthalate Natural products CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- DJDSLBVSSOQSLW-UHFFFAOYSA-N mono(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(O)=O DJDSLBVSSOQSLW-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 239000011258 core-shell material Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、各種塗工法、特にロータリースクリーン印刷法に適したアクリル系プラスチゾルに関する。
【０００２】
【従来技術】
エマルジョン重合されたポリ塩化ビニル系樹脂用い、可塑剤を配合したポリ塩化ビニル系プラスチゾルは、さまざまな用途に使用されている。
しかしながら、燃焼時の塩素系ガスの発生等の問題でポリ塩化ビニル系樹脂の代替として、可塑剤を配合することによりプラスチゾルとすることができる点で、アクリル系樹脂を使用したアクリル系プラスチゾルの開発が行われるようになった。
【０００３】
このようにアクリル系プラスチゾルは、主としてアクリル系樹脂と可塑剤とを配合してなるものであるが、アクリル系樹脂の樹脂組成が可塑剤への溶解性の大なるものとすると、得られたプラスチゾルは、急速な粘度上昇を起こしてしまい、ナイフコート、グラビアコート等の塗工や、特にロータリースクリーン印刷法による塗工に使用できなくなる。反対に樹脂組成が可塑剤への溶解性の小なるものとすると、粘度上昇を防ぐことができるものの、加熱固化後に経時で可塑剤がブリードアウトしやすいといった問題がある。
【０００４】
特開平７−２３３２９９号公報には、上述の問題を解決するために、コア・シェル構造のアクリル系樹脂微粒子とジアルキルフタルレート系可塑剤と用いたアクリルゾルであって、シェル部を前記可塑剤への溶解性の小なるものとして急激な粘度上昇を防ぎ、コア部を前記可塑剤への溶解性の大なる樹脂組成のものとして、加熱固化後のブリードアウトを防ぐことが記載されている。
【０００５】
一方、このようなアクリル系プラスチゾルを、ロータリースクリーン印刷法等にて、プラスチックスフィルムや不織布等の基材に散点状に塗工して加熱固化させた建材が、産業上利用されるようになってきた。
【０００６】
その際、例えば、ロータリースクリーン印刷法では、プラスチゾルが、それ自体の持つ粘り特性のために、スクリーンから抜けにくくなる、所謂糸引き現象を招くことがあり良好な建材とすることができないという問題があった。
【０００７】
【発明が解決しようとする課題】
本発明は、上述の問題を解決するためになされたものであって、各種塗工法、特にロータリースクリーン印刷法に適した特性を有するアクリル系プラスチゾルを提供するものである。
【０００８】
【課題を解決するための手段】
本発明のロータリースクリーン印刷用アクリル系プラスチゾルは、主としてアクリル系樹脂微粒子とフタル酸エステル系可塑剤と無機充填材からなり、アクリル系樹脂微粒子が、コア・シェル構造の微粒子からなり、コア・シェル構造の微粒子のコア部が、エチルメタクリレート、ノルマルブチルメタクリレート、イソブチルメタクリレート、ターシャリーブチルメタクリレート、シクロヘキシルメタクリレート、エチルヘキシルメタクリレートから選ばれるモノマー単位を５０重量％以上含有した樹脂にて構成され、シェル部が、メチルメタクリレート、ベンジルメタクリレート、スチレンから選ばれるモノマー単位を５０重量％以上含有した樹脂にて構成され、フタル酸エステル系可塑剤が、フタル酸−２−エチルヘキシル、フタル酸ジイソノニル、フタル酸ブチルベンジルから選ばれる一種以上であり、無機充填材は、平均粒子径０．１〜１．５μｍのコロイド状炭酸カルシウムであり、かつ前記コロイド状炭酸カルシウム１００ｇ当たりの前記フタル酸エステル系可塑剤最大吸収量が、２５〜３５ｇであり、アクリル系樹脂微粒子１００重量部に対し、フタル酸エステル系可塑剤は７０〜１５０重量部、無機充填材は１０〜３０重量部配合されることを特徴とする。
なお、無機充填材がフタル酸エステル系可塑剤を吸収する最大吸収量を、単に吸油量という場合もある。この吸油量は、可塑剤の種類によって変化するが、前記した可塑剤の間では、ほとんど変化がない。吸油量は、ＪＩＳ Ｋ５１０１吸油量測定法に準じる。
【０００９】
コア・シェル構造の微粒子は、乳化重合あるいは懸濁重合によって得られるが、乳化重合によることが好ましい。乳化重合による場合、まずコア部を含むエマルジョンを作製し、引き続き前記コア部を被覆した形のシェル部を含むエマルジョンを作製した後、乾燥させて得られるものである。
コア・シェル構造の微粒子のコア部／シェル部の重量比率は、ブリードアウトを防ぐ意味からコア部を２５重量％以上とすることが好ましく、粘度上昇を抑える意味からシェル部を３０重量％以上とすることが好ましい。
このようなアクリル系樹脂樹脂微粒子は、市販されているものを使用してもよく、三菱レイヨン社製ダイアナールＬＰ−３１０２がある。
【００１０】
上述のこれらの微粒子には、他のモノマーを共重合させたものであっても良い。他のモノマーとしては、Ｎ−オクチル（メタ）アクリレート、デシル（メタ）アクリレート、等の（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸、イタコン酸、クロトン酸等の不飽和カルボン酸、アクリロニトリル、（メタ）アクリルアミド、Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ−ジエチルアミノエチル（メタ）アクリレート、酢酸ビニル、α−メチルスチレン、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ジビニルベンゼン、グリシジル（メタ）アクリレート、アリル（メタ）アクリレート等が挙げられる。
【００１１】
また、コア・シェル構造のアクリル系樹脂微粒子の他に、プラスチゾルのスクリーン印刷適正を微調整する目的で、メチルメタクリレート、ベンジルメタクリレートから選ばれるモノマー単位を８０重量％以上含有する単一構造の微粒子を用いることが好ましい。この場合、アクリル系樹脂微粒子全体に対する単一構造の微粒子の重量比率は、単一構造の微粒子の粘度調整効果の大きい範囲である、５重量％〜３０重量％とすることが好ましい。
【００１２】
フタル酸エステル系可塑剤は、フタル酸ジ−ｎ−オクチル（ＤＯＰ）、フタル酸ジ−２−エチルヘキシル（ＤＩＮＰ）、フタル酸ブチルベンジル（ＢＢＰ）が使用され、特にフタル酸ジイソノニル（ＤＩＮＰ）が好適に使用される。
可塑剤の配合量は、特に制限はないが、アクリル系樹脂微粒子１００重量部に対し７０〜１５０重量部が好ましく、さらに好ましくは８０〜１００重量部である。７０重量部より少ないと、プラスチゾル粘度が上昇するために、スクリーンからの印刷適正が悪く、１５０重量部よい多いと、加熱固化された樹脂表面からの可塑剤のブリードアウトが問題になる。
また、その他の可塑剤を２次可塑剤として最大１０重量％程度であれば併用使用することも可能である。
【００１３】
無機充填材は、平均粒子径０．１〜１．５μｍであり、上記したフタル酸エステル系可塑剤の吸油量が前記充填材１００ｇに対して２５〜３５ｇのものを使用する。
平均粒子径が０．１μｍより小さい場合は、プラスチゾルの粘りが減少せず、ロータリースクリーン印刷法で基材に転写する際に、プラスチゾルがスクリーンから抜けにくくなる、所謂糸引き現象を生ずることになる。
平均粒径が、１．５μｍより大きい場合は、スクリーンに設けられるスクリーンメッシュにつまってしまう虞がある。
また、無機充填材の上記した可塑剤の吸収量が２５ｇより小さい場合、プラスチゾル中の無機充填材との親和性が悪いことになり、加熱固化された物の強度が劣り、特に耐摩耗性に劣るものとなる。上記の吸収量が３５ｇより大きいとプラスチゾルの粘度上昇が起こり、プラスチゾルの粘りも減少しない。
無機充填材の添加量は、特に制限されるものではないが、アクリル系樹脂微粒子１００重量部に対して、好ましくは１０〜３０重量部である。３０重量部より多いとプラスチゾルの粘度上昇のために塗工適正が悪化する傾向にあり、１０重量部より少ないと、粘り特性が改善されない傾向にある
無機充填材の材料としては、上記の条件を満たしたものであれば、特に制限はないが、例えば、コロイド状微粒子を呈する炭酸カルシウム（通称「コロイダル炭酸カルシウム」と呼ばれる）があり、表面を脂肪酸により処理した平均粒子径が０．１５μｍのものが好適に使用できる。
【００１４】
上記した配合のアクリル系プラスチゾル組成物には、さらに発泡剤を添加することができる。基材にある程度の高さの突起を無数有した建材を作製するには、熱可塑性殻体の内部に膨張性物質を含んだマイクロカプセル型発泡剤をプラスチゾルに混入させて加熱固化時に発泡させることによって高さアップがなされる。
【００１５】
また、アクリル系プラスチゾルは、塩化ビニル系プラスチゾルに比較して熱安定性や耐候性が良好であるが、必要ならば耐候安定剤、耐光安定剤等を添加しても良い。
必要に応じて、充填材、着色のための顔料等を添加しても良い。
【００１６】
アクリル系樹脂微粒子、フタル酸エステル系可塑剤を十分に混合攪拌して均一なプラスチゾルに調整する装置としては、その粘度特性などからディゾルバーミキサー、ホモミキサーなどの撹拌機が好適に使用される。
【００１７】
得られたアクリル系プラスチゾルは、ロータリースクリーン印刷法によって基材へ塗工され加熱されることによって固化する。加熱に関しては、樹脂の種類、可塑剤の配合量、塗工量により変化するが、一般的にオーブン加熱の場合は１１０℃〜１５０℃程度の温度で１分〜５分間程度が好ましい。
【００１８】
【実験例】
以下に具体的な実験例を挙げ、本発明のアクリル系樹脂プラスチゾル組成物に関して詳細に説明するが、本願発明は以下に挙げる例に限定されるものではない。
（アクリル系樹脂プラスチゾルの調製）
表１に示す薬品を計量混合し、プロペラミキサーで十分攪拌し実施例１及び２、比較例２〜８のプラスチゾルを調製した。なお、配合量は重量部で表した。
【表１】
アクリル系樹脂微粒子Ａ：コア・シェル構造アクリル重合体（コア部＝ノルマルブチルメタクリレート単独重合体、シェル部＝メチルメタクリレート／メタクリル酸のモノマー単位重量比が９９／１の共重合体、コア部／シェル部の重量比＝３０／７０、）、平均分子量＝約７０万
アクリル系樹脂微粒子Ｂ：メタクリル酸／メチルメタクリレートのモノマー単位重量比が９５／５の共重合体、平均分子量＝約２００万
アクリル系樹脂微粒子Ｃ：メチルメタクリレート単独重合体、平均分子量＝３００万
可塑剤Ａ：フタル酸ジ−２−エチルヘキシル（ＤＯＰ）
可塑剤Ｂ：フタル酸ジイソノニル（ＤＩＮＰ）
可塑剤Ｃ：アジピン酸ジオクチル（ＤＯＡ）
無機充填剤Ａ：コロイド状炭酸カルシウム（竹原化学工業社製、ネオライトＳＴ−Ｐ）、平均粒径０．１５μｍ、対ＤＯＰ吸油量２９ｇ
無機充填剤Ｂ：重質炭酸カルシウム（日東粉化工業社製、ＮＮ−１００）平均粒径２．１μｍ、対ＤＯＰ吸油量２４ｇ
無機充填剤Ｃ：タルク（富士タルク工業社製、ＬＳＭ１００）平均粒径４μｍ、吸油量４８ｇ
【００２０】
（性能評価）
表１の配合のアクリル系プラスチゾルについて、配合調製したアクリル系プラスチゾルの粘度をＢＭ型回転式粘度計（東京計器社製）を用いローター回転速度４ｒｐｍ、２０ｒｐｍにて調製直後、調製後１日保存後、調製後７日保存後にそれぞれ測定した。
そして、例えば調製直後で４ｒｐｍの粘度（Ｐａ・ｓ）測定値をη０−４に記すようにして、また例えば調製後７日保存後で２０ｒｐｍの粘度（Ｐａ・ｓ）測定値をη７−２０に記すようにして、その粘度測定結果を表１に示す。
【００２１】
また、配合調製したアクリル系プラスチゾルを紙上に、ナイフコーターにて０．１ｍｍの厚さでコーティングした後、１５０℃オーブンで２分間加熱してプラスチゾル固化物積層シートを得た。
得られたプラスチゾル固化物積層シートを常温にて７日間保管した後、プラスチゾル固化物表面のブリードアウトを触感にて評価した。
○：ブリードアウトなし
△：表面に僅かにブリードアウト有り
×：激しくブリードアウト有り
【００２２】
また、配合調製したアクリル系プラスチゾルを、１日保存後、ロータリースクリーン印刷法にて紙上に塗工した。
ロータリースクリーン装置としては、４０メッシュシリンダー上に、散点（ドット）状で３ｍｍの径の孔を有するスクリーンを使用し、塗工速度１０〜３０ｍ／ｍｉｎで塗工適性を評価した。
○：３０ｍ／ｍｉｎで塗工性良好
△：３０ｍ／ｍｉｎでは糸引き現象発生、１５ｍ／ｍｉｎならば塗工性良好
×：１０ｍ／ｍｉｎでも糸引き現象発生
【００２３】
ここで、糸引き現象とは、スクリーンより、プラスチゾルが完全に基材に転写されず、スクリーンメッシュで糸を引く状態を示す。主に、プラスチゾルの粘性が大きく、分子（粒子）間の相互作用が強いときに発生する。
【００２４】
【発明の効果】
以上説明したように、本発明のプラスチゾル組成物によれば、ブリードアウト及び経時による粘度上昇がほとんどなく、そして、スクリーン印刷法における糸引き現象の発生を大幅に抑制できるので、従来の塗工速度より大幅な速度アップを図ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an acrylic plastisol suitable for various coating methods, particularly a rotary screen printing method.
[0002]
[Prior art]
BACKGROUND ART Polyvinyl chloride plastisols using emulsion polymerized polyvinyl chloride resins and blended with plasticizers are used in various applications.
However, the development of acrylic plastisols using acrylic resins can be made by adding plasticizers as an alternative to polyvinyl chloride resins due to problems such as the generation of chlorine-based gases during combustion. Came to be done.
[0003]
As described above, the acrylic plastisol is mainly composed of an acrylic resin and a plasticizer. If the resin composition of the acrylic resin is highly soluble in the plasticizer, the obtained plastisol is obtained. Causes a rapid increase in viscosity, and cannot be used for coating such as knife coating and gravure coating, especially coating by the rotary screen printing method. On the other hand, if the resin composition has a low solubility in the plasticizer, an increase in viscosity can be prevented, but there is a problem that the plasticizer tends to bleed out over time after solidification by heating.
[0004]
JP-A-7-233299 discloses an acrylic sol using an acrylic resin fine particle having a core / shell structure and a dialkylphthalate plasticizer in order to solve the above-mentioned problem, and the shell portion is formed of the plasticizer. It is described that a rapid increase in viscosity is prevented as having a low solubility in water, and that the core portion is made of a resin composition having a high solubility in the plasticizer to prevent bleed-out after heating and solidification.
[0005]
On the other hand, building materials in which such acrylic plastisol is applied to a substrate such as plastics film or nonwoven fabric in the form of dots by a rotary screen printing method or the like and heated and solidified are used industrially. It has become.
[0006]
At that time, for example, in the rotary screen printing method, there is a problem that the plastisol cannot be made a good building material because it may cause a so-called stringing phenomenon that makes it difficult to come off from the screen due to its own stickiness characteristic. there were.
[0007]
[Problems to be solved by the invention]
The present invention has been made to solve the above-described problems, and provides an acrylic plastisol having characteristics suitable for various coating methods, particularly, a rotary screen printing method.
[0008]
[Means for Solving the Problems]
The acrylic plastisol for rotary screen printing of the present invention mainly comprises acrylic resin fine particles, a phthalate ester plasticizer, and an inorganic filler, and the acrylic resin fine particles comprise fine particles of a core / shell structure. The core portion of the fine particles is composed of a resin containing 50% by weight or more of a monomer unit selected from ethyl methacrylate, normal butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, and ethyl hexyl methacrylate, and the shell portion is methyl. Consists of a resin containing 50% by weight or more of a monomer unit selected from methacrylate, benzyl methacrylate, and styrene. The phthalate ester plasticizer is phthalate-2-ethylhexyl, phthalate di Sononiru is at least one selected from butyl benzyl phthalate, inorganic filler is a colloidal calcium carbonate having an average particle diameter of 0.1 to 1.5 [mu] m, and the phthalic acid ester per the colloidal calcium carbonate 100g system plasticizer maximum absorption is, 25 to 35 g der is, relative to 100 parts by weight of the acrylic resin fine particles, a phthalate plasticizer 70 to 150 parts by weight, the inorganic filler is 10 to 30 parts by weight of formulation It is characterized by that.
The maximum absorption amount that the inorganic filler absorbs the phthalate ester plasticizer may be simply referred to as oil absorption amount. The amount of oil absorption varies depending on the type of plasticizer, but there is almost no change between the above-mentioned plasticizers. The oil absorption is in accordance with the JIS K5101 oil absorption measurement method.
[0009]
The fine particles having a core / shell structure can be obtained by emulsion polymerization or suspension polymerization, but preferably by emulsion polymerization. In the case of emulsion polymerization, an emulsion including a core portion is first prepared, and subsequently an emulsion including a shell portion coated with the core portion is prepared, followed by drying.
The core / shell weight ratio of the fine particles of the core / shell structure is preferably 25% by weight or more from the viewpoint of preventing bleed out, and 30% by weight or more of the shell part from the viewpoint of suppressing an increase in viscosity. It is preferable to do.
As such acrylic resin resin fine particles, commercially available ones may be used, and there is Dianaal LP-3102 manufactured by Mitsubishi Rayon Co., Ltd.
[0010]
These fine particles described above may be those obtained by copolymerizing other monomers. Other monomers include N-octyl (meth) acrylate, decyl (meth) acrylate and other (meth) acrylic acid alkyl esters, (meth) acrylic acid, itaconic acid, crotonic acid and other unsaturated carboxylic acids, acrylonitrile, (Meth) acrylamide, N-dimethyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, vinyl acetate, α-methylstyrene, hydroxyethyl (meth) acrylate, hydroxypropyl ( Examples include meth) acrylate, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, divinylbenzene, glycidyl (meth) acrylate, and allyl (meth) acrylate.
[0011]
In addition to the core / shell structure acrylic resin fine particles, single-structure fine particles containing 80% by weight or more of a monomer unit selected from methyl methacrylate and benzyl methacrylate for the purpose of fine-tuning the suitability of plastisol for screen printing. It is preferable to use it. In this case, the weight ratio of the fine particles having a single structure to the entire acrylic resin fine particles is preferably 5% by weight to 30% by weight, which is a range in which the viscosity adjusting effect of the fine particles having a single structure is large.
[0012]
As the phthalate ester plasticizer, di-n-octyl phthalate (DOP), di-2-ethylhexyl phthalate (DINP), and butylbenzyl phthalate (BBP) are used, and diisononyl phthalate (DINP) is particularly preferable. Used for.
Although the compounding quantity of a plasticizer does not have a restriction | limiting in particular, 70-150 weight part is preferable with respect to 100 weight part of acrylic resin fine particles, More preferably, it is 80-100 weight part. If the amount is less than 70 parts by weight, the viscosity of the plastisol increases, so that the printing suitability from the screen is poor, and if it is more than 150 parts by weight, bleeding out of the plasticizer from the heat-solidified resin surface becomes a problem.
Also, other plasticizers can be used in combination as long as the secondary plasticizer is about 10% by weight at the maximum.
[0013]
The inorganic filler has an average particle diameter of 0.1 to 1.5 μm, and the oil absorption amount of the phthalate ester plasticizer is 25 to 35 g with respect to 100 g of the filler.
When the average particle size is smaller than 0.1 μm, the viscosity of the plastisol does not decrease, and a so-called stringing phenomenon occurs in which the plastisol is difficult to come off from the screen when transferred to the substrate by the rotary screen printing method. .
If the average particle size is larger than 1.5 μm, the screen mesh provided on the screen may become clogged.
In addition, when the above-described plasticizer absorption amount of the inorganic filler is less than 25 g, the affinity with the inorganic filler in the plastisol is poor, and the strength of the heat-solidified product is inferior, particularly in wear resistance. It will be inferior. If the absorption amount is larger than 35 g, the viscosity of the plastisol increases and the viscosity of the plastisol does not decrease.
The addition amount of the inorganic filler is not particularly limited, but is preferably 10 to 30 parts by weight with respect to 100 parts by weight of the acrylic resin fine particles. When the amount is more than 30 parts by weight, the coating suitability tends to deteriorate due to an increase in the viscosity of the plastisol. When the amount is less than 10 parts by weight, the above-mentioned conditions are used as the inorganic filler material which tends to not improve the stickiness characteristics. There is no particular limitation as long as it is satisfied, but for example, there is calcium carbonate exhibiting colloidal fine particles (commonly called “colloidal calcium carbonate”), and the average particle diameter of the surface treated with fatty acid is 0.15 μm Can be suitably used.
[0014]
A foaming agent can be further added to the acrylic plastisol composition having the above composition. To produce a building material with countless protrusions of a certain height on the base material, a microcapsule-type foaming agent containing an expandable substance inside the thermoplastic shell is mixed into the plastisol and foamed when heated and solidified. Increases the height.
[0015]
Acrylic plastisol has better thermal stability and weather resistance than vinyl chloride plastisol, but if necessary, a weather stabilizer, a light stabilizer and the like may be added.
You may add a filler, the pigment for coloring, etc. as needed.
[0016]
As an apparatus for sufficiently mixing and stirring the acrylic resin fine particles and the phthalate ester plasticizer to prepare a uniform plastisol, a stirrer such as a dissolver mixer or a homomixer is preferably used because of its viscosity characteristics.
[0017]
The obtained acrylic plastisol is solidified by being applied to a substrate by a rotary screen printing method and being heated. Regarding heating, it varies depending on the type of resin, the blending amount of the plasticizer, and the coating amount, but generally in the case of oven heating, a temperature of about 110 ° C. to 150 ° C. is preferably about 1 minute to 5 minutes.
[0018]
[Experimental example]
Specific experimental examples will be given below, and the acrylic resin plastisol composition of the present invention will be described in detail. However, the present invention is not limited to the following examples.
(Preparation of acrylic resin plastisol)
The chemicals shown in Table 1 were weighed and mixed and sufficiently stirred with a propeller mixer to prepare plastisols of Examples 1 and 2 and Comparative Examples 2 to 8. The blending amount was expressed in parts by weight.
[Table 1]
Acrylic resin fine particle A: core / shell structure acrylic polymer (core portion = normal butyl methacrylate homopolymer, shell portion = methyl methacrylate / methacrylic acid monomer unit weight ratio 99/1 copolymer, core portion / shell Part weight ratio = 30/70), average molecular weight = about 700,000 acrylic resin fine particles B: copolymer having a methacrylic acid / methyl methacrylate monomer unit weight ratio of 95/5, average molecular weight = about 2 million acrylic Resin fine particles C: methyl methacrylate homopolymer, average molecular weight = 3 million plasticizer A: di-2-ethylhexyl phthalate (DOP)
Plasticizer B: Diisononyl phthalate (DINP)
Plasticizer C: Dioctyl adipate (DOA)
Inorganic filler A: colloidal calcium carbonate (manufactured by Takehara Chemical Industries, Neolite ST-P), average particle size 0.15 μm, oil absorption DOP 29 g
Inorganic filler B: heavy calcium carbonate (manufactured by Nitto Flour Chemical Co., Ltd., NN-100) average particle diameter 2.1 μm, oil absorption DOP 24 g
Inorganic filler C: talc (manufactured by Fuji Talc Kogyo Co., Ltd., LSM100) average particle size 4 μm, oil absorption 48 g
[0020]
(Performance evaluation)
For the acrylic plastisol blended in Table 1, the viscosity of the acrylic plastisol blended and prepared was immediately after preparation at a rotor rotational speed of 4 rpm and 20 rpm using a BM type rotary viscometer (manufactured by Tokyo Keiki Co., Ltd.) and after storage for 1 day after preparation. The measurement was made after storage for 7 days after preparation.
And, for example, the viscosity (Pa · s) measurement value at 4 rpm is written in η0-4 immediately after the preparation, and the viscosity (Pa · s) measurement value at 20 rpm is stored in η7-20 after storage for 7 days after the preparation. The viscosity measurement results are shown in Table 1 as described.
[0021]
The acrylic plastisol thus prepared was coated on paper with a thickness of 0.1 mm using a knife coater, and then heated in a 150 ° C. oven for 2 minutes to obtain a plastisol-solidified laminate sheet.
The obtained plastisol solidified product laminated sheet was stored at room temperature for 7 days, and then the bleedout on the surface of the plastisol solidified product was evaluated by tactile sensation.
○: No bleed-out △: Slightly bleed-out on the surface ×: Strongly bleed-out [0022]
Further, the acrylic plastisol prepared and prepared was stored for 1 day and then coated on paper by a rotary screen printing method.
As a rotary screen device, a screen having dots of 3 mm diameter on a 40 mesh cylinder was used, and coating suitability was evaluated at a coating speed of 10 to 30 m / min.
◯: Good coating property at 30 m / min Δ: Threading phenomenon occurs at 30 m / min, Good coating property at 15 m / min ×: Threading phenomenon occurs even at 10 m / min
Here, the thread drawing phenomenon indicates a state in which the plastisol is not completely transferred from the screen to the base material, and the thread is pulled by the screen mesh. This occurs mainly when plastisol has a high viscosity and a strong interaction between molecules (particles).
[0024]
【The invention's effect】
As described above, according to the plastisol composition of the present invention, there is almost no increase in viscosity due to bleed-out and aging, and the occurrence of stringing phenomenon in the screen printing method can be greatly suppressed, so that the conventional coating speed A greater speed increase can be achieved.
Claims (1)
アクリル系樹脂微粒子が、コア・シェル構造の微粒子からなり、コア・シェル構造の微粒子のコア部が、エチルメタクリレート、ノルマルブチルメタクリレート、イソブチルメタクリレート、ターシャリーブチルメタクリレート、シクロヘキシルメタクリレート、エチルヘキシルメタクリレートから選ばれるモノマー単位を５０重量％以上含有した樹脂にて構成され、シェル部が、メチルメタクリレート、ベンジルメタクリレート、スチレンから選ばれるモノマー単位を５０重量％以上含有した樹脂にて構成され、
フタル酸エステル系可塑剤が、フタル酸−２−エチルヘキシル、フタル酸ジイソノニル、フタル酸ブチルベンジルから選ばれる一種以上であり、
無機充填材は、平均粒子径０．１〜１．５μｍのコロイド状炭酸カルシウムであり、かつ、前記コロイド状炭酸カルシウム１００ｇ当たりの前記フタル酸エステル系可塑剤最大吸収量が、２５〜３５ｇであり、
アクリル系樹脂微粒子１００重量部に対し、フタル酸エステル系可塑剤は７０〜１５０重量部、無機充填材は１０〜３０重量部配合されることを特徴とするロータリースクリーン印刷用アクリル系プラスチゾル。Mainly composed of acrylic resin fine particles, phthalate plasticizer and inorganic filler,
Acrylic resin fine particles composed of core / shell structured fine particles, and the core of the core / shell structured fine particles is a monomer selected from ethyl methacrylate, normal butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, and ethyl hexyl methacrylate. It is composed of a resin containing 50% by weight or more of the unit, and the shell part is composed of a resin containing 50% by weight or more of a monomer unit selected from methyl methacrylate, benzyl methacrylate, and styrene,
The phthalate ester plasticizer is at least one selected from 2-ethylhexyl phthalate, diisononyl phthalate, and butyl benzyl phthalate,
The inorganic filler is colloidal calcium carbonate having an average particle size of 0.1 to 1.5 μm, and the maximum absorption amount of the phthalate plasticizer per 100 g of the colloidal calcium carbonate is 25 to 35 g. The
Acrylic plastisol for rotary screen printing , wherein 70 to 150 parts by weight of phthalate ester plasticizer and 10 to 30 parts by weight of inorganic filler are blended with 100 parts by weight of acrylic resin fine particles .
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| JP4770540B2 (en) * | 2006-03-27 | 2011-09-14 | Ｔｄｋ株式会社 | Ceramic paste, method for producing the same, and method for producing multilayer ceramic electronic component using the ceramic paste |
| KR100971509B1 (en) | 2008-11-21 | 2010-07-21 | (주)엘지하우시스 | Composition for rotary screen printing, interior wallpaper comprising the above and manufacturing method thereof |
| CN102585644B (en) * | 2012-03-05 | 2013-12-25 | 湖北联合天诚防伪技术股份有限公司 | Anti-counterfeiting electrochemical aluminum paint and preparation method thereof |
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| JPS58179278A (en) * | 1982-04-12 | 1983-10-20 | Mitsubishi Rayon Co Ltd | Ink composition |
| JPH06340836A (en) * | 1993-05-31 | 1994-12-13 | Sumitomo Chem Co Ltd | Paste sol composition for rotary screen printing and preparation thereof |
| JPH07233299A (en) * | 1994-02-23 | 1995-09-05 | Mitsubishi Rayon Co Ltd | Acrylic sol |
| JPH0931860A (en) * | 1995-07-19 | 1997-02-04 | Kyowa Leather Cloth Co Ltd | Wall covering |
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