JPH03250062A - Active energy ray-curable coating composition - Google Patents
Active energy ray-curable coating compositionInfo
- Publication number
- JPH03250062A JPH03250062A JP2048853A JP4885390A JPH03250062A JP H03250062 A JPH03250062 A JP H03250062A JP 2048853 A JP2048853 A JP 2048853A JP 4885390 A JP4885390 A JP 4885390A JP H03250062 A JPH03250062 A JP H03250062A
- Authority
- JP
- Japan
- Prior art keywords
- active energy
- energy ray
- curable
- curable coating
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000008199 coating composition Substances 0.000 title claims description 15
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000004094 surface-active agent Substances 0.000 abstract description 10
- -1 acryloyloxy groups Chemical group 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 abstract description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 4
- 230000002411 adverse Effects 0.000 abstract description 2
- 238000010894 electron beam technology Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004634 thermosetting polymer Substances 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 9
- 229920003002 synthetic resin Polymers 0.000 description 9
- 239000000057 synthetic resin Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920000298 Cellophane Polymers 0.000 description 4
- 239000000113 methacrylic resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は合成樹脂成形品に用いられるコーティング用組
成物に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a coating composition used for synthetic resin molded articles.
〈従来の技術〉
合成樹脂成形品はガラス製品に比較して軽量であり、か
つ強靭性などの特性に優れているばかりでなく、安価で
成形加工が容易であるなどの利点があり広い分野で使用
されている。<Conventional technology> Compared to glass products, synthetic resin molded products are not only lighter and have superior properties such as toughness, but also have advantages such as being inexpensive and easy to mold, so they are used in a wide range of fields. It is used.
しかしながら、これらの合成樹脂成形品はその表面の硬
度や耐摩耗性が不足しているために、接触、衝撃、引っ
掻きなどの作用によって表面が損傷を受は易いという欠
点がある。However, these synthetic resin molded products have a drawback in that their surfaces are easily damaged by contact, impact, scratching, and the like because their surfaces lack hardness and wear resistance.
これらの欠点を改良するために、合成樹脂成形品の表面
に架橋硬化被膜を形成させる方法が種々検討されている
。例えば、重合性七ツマ−を合成樹脂成形品の表面に塗
布し、ついで紫外線を照射し、架橋硬化被膜を形成し、
耐摩耗性に優れた表面を有する成形品を得る方法等が提
案されている。 （特公昭４８−４２２１１号公報、
特公昭４９−２２９５１号公報、特開昭５３１０２９３
６号公報、特開昭５３−１０４６３８号公報、特開昭５
８−１０１１２１号公報、及び特公昭５Ｂ−１２９０１
８号公報）しかし架橋硬化被膜を形成する重合性モノマ
ーは高粘度であり、樹脂成形品に塗布したとき平滑な表
面が得られ難い。表面平滑性を改良する方法として重合
性七ツマー組成物に各種のレベリング剤を添加したり、
シリコーン系の界面活性剤を添加することが行われてい
る。（特開昭５５−９８２６５号公報、特開昭５６−８
６１号公１！
〈発明が解決しようとする！！題〉
しかしながら、レベリング剤は表面を平滑にする効果は
大きいが、フッ素或いはシリコーン系の化合物が用いら
れているために、得られた架橋被膜上に印刷や塗装をす
ることが出来ない。シリコーン系の界面活性剤を添加す
る方法も同様の問題がある。In order to improve these drawbacks, various methods of forming a crosslinked cured film on the surface of a synthetic resin molded article have been studied. For example, a polymerizable 7-mer is applied to the surface of a synthetic resin molded product, and then UV rays are irradiated to form a crosslinked cured film.
Methods for obtaining molded products having surfaces with excellent wear resistance have been proposed. (Special Publication No. 48-42211,
Japanese Patent Publication No. 49-22951, Japanese Patent Publication No. 5310293
Publication No. 6, JP-A-53-104638, JP-A-5
Publication No. 8-101121, and Special Publication No. 5B-12901
(No. 8) However, the polymerizable monomer that forms the crosslinked cured film has a high viscosity, and it is difficult to obtain a smooth surface when applied to a resin molded product. As a method of improving surface smoothness, various leveling agents are added to the polymerizable 7-mer composition,
Addition of silicone-based surfactants has been carried out. (Unexamined Japanese Patent Publication No. 55-98265, Unexamined Japanese Patent Publication No. 56-8
No. 61 Public 1! <Invention tries to solve! ! Problem> However, although leveling agents have a great effect on smoothing the surface, since fluorine or silicone-based compounds are used, it is not possible to print or paint on the resulting crosslinked film. Similar problems arise with the method of adding silicone surfactants.
〈課題を解決するための手段〉
本発明はアニオン系界面活性剤を硬化後の固形分１００
重量部に対して０．００１〜１０重量部含有することを
特徴とする活性エネルギー線硬化性コーティング用組成
物に関する。<Means for Solving the Problems> The present invention provides anionic surfactants with a solid content of 100% after curing.
It relates to an active energy ray-curable coating composition characterized by containing 0.001 to 10 parts by weight.
本発明に用いられるアニオン系界面活性剤は硬化被膜の
表面の平滑性を改良するために特に効果があるものであ
り、例えば、スルホン酸塩、スルホコハク酸塩、脂肪酸
塩、硫酸エステル塩、燐酸塩、燐酸エステル、炭酸塩等
を示すことができる０合成樹脂成形品と活性エネルギー
線硬化性コーティング組成物液との濡れを改良し、ハジ
キを無くし、さらには硬化被膜の表面の平滑性を特に優
れたものにするためには、これらのアニオン系界面活性
剤の中でスルホン酸塩系又はスルホコハク酸塩系の界面
活性剤が最も好ましい、これらを具体的に例示すれば、
アルキルベンセーンスルホン酸ソーダ、ベンゼンスルホ
ン酸ソーダ、及びスルホコハク酸ソーダが活性エネルギ
ー線硬化性コーティング組成物液に対する溶解性及び硬
化被膜の優れた平滑性を得るために特に好ましい。これ
らのアニオン系界面活性剤は２種類以上を併用すること
もできる。本発明において、アニオン系界面活性剤の使
用量は、活性エネルギー線硬化性コーティング組成物液
の硬化後の固形分１００重量部に対して０．００１〜１
０重量部、好ましくは０．０５〜８重量部の範囲で用い
ることができる。The anionic surfactants used in the present invention are particularly effective for improving the surface smoothness of the cured film, and include, for example, sulfonates, sulfosuccinates, fatty acid salts, sulfate ester salts, and phosphates. , phosphoric acid ester, carbonate, etc. It improves the wetting of the active energy ray-curable coating composition liquid with the synthetic resin molded product, eliminates repelling, and furthermore, the surface smoothness of the cured film is particularly excellent. Among these anionic surfactants, sulfonate-based or sulfosuccinate-based surfactants are most preferred.Specific examples of these include:
Sodium alkylbenzene sulfonate, sodium benzenesulfonate, and sodium sulfosuccinate are particularly preferred in order to obtain solubility in the active energy ray-curable coating composition liquid and excellent smoothness of the cured film. Two or more types of these anionic surfactants can also be used in combination. In the present invention, the amount of anionic surfactant used is 0.001 to 1 part by weight based on 100 parts by weight of the solid content after curing of the active energy ray-curable coating composition liquid.
It can be used in an amount of 0 parts by weight, preferably 0.05 to 8 parts by weight.
アニオン系界面活性剤の添加量が０．００１重量部より
少ないと硬化被膜の表面の平滑化の効果は認められず、
また、１０重量部より多くなると、硬化被膜の硬度の低
下や合成樹脂成形品への密着性の低下等の問題が発生ず
る。If the amount of anionic surfactant added is less than 0.001 part by weight, no effect on smoothing the surface of the cured film will be observed.
If the amount exceeds 10 parts by weight, problems such as a decrease in the hardness of the cured film and a decrease in adhesion to synthetic resin molded articles will occur.
本発明に使用される活性エネルギー線硬化性コーティン
グ組成物は紫外線、電子線、ガンマ線等によって硬化す
るものがあげられる。なかでも紫外線によって硬化する
組成物が取り扱い易く好ましい。The active energy ray-curable coating composition used in the present invention includes those that are cured by ultraviolet rays, electron beams, gamma rays, and the like. Among these, compositions that are cured by ultraviolet light are preferred because they are easy to handle.
紫外線によって硬化するコーティング組成物としては、
１分子中に２個以上のアクリロイルオキシ基またはメタ
クリロイルオキシ基を含有した七ツマまたはオリゴマー
或いはそれらの混合物があげられる。これらのモノマー
またはオリゴマーには粘度のＥＪＩ整や性能改質のため
に各種重合性モノマーや希釈剤等を混合して用いてもよ
い。本発明に用いられる活性エネルギー線硬化性コーテ
ィング組成物としては、例えば、特開昭５０−８２１７
３号公報、同５０−１１０４７７号公報、同５４−１１
３６９３号公報、同５５−６９６７０号公報、同５６−
８６１号公報、同５６−１２２８４０号公報、同５８−
８７１１７号公報、同５Ｂ−１０１１２１号公報、同５
８−１２９０１８号公報、同６３−６８６４２号公報、
同６３−１６８４１９号公報特開平１−１７４５１５号
公報に記載されているものがあげられる。As a coating composition that is cured by ultraviolet light,
Examples include monomers or oligomers containing two or more acryloyloxy groups or methacryloyloxy groups in one molecule, or mixtures thereof. These monomers or oligomers may be mixed with various polymerizable monomers, diluents, etc. for EJI adjustment of viscosity and performance improvement. The active energy ray-curable coating composition used in the present invention includes, for example, JP-A-50-8217
Publication No. 3, Publication No. 50-110477, Publication No. 54-11
Publication No. 3693, Publication No. 55-69670, Publication No. 56-
No. 861, No. 56-122840, No. 58-
No. 87117, No. 5B-101121, No. 5
No. 8-129018, No. 63-68642,
Examples include those described in JP-A No. 63-168419 and JP-A-1-174515.
本発明の活性エネルギー線硬化性コーティング組組物を
塗布する合成樹脂としては、熱可塑性樹脂、熱硬化性樹
脂の区別なく使用され、例えば、ポリメチルメタクリレ
ート等のアクリル系樹脂、ポリカーボネート、ポリアリ
ルジグリコールカーボネート樹脂、ＡＢＳ樹脂、ポリス
チレン、ポリ塩化ビニル、ポリエステル樹脂、アセテー
ト樹脂等が用いられる。The synthetic resin to which the active energy ray-curable coating assembly of the present invention is applied may be either thermoplastic resin or thermosetting resin. For example, acrylic resin such as polymethyl methacrylate, polycarbonate, polyallyl Glycol carbonate resin, ABS resin, polystyrene, polyvinyl chloride, polyester resin, acetate resin, etc. are used.
合成樹脂成形品への塗布方法は特に限定されず、スプレ
ー塗装、ロールコート、浸せき塗装、スピンコード等公
知の方法により塗布することができる。The method of coating the synthetic resin molded product is not particularly limited, and can be coated by known methods such as spray coating, roll coating, dip coating, and spin cord.
本発明の活性エネルギー線硬化性コーティング組成物は
、硬化被股上の印刷性及び塗装性に悪影響を及ぼすこと
なく、硬化被膜の表面の平滑性を改良できるものである
。The active energy ray-curable coating composition of the present invention can improve the surface smoothness of a cured film without adversely affecting the printability and paintability of the cured coating.
〈実施例〉 以下、実施例により本発明をさらに具体的に説明する。<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.
Ａ、コーティング用組成物の成分の製造例（１）多官能
上ツマーニジペンタエリスリトールへキサアクリレート
の合成
攪拌糎、温度針、水分離器を備えつけた１リットルのガ
ラス製反応器にジペンタエリスリトール１２７ｇ、アク
リル＃２５９ｇ、混合溶媒（ベンゼン：シクロヘキサン
＝２： １）１２７ｇ：硫酸６．３５ｇ、硫酸銅０．５
１ｇ、ハイドロキノンモノメチルエーテル０．０３ｇを
仕込んだ。A. Example of manufacturing components of coating composition (1) Synthesis of polyfunctional dipentaerythritol hexaacrylate 127 g of dipentaerythritol was placed in a 1-liter glass reactor equipped with a stirring starch, a temperature needle, and a water separator. , Acrylic #259g, mixed solvent (benzene:cyclohexane=2:1) 127g: sulfuric acid 6.35g, copper sulfate 0.5g
1 g of hydroquinone monomethyl ether and 0.03 g of hydroquinone monomethyl ether were charged.
攪拌と空気吹き込みを行いつつ還流下で反応を行い、留
出する有機溶媒・水共沸混合物は冷却後水と分離し、有
機溶媒は反応系へ返すようにして反応させ、水５２ｃｃ
が留出した。そこで反応液を冷却し、混合溶媒（ベンゼ
ン：シクロヘキサン＝２ ： １）２５４ｇを加え、濃
度１０％の苛性ソーダ水溶液で中和した後、分液し油層
を１０％の食塩水で洗浄した。ついで、油層は無水硫酸
マグネシウムで乾燥後、５０〜６０度（摂氏）で減圧下
に混合溶媒を除き、釜残としてジペンタエリスリトール
へキサアクリレート２７１ｇを得た。このものの粘度は
９４１０ ｃｐｓ／２５度（摂氏）、エステル価は５５
２（理論値５８２．５）であった。The reaction is carried out under reflux while stirring and blowing air, and the distilled organic solvent/water azeotrope is separated from water after cooling, and the organic solvent is returned to the reaction system.
was distilled out. Thereupon, the reaction solution was cooled, 254 g of a mixed solvent (benzene: cyclohexane = 2:1) was added, and after neutralization with a 10% aqueous solution of caustic soda, the mixture was separated and the oil layer was washed with 10% brine. Then, the oil layer was dried over anhydrous magnesium sulfate, and the mixed solvent was removed under reduced pressure at 50 to 60 degrees Celsius to obtain 271 g of dipentaerythritol hexaacrylate as a residue. The viscosity of this product is 9410 cps/25 degrees (Celsius), and the ester value is 55.
2 (theoretical value 582.5).
（２）多官能ウレタンアクリレート
攪拌機、温度計、滴下ロートを備えた１リツトルのガラ
ス製反応器にトリメチロールプロパンジアクリレート２
４２ｇ、ハイドロキノンモノメチルエーテル０８２５ｇ
を入れ、温度を６０度（摂氏）に保持した中に、２．、
ｌ）リレンジイソシアネー）８５ｇを１時間を要して滴
下した。同温度で１時間攪拌し、ジブチル錫ジアセテー
トを０．０５ｇ添加してさらに２時間反応を続け、反応
を完結させた後、多官能ウレタンアクリレート３２５ｇ
を得た。このもののイソシアネート含量は０．０３％で
あった。(2) Polyfunctional urethane acrylate Trimethylolpropane diacrylate 2.
42g, hydroquinone monomethyl ether 0825g
2. ,
l) lylene diisocyanate) was added dropwise over a period of 1 hour. After stirring at the same temperature for 1 hour, 0.05 g of dibutyltin diacetate was added and the reaction was continued for another 2 hours. After the reaction was completed, 325 g of polyfunctional urethane acrylate was added.
I got it. The isocyanate content of this was 0.03%.
Ｂ、界面活性剤
本実施例及び比較例において用いた界面活性剤を次に記
した。これらはいずれも日本油脂（株）製のものを用い
た。B. Surfactant The surfactant used in this example and comparative example is described below. All of these were manufactured by Nippon Oil & Fats Co., Ltd.
（１）アニオン系界面活性剤
・バーソフトＳＦ（商品名） ：
アルキルサルフェー）Ｎａ塩
・バーソフトＥＬＴ（＊品名）：
アルキルエーテルサルフェートＮａ塩
ニューレックスＲ（商品名）ニ
ドデシルベンゼンスルホン酸Ｎ ａ 塩・ダイヤボンＳ
（商品名）ニ
アシルメチルタウリン酸Ｎ ａ 塩
・ラビゾールＢ−９０（商品名）ニ
ジオクチルスルホコハクｆｌｉ Ｎ ａ Ｐ。(1) Anionic surfactant/Barsoft SF (product name): Alkyl sulfate) Na salt/Barsoft ELT (*product name): Alkyl ether sulfate Na salt Newlex R (product name) Nidodecylbenzenesulfonic acid N a Salt/Diabon S
(Product name) Niacylmethyltauric acid Na salt/Rabisol B-90 (Product name) Nidioctyl sulfosuccinic acid Na P.
・ポリスターＭ（商品名） ：
カルボン酸型アニオン
（２）ノニオン系界面活性剤
ノニオンＥ−２０６（商品名）：
ポリオキシエチレンオレイルエーテル
（３）カチオン系界面活性剤
・カチオンＡＢ（商品名）：
オクタデシルトリメチルアンモニウムクロライド
実施例１〜６、比較例１〜４
前記の方法で合成したジペンタエリスリトールへキサア
クリレート２５０ｇ、多官能ウレタンアクリレート２５
０ｇに希釈剤としてキシレン４６７ ｇ。・Polystar M (product name): Carboxylic acid type anion (2) Nonionic surfactant Nonion E-206 (product name): Polyoxyethylene oleyl ether (3) Cationic surfactant ・Cation AB (product name): Octadecyltrimethylammonium chloride Examples 1 to 6, Comparative Examples 1 to 4 250 g of dipentaerythritol hexaacrylate synthesized by the above method, 25 g of polyfunctional urethane acrylate
467 g of xylene as diluent to 0 g.
酢酸ブチル２９２ｇ、エチルセロソルブ２３３ｇ、ジア
セトンアルコール１７５ｇ、及び光増感剤としてｌ−ヒ
ドロキシシクロへキシルフェニルケトンを７．５ｇを加
えて十分に混合した。292 g of butyl acetate, 233 g of ethyl cellosolve, 175 g of diacetone alcohol, and 7.5 g of l-hydroxycyclohexylphenyl ketone as a photosensitizer were added and thoroughly mixed.
この混合液１００ｇに前記の各種の界面活性剤を０．０
６ｇ （硬化被膜固形分１００重量部に対して０．２重
量部に相当する）を添加して十分混合して紫外線硬化性
コーティング組成物溶液とした。Add 0.0 of the various surfactants mentioned above to 100 g of this mixed solution.
6 g (corresponding to 0.2 parts by weight based on 100 parts by weight of the solid content of the cured film) was added and thoroughly mixed to prepare an ultraviolet curable coating composition solution.
この紫外線硬化性コーティング組成物溶液に厚さ２１の
メタクリル樹脂板（スミペックス”＃０００−住友化学
工業（株）製）を浸せきして被膜を形成させ、２０分間
放置後、空気中にて高圧水銀灯（アイグラフィックス社
製、アイキュアーＵＥＯ２１４０３Ｃ１５００Ｖ、ＨＯ
２−Ｌ４１ （２））を用いて２５０ｍ５の距離から
１２０Ｗ、５秒間紫外線照射を行った。得られた表面硬
化メタクリル樹脂板の硬化被膜の密着性、印刷性、外観
及び硬度を評価して第１表及び第２表に記した。A 21-thick methacrylic resin plate (Sumipex #000, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in this ultraviolet curable coating composition solution to form a film, and after being left for 20 minutes, it was exposed to a high-pressure mercury lamp in the air. (manufactured by iGraphics, iCure UEO21403C1500V, HO
2-L41 (2)) was used to irradiate ultraviolet light at 120 W for 5 seconds from a distance of 250 m5. The adhesion, printability, appearance, and hardness of the cured film of the obtained surface-cured methacrylic resin plate were evaluated and are listed in Tables 1 and 2.
評価方法
（１）密着性
クロスカットセロハンテープ剥離テスト：硬化被膜に１
１１Ｉ１１間隔に基材に達する被膜切断線を縦横それぞ
れ１１本人れて、［ｌの目数を１００個つくり、その上
にセロハンテープを貼り付は急激に剥がす。Evaluation method (1) Adhesion cross-cut cellophane tape peeling test: 1 on the cured film
Cut 11 film cutting lines vertically and horizontally to reach the base material at intervals of 11I11 to make 100 [l] grids, and then apply cellophane tape on top of it and peel it off rapidly.
このセロハンテープ剥離の操作を同一箇所で３回繰り返
した後、剥離しなかった目数の数で表した。After repeating this cellophane tape peeling operation three times at the same location, it was expressed as the number of stitches that did not peel off.
（２）印刷性
印刷インキ５Ｓ−２５（東洋インキ（株）製）を使用し
て１５＊１５ｍｍのマス目にスクリーン印刷を行い、硬
化後そのままでセロハンテープで密着性をしらべた。(2) Printability Screen printing was performed using printing ink 5S-25 (manufactured by Toyo Ink Co., Ltd.) in squares of 15*15 mm, and after curing, adhesion was checked using cellophane tape.
良 ：全く剥離の無いもの
不可ニ一部または全部剥離したもの
（３）外観
優 ：平滑性に優れ、コート液のハジキによるピンホー
ルが全く無いもの
良 ：平滑性に優れ、コート液のハジキによるピンホー
ルが２個以下のもの
不可：平滑性が悪く、コート液のハジキによるピンホー
ルが多数あるもの
（４）硬度
＃１０００のスチールウールによる擦傷テスＡ：強（こ
すっても傷がつかない
Ｂ；強くこするとわずかに傷がつく
Ｃ：軽くこするとわずかに傷がつく
Ｄ：軽くこすっても著しく傷がつく
ト
第１表
第２表
Ａ−１：パーソフトＳＦ、Ａ−２：パーソフトＥＬＴＡ
−３：ニューレフクスＲ，Ａ−４：ダイヤボン５Ａ−５
：ラビソールＢ−９０、Ａ−６：ボリスターＭＮ−１＝
ノニオンＥ−２０６、Ｃ−１：カチオンＡＢＳ：シリコ
ン５Ｈ２８ＰＡ （シリコーン系レベリング剤−東しシ
リコン（株）製）
Ｆ：フロラードＦＣ−４３０（フッ素系界面活性剤住友
スリーエム（株）製）
アニオン系界面活性剤を用いた場合には外観、印刷性と
もに良好であった。なかでも実施例３及び５においては
、ハジキも無く外観がと（に優れていた。Good: No peeling at all. Partial or total peeling. (3) Excellent appearance: Excellent smoothness, no pinholes caused by repelling of the coating liquid. Good: Excellent smoothness, no pinholes due to repelling of the coating liquid. Items with 2 or less pinholes are not acceptable: Items with poor smoothness and many pinholes due to repellency of the coating liquid (4) Scratch test with #1000 hardness steel wool A: Strong (no scratches even when rubbed B) ; Slight scratches when rubbed strongly C: Slight scratches when rubbed lightly D: Significant scratches even when rubbed lightly T Table 1 Table 2 A-1: Per Soft SF, A-2: Per Soft ELTA
-3: New Refx R, A-4: Diabon 5A-5
: Lavisole B-90, A-6: Bolister MN-1=
Nonionic E-206, C-1: Cationic ABS: Silicone 5H28PA (Silicone leveling agent - manufactured by Toshi Silicon Co., Ltd.) F: Florado FC-430 (fluorosurfactant manufactured by Sumitomo 3M Co., Ltd.) Anionic interface When the activator was used, both the appearance and printability were good. In particular, in Examples 3 and 5, there was no repellency and the appearance was excellent.
カチオン系及びノニオン系界面活性剤を用いた場合には
共に印刷性は良好であったが、硬化被膜表面の平滑性が
悪く、コーテイング液のハジキも発生した。When both cationic and nonionic surfactants were used, printability was good, but the surface smoothness of the cured film was poor, and repellency of the coating liquid occurred.
シタコーン系及びフッ素系のレベリング剤を用いた場合
は、表面の平滑性は非常に優れていたが、インキのハジ
キが発生して表面に印刷することが出来なかった。When using a leveling agent based on shitacone or fluorine, the surface smoothness was very good, but the ink repelled and it was not possible to print on the surface.
表面の硬度はいずれの場合においても良好であった。The surface hardness was good in all cases.
実施例７．８、比較例５〜９
実施例１と同じようにして、ジペンタエリスリトルへキ
サアクリレート、多官能ウレタンアクリレート、希釈剤
、光増感剤の混合液を調製した。この混合液に第３表の
とおりに界面活性剤を添加して十分に混合した。Example 7.8, Comparative Examples 5 to 9 In the same manner as in Example 1, a mixed solution of dipentaerythritor hexaacrylate, polyfunctional urethane acrylate, diluent, and photosensitizer was prepared. A surfactant was added to this liquid mixture as shown in Table 3 and thoroughly mixed.
このコーテイング液を用いて実施例１と同様にメタクリ
ル樹脂板を処理した。得られた表面硬化メタクリル樹脂
板を実施例１と同様に評価した結果を第３表に記した。A methacrylic resin plate was treated in the same manner as in Example 1 using this coating liquid. The obtained surface-cured methacrylic resin plate was evaluated in the same manner as in Example 1, and the results are shown in Table 3.
第３表
（添加量は固形分に対する重量部）
アニオン系界面活性剤のなかでもスルホン酸塩系の界面
活性剤が添加量の広い範囲で外観、印刷性および密着性
の全てにおいて優れ°ζいた。Table 3 (Amounts added are parts by weight based on solid content) Among anionic surfactants, sulfonate surfactants were excellent in appearance, printability, and adhesion over a wide range of addition amounts. .
シリコーン系及びフッ素系のレベリング剤は添加量を減
少しても外観及び密着性共に満足できる結果は得られな
かった。Even if the amount of silicone-based and fluorine-based leveling agents added was reduced, satisfactory results in terms of appearance and adhesion could not be obtained.
Claims (2)
量部に対して０．００１〜１０重量部含有することを特
徴とする活性エネルギー線硬化性コーティング用組成物
。(1) An active energy ray-curable coating composition containing 0.001 to 10 parts by weight of an anionic surfactant per 100 parts by weight of solid content after curing.
アニオン系界面活性剤であることを特徴とする請求項１
記載の活性エネルギー線硬化性コーティング用組成物。(2) Claim 1, wherein the anionic surfactant is an anionic surfactant having an SO_3Na group.
The active energy ray-curable coating composition described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2048853A JPH03250062A (en) | 1990-02-27 | 1990-02-27 | Active energy ray-curable coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2048853A JPH03250062A (en) | 1990-02-27 | 1990-02-27 | Active energy ray-curable coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03250062A true JPH03250062A (en) | 1991-11-07 |
Family
ID=12814828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2048853A Pending JPH03250062A (en) | 1990-02-27 | 1990-02-27 | Active energy ray-curable coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03250062A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002102907A1 (en) * | 2001-06-13 | 2002-12-27 | Nippon Arc Co., Ltd. | Coating composition and article coated with the composition |
-
1990
- 1990-02-27 JP JP2048853A patent/JPH03250062A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002102907A1 (en) * | 2001-06-13 | 2002-12-27 | Nippon Arc Co., Ltd. | Coating composition and article coated with the composition |
| US6946498B2 (en) | 2001-06-13 | 2005-09-20 | Nippon Arc Co., Ltd. | Coating composition and article coated with the composition |
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