JPH0220665B2 - - Google Patents
Info
- Publication number
- JPH0220665B2 JPH0220665B2 JP60219525A JP21952585A JPH0220665B2 JP H0220665 B2 JPH0220665 B2 JP H0220665B2 JP 60219525 A JP60219525 A JP 60219525A JP 21952585 A JP21952585 A JP 21952585A JP H0220665 B2 JPH0220665 B2 JP H0220665B2
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- glass beads
- coating composition
- ultraviolet curable
- coating
- 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.)
- Expired - Lifetime
Links
- 238000000576 coating method Methods 0.000 claims description 63
- 239000011248 coating agent Substances 0.000 claims description 62
- 239000011521 glass Substances 0.000 claims description 36
- 239000011324 bead Substances 0.000 claims description 34
- 239000008199 coating composition Substances 0.000 claims description 30
- 239000000049 pigment Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 10
- 238000005299 abrasion Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000005083 Zinc sulfide Substances 0.000 description 8
- 229910052984 zinc sulfide Inorganic materials 0.000 description 8
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000004040 coloring Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- -1 2-ethylhexyl Chemical group 0.000 description 5
- 239000004606 Fillers/Extenders Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000005355 lead glass Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- NSOAQRMLVFRWIT-UHFFFAOYSA-N 1-ethenoxydecane Chemical compound CCCCCCCCCCOC=C NSOAQRMLVFRWIT-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- KIGJWIPKAWAGCE-UHFFFAOYSA-L gun blue Chemical compound Cl.[Cu+2].O[Se](=O)=O.[O-]S([O-])(=O)=O KIGJWIPKAWAGCE-UHFFFAOYSA-L 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
〈産業上の利用分野〉
本発明は、着色顔料を含む、紫外線硬化可能
で、かつ厚膜で耐摩耗性等の優れた塗膜が得られ
る紫外線硬化型被覆組成物に関するものである。
〈従来の技術〉
近年、無公害、省資源などの社会的要請に伴
い、無溶剤もしくは、有機溶剤量の少ない紫外線
硬化型被覆組成物が、一部採用される傾向にあ
る。しかしながら、従来の紫外線硬化型被覆組成
物は、着色顔料を含まないクリヤーが主流であ
り、着色顔料を含むエナメルは、厚膜化出来ない
ため一部で実用化されているにすぎず、伸び悩み
の状況にある。
前述の如く、着色顔料を含有する紫外線硬化型
被覆組成物は、厚膜にすると紫外線が塗膜内部に
十分透過せず、そのため硬化不良を起し、塗膜膜
表面のみの硬化で、シワが生じたりして塗膜外観
が悪く、また塗膜膜性能も悪いものであつた。
そこで、着色顔料として紫外線を吸収しにくい
顔料を使用する方法、高反応性の紫外線重合性化
合物や光増感剤を使用する方法、紫外線ランプと
して長波長サイドの光線を発するランプを使用す
る方法等が提案されているが、いずれも膜厚が
30μ程度が限界であり、それ以上になると硬化不
良を起したり、また着色力、隠蔽力も通常のエナ
メルに比較し劣るものであつた。
〈発明が解決しようとする問題点〉
本発明は、以上の如き現状に鑑み、厚膜化出来
かつ耐摩耗性、耐衝撃性、耐スリ傷性、難燃性、
遮音性、密着性等の優れた塗膜が得られる紫外線
硬化型被覆組成物を提供することを目的とするも
のである。
〈問題点を解決するための手段〉
すなわち本発明は、
着色顔料を含有する紫外線硬化型被覆組成物に
おいて、前記着色顔料を除く紫外線硬化型被覆組
成物のクリヤー塗膜との屈折率の差が0.3以内で、
かつ中心粒径100μ以下の透明な球状ガラスビー
ズを全被覆組成物固形分中に20〜80重量%含有せ
しめること
を特徴とする紫外線硬化型被覆組成物に関する。
本発明の紫外線硬化型被覆組成物は、着色顔料を
含有せしめているにもかかわらず、特定のガラス
ビーズを含有せしめたことにより、光エネルギー
が塗膜内部に伝播されそれ故、数百μというオー
ダーまで厚膜化しても、塗膜深部においても十分
硬化し、また従来の紫外線硬化型被覆組成物では
得られなかつた塗膜強度、耐摩耗性、難燃性等の
優れた塗膜が得られるという特徴を有しているも
のである。本発明においてガラスビーズを除く、
紫外線硬化型被覆組成物は、従来から通常使用さ
れているものが特に制限なく使用出来る。すなわ
ち本発明における紫外線硬化型被覆組成物は、紫
外線重合性化合物、光開始剤を必須成分とし、さ
らに必要に応じ体質顔料、溶剤、添加剤等からな
るものである。
さらに詳しく説明すると、前記「紫外線重合性
化合物」としては、分子内にラジカル重合可能な
不飽和二重結合を有する化合物が用いられる。具
体的には、比較的低分子量のポリエステル樹脂、
アルキド樹脂、ポリエーテル樹脂、アクリル樹
脂、エポキシ樹脂、ウレタン樹脂、シリコン樹
脂、ポリブタジエン樹脂、アクリル系オリゴマー
又はプレポリマー及び2−エチルヘキシル(メ
タ)アクリレート、2−ヒドロキエチル(メタ)
アクリレート、テトラヒドロフルフリル(メタ)
アクリレート、ジプロピレングリコールモノ(メ
タ)アクリレート、(メタ)アクリルアミド、N
−ビニルピロリドン、トリエチレングリコールジ
(メタ)アクリレート、トリメチロールプロパン
トリ(メタ)アクリレート、ジペンタエリスリト
ールヘキサ(メタ)アクリレート等の反応性モノ
マーの単独又は混合物が代表的なものとして挙げ
られる。また紫外線重合性化合物としてカチオン
開環重合型のビニル−2−エチルヘキシルエーテ
ル、ビニルデシルエーテル、1,2−エポキシシ
クロキサン、ジシクロペンタジエンジオキサイ
ド、ソルビトールポリグリシジルエーテル等も使
用出来る。また、「光開始剤」としてはベンゾイ
ン、ベンゾフエノンあるいはそれらのエステルな
どのカルボニル化合物、過酸化ベンゾイル、アゾ
ビスイソブチロニトリル、ジフエニルジサルフフ
アイド、N−メチルジエタノールアミン、2,5
−ジエトキシ−4−(p−リトルチオ)ベンゼン
ジアゾニウムヘキサフルオロホスフエート等が代
表的なものとして挙げられる。体質顔料としては
硅砂、硅酸塩、タルク、カオリン、硫酸バリウ
ム、炭酸カルシウム、粉末状、フレーク状、フア
イバー状のガラス、ポリウレタン、ポリエステ
ル、ポリエチレン、ポリスチレン等の樹脂粉末等
が代表的なものとして挙げられる。さらに「溶
剤」としては、トルオール、キシロール、アセト
ン、メチルエチルケトン、酢酸エチル、等が代表
的なものとして挙げられる。
本発明の紫外線硬化型被覆組成物は、以上の如
き組成からなるクリヤー組成物に、着色顔料とガ
ラスビーズを配合したものである。しかして、前
記着色顔料としては、通常の無機・有機染顔料が
使用出来る。具体的には、酸化チタン、硫化亜
鉛、亜鉛華、鉛白、リトポン、カーボンブラツ
ク、油煙、紺青、フタロシアニンブルー、郡青、
カーミンFB、黄鉛、亜鉛黄、ハンザイエロー、
オーカー、ベンガラ、不溶性含金属アゾ染料等が
代表的なものとして挙げられる。特に本発明にお
いては、紫外線吸収率の小さな硫化亜鉛、油煙、
郡青、フタロシアニンブルー、カーミンFB、黄
鉛、オーカー、ベンガラ、不溶性含金属アゾ染料
等が好適である。
本発明においては、前記の如くガラスビーズを
用いる。かかるガラスビーズとしては、光エネル
ギーを塗膜内部に伝播させる機能を有するもので
あることが必要であり、それ故次の条件を満たさ
ななければならない。
(イ) 中心粒径は100μ以下、好ましくは10〜60μで
ある。なお、中心粒径が100μを越えると塗膜
硬化性については影響を及ぼさないか、ガラス
ビーズが生成塗膜中で目立ち、ざらつき等が出
るので塗膜外観上好ましくない。また引張り強
度等の物理的特性の低下が見られる。
一方、粒径の下限は、特に制限がないが、透
過率が実質的に低下する傾向にあるため、前記
範囲内とする。
(ロ) 透明で球状である。なお、球状のガラスビー
ズはレンズの働きをし、透過率を上げる効果を
有する。それ以外の形状のものは乱反射しやす
く、再帰反射が生じ塗膜を硬化させる光エネル
ギーが、塗膜深部において大幅に減衰するため
適当でない。
(ハ) ガラスビーズの屈折率が、着色顔料を除く紫
外線硬化型被覆組成物のクリヤー塗膜の屈折率
との差が0.3以内のものである。なお、屈折率
の差が0.3を越えると、厚膜化した場合塗膜を
硬化させる光エネルルギーが塗膜深部において
大幅に減衰し、硬化不良を生じるので適当でな
い。
本発明において使用されるガラスビーズは、以
上の条件を満たすものであれば特に制限なく利用
出来る。
通常、紫外線硬化型被覆組成物のクリヤー塗膜
の屈折率NDは、約1.4〜1.6であり、したがつて屈
折率NDが1.5前後のソーダライムガラス、ソーダ
ライム・鉛ガラス、カリ・鉛ガラス、カリ・鉛ガ
ラス、カリ・ソーダ・鉛ガラス、硼珪酸ガラス、
高アルミナガラス、カリ・ソーダ・バリウムガラ
ス等を具体例として挙げられるが、これらに限定
されるものでないことは自明であろう。
本発明の紫外線硬化型被覆組成物は、以上のよ
うな構成成分からなり、その配合割合は全被覆組
成物固形分中、ガラスビーズが20〜80重量%、特
に好ましくは30〜70重量%、紫外線重合性化合物
が10〜60重量%、特に好ましくは20〜50重量%、
着色顔料が40重量%以下でああり、その下限は生
成塗膜に所望する隠蔽力や着色力に応じ任意に決
定される。
なお、ガラスビーズが前記範囲より少ないと、
塗膜中におけるガラスビーズによる光エネルギー
の伝播が悪くなり、塗膜の硬化不良を生じ、逆に
多過ぎると塗膜の物理的強度が悪くなるため好ま
しくない。
また紫外線重合性化合物が前記範囲より少ない
と塗膜の物理的強度が悪くなり、逆に多過ぎる
と、着色顔料を多い場合、相対的にガラスビーズ
量が少なくなり塗膜の硬化不良が生じるため好ま
しくない。
また着色顔料は前記範囲より多過ぎると相対的
にガラスビーズ量が少なくなり塗膜の硬化不良が
生じやすくなり、また、多く配合しても塗膜の隠
蔽力、着色力はさほど向上しない。
本発明の紫外線硬化型被覆組成物は、通常の塗
布手段もしくは印刷手段を用いて被覆基材に塗布
もしくは印刷した後、紫外線を照射して光重合反
応を誘起させ塗膜を硬化させる。
なお、紫外線を照射するに用いられる光源とし
ては低圧水銀灯、高圧水銀灯、メタルハライドラ
ンプ、カーボンアーク灯、キセノンランプ、ケミ
カルランプ等が使用される。
また被覆基材としては金属、木材、プラスチツ
ク、ガス、陶磁器、コンクリート、紙等の各種基
材に適用出来る。特に、耐摩耗性、耐衝撃性、耐
スリ傷性、難燃性、遮音性能において優れた塗膜
が得られるので、建築内装用に好適に使用出来
る。
〈発明の効果〉
本発明の紫外線硬化型被覆組成物は特定のガラ
スビーズを配合しているため、着色顔料を含んで
いる場合に不可能とされれていた数百μ(例えば
500μ)という厚膜においてさえも、紫外線照射
により十分硬化可能で、しかも厚膜化が可能であ
り、隠蔽力、着色力のある塗膜が得られ、それ故
実用面においては画期的なものである。また、ガ
ラスビーズを配合しているため、得られた塗膜
は、耐摩耗性、耐衝撃性、耐スリ傷性、難燃性、
遮音性、密着性等に優れており、さらに紫外線照
射時、熱も生じ難いので熱に弱い基材にも適用出
来、また熱による塗膜のシワ等の発生が防止出来
るというような特徴をあわせ有してる。
以下、本発明を実施例により説明する。
なお、実施例中「部」、「%」は重量基準で示
す。
実施例 1
下記配合からなる紫外線硬化型被覆組成物を黒
色硬質塩ビ材に3ミルアプリケーターにて塗布
し、120W/cmのFe・Snハライドランプで15cmの
距離から紫外線を2秒照射し、塗膜を硬化させ
た。得られた塗膜につき性能試験をした結果を第
1表に示す。なお、下記配合からソーダガラスビ
ーズ及び硫化亜鉛顔料を除いたクリヤー塗膜の屈
折率NDは1.5であつた。
〈組成配合〉
アクリルウレタンオリゴマー注1)
22部
N−ビニルピロリドン 6部
アセトフエノン系光開始剤 1部
ソーダガラスビーズ注2)
40部
硫化亜鉛顔料 14部
n−酢酸ビニル 17部
注1)「ユニデイツクV4001」(大日本インキ化
学工業社製商品名)
注2)屈折率ND=1.52、中心粒径60μの透明な
球状ビーズ
実施例 2
下記配合からなる紫外線硬化型被覆組成物を、
10ミルアプケーターにて塗布し、紫外線を2秒照
射する以外は実施例1と同様にして塗膜を硬化さ
せた。得られた塗膜につき性能試験をした結果を
第1表に示す。なお下記配合からソーダガラスビ
ーズ及び硫化亜鉛顔料を除いたクリヤー塗報の屈
折率NDは1.5であつた。
〈組成配合〉
アクリルウレタンオリゴマー注1)
25部
N−ビニルピロリドン 7部
アセトフエノン系光開始剤 1部
ソーダガラスビーズ注2)
65部
硫化亜鉛顔料 2部
比較例 1
実施例1においてソーダガラスビーズの代りに
屈折率NDが2.2、中心粒径が60μの透明な球状鉛
ガラスビーズを使用する以外は実施例1と同一条
件にして塗布、紫外線を照射した。得られた塗膜
は表層のみ硬化し、シワが発生しており、かつ塗
膜下層はベトベトしており、未硬化であつた。
比較例 2
実施例1においてソーダガラスビーズの配合量
を10部にする以外は、実施例1と同一条件にて塗
布、紫外線を照射した結果、比較例1と同様塗膜
下層は未硬化であつた。
比較例 3
実施例1においてソーダガラスビーズの配合量
を300部にする以外は実施例1と同一条件にて塗
布、紫外線を照射し、得られた塗膜につき性能試
験をした結果を第1表に示す。
比較例 4
実施例1において中心粒径111μのソーダガラ
スビーズを使用し、かつ6ミルのアプリケータに
て塗布する以外は実施例1と同一条件にして塗
布、紫外線を照射し、得られた塗膜につき性能試
験をした結果を第1表に示す。
比較例 5
実施例1においてソーダガラスビーズの代りに
体質顔料として炭酸カルシウムを使用する以外は
実施例1と同一条件にて塗布、紫外線を照射した
結果比較例1と同様塗膜下層は未硬化であつた。
比較例 6
実施例1において、硫化亜鉛顔料を除き、かつ
ガラスビーズの代りに体質顔料として炭酸カルシ
ウムを使用する以外は実施例1と同一条件にて塗
布、紫外線を照射し、得られた塗膜につき性能試
験をした結果を第1表に示す。但し得られた塗膜
はクリヤー塗膜であつた。
<Industrial Field of Application> The present invention relates to an ultraviolet curable coating composition containing a colored pigment, which can be cured by ultraviolet rays, and provides a thick coating film with excellent abrasion resistance. <Prior Art> In recent years, due to social demands such as non-pollution and resource saving, there has been a tendency to partially adopt ultraviolet curable coating compositions that are solvent-free or contain a small amount of organic solvent. However, the mainstream of conventional UV-curable coating compositions is clear, which does not contain colored pigments, and enamels containing colored pigments have only been put into practical use in some areas because they cannot be made into thick films. situation. As mentioned above, when an ultraviolet curable coating composition containing a colored pigment is formed into a thick film, the ultraviolet rays do not penetrate sufficiently into the coating, resulting in poor curing, and only the surface of the coating is cured, causing wrinkles. The appearance of the coating film was poor, and the performance of the coating film was also poor. Therefore, methods include using pigments that do not easily absorb ultraviolet rays as coloring pigments, using highly reactive ultraviolet polymerizable compounds and photosensitizers, and using lamps that emit light on the long wavelength side as ultraviolet lamps. have been proposed, but in both cases the film thickness is
The limit is about 30μ, and if it exceeds this, curing failure occurs, and the coloring power and hiding power are inferior to that of ordinary enamel. <Problems to be Solved by the Invention> In view of the above-mentioned current situation, the present invention has been developed to provide a film that can be thickened and has wear resistance, impact resistance, scratch resistance, flame retardancy,
The object of the present invention is to provide an ultraviolet curable coating composition that provides a coating film with excellent sound insulation and adhesion properties. <Means for Solving the Problems> In other words, the present invention provides an ultraviolet curable coating composition containing a colored pigment, in which the difference in refractive index between the ultraviolet curable coating composition excluding the colored pigment and the clear coating film is Within 0.3,
The present invention also relates to an ultraviolet curable coating composition, characterized in that the total solid content of the coating composition contains 20 to 80% by weight of transparent spherical glass beads having a center particle diameter of 100 μm or less.
Although the ultraviolet curable coating composition of the present invention contains a colored pigment, the inclusion of specific glass beads allows light energy to be propagated inside the coating film. Even when the film is made to be as thick as the order of magnitude, it is sufficiently cured even in the deep part of the film, and provides a film with excellent film strength, abrasion resistance, flame retardance, etc. that cannot be obtained with conventional UV-curable coating compositions. It has the characteristic of being In the present invention, excluding glass beads,
As the ultraviolet curable coating composition, any conventionally used coating composition can be used without particular limitation. That is, the ultraviolet curable coating composition of the present invention contains an ultraviolet polymerizable compound and a photoinitiator as essential components, and further contains extender pigments, solvents, additives, etc. as necessary. To explain in more detail, as the "ultraviolet polymerizable compound", a compound having an unsaturated double bond capable of radical polymerization in the molecule is used. Specifically, relatively low molecular weight polyester resin,
Alkyd resin, polyether resin, acrylic resin, epoxy resin, urethane resin, silicone resin, polybutadiene resin, acrylic oligomer or prepolymer, and 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)
Acrylate, tetrahydrofurfuryl (meth)
Acrylate, dipropylene glycol mono(meth)acrylate, (meth)acrylamide, N
Typical examples include reactive monomers such as vinylpyrrolidone, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, alone or in mixtures. Further, as ultraviolet polymerizable compounds, cationic ring-opening polymerizable vinyl-2-ethylhexyl ether, vinyldecyl ether, 1,2-epoxycycloxane, dicyclopentadiene dioxide, sorbitol polyglycidyl ether, etc. can be used. Examples of the "photoinitiator" include carbonyl compounds such as benzoin, benzophenone or their esters, benzoyl peroxide, azobisisobutyronitrile, diphenyl disulfide, N-methyldiethanolamine, 2,5
Typical examples include -diethoxy-4-(p-littlethio)benzenediazonium hexafluorophosphate. Typical extender pigments include silica sand, silicates, talc, kaolin, barium sulfate, calcium carbonate, glass in powder, flake, and fiber shapes, and resin powders such as polyurethane, polyester, polyethylene, and polystyrene. It will be done. Furthermore, typical examples of the "solvent" include toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, and the like. The ultraviolet curable coating composition of the present invention is a clear composition having the above composition, mixed with a colored pigment and glass beads. As the coloring pigment, ordinary inorganic and organic dyes and pigments can be used. Specifically, titanium oxide, zinc sulfide, zinc white, lead white, lithopone, carbon black, oil smoke, dark blue, phthalocyanine blue, gun blue,
Carmine FB, yellow lead, zinc yellow, Hansa yellow,
Typical examples include ocher, red iron oxide, and insoluble metal-containing azo dyes. In particular, in the present invention, zinc sulfide, oil smoke,
Suitable dyes include Gunsei, phthalocyanine blue, carmine FB, yellow lead, ocher, red iron, and insoluble metal-containing azo dyes. In the present invention, glass beads are used as described above. Such glass beads must have the ability to propagate light energy into the coating film, and therefore must satisfy the following conditions. (a) The center particle size is 100μ or less, preferably 10 to 60μ. If the center particle size exceeds 100 μm, the coating film curing properties are not affected, or the glass beads become noticeable in the resulting coating film, resulting in roughness and the like, which is unfavorable in terms of coating film appearance. In addition, a decrease in physical properties such as tensile strength is observed. On the other hand, the lower limit of the particle size is not particularly limited, but it is set within the above range since the transmittance tends to decrease substantially. (b) Transparent and spherical. Note that the spherical glass beads function as lenses and have the effect of increasing transmittance. Other shapes are not suitable because they tend to cause diffused reflection, and the light energy that causes retroreflection and hardens the coating is significantly attenuated in the deep part of the coating. (c) The refractive index of the glass beads is within 0.3 of the refractive index of the clear coating film of the ultraviolet curable coating composition excluding colored pigments. It should be noted that if the difference in refractive index exceeds 0.3, the light energy for curing the coating film will be significantly attenuated in the deep part of the coating film when the film is thickened, which is not suitable, as this will result in poor curing. The glass beads used in the present invention can be used without particular limitations as long as they satisfy the above conditions. Usually, the refractive index N D of a clear coating film of an ultraviolet curable coating composition is about 1.4 to 1.6 . Glass, potash/lead glass, potash/soda/lead glass, borosilicate glass,
Specific examples include high alumina glass and potash/soda/barium glass, but it is obvious that the glass is not limited to these. The ultraviolet curable coating composition of the present invention consists of the above-mentioned components, and the proportion of glass beads is 20 to 80% by weight, particularly preferably 30 to 70% by weight, based on the solid content of the total coating composition. The ultraviolet polymerizable compound is 10 to 60% by weight, particularly preferably 20 to 50% by weight,
The content of the colored pigment is 40% by weight or less, and the lower limit is arbitrarily determined depending on the hiding power and coloring power desired for the resulting coating film. In addition, if the number of glass beads is less than the above range,
The propagation of light energy by the glass beads in the coating film becomes poor, resulting in poor curing of the coating film, and conversely, if it is too large, the physical strength of the coating film deteriorates, which is not preferable. In addition, if the amount of the UV polymerizable compound is less than the above range, the physical strength of the coating film will deteriorate, and if it is too much, the amount of glass beads will be relatively reduced when the color pigment is used, resulting in poor curing of the coating film. Undesirable. Furthermore, if the amount of coloring pigment is more than the above-mentioned range, the amount of glass beads will be relatively reduced and the coating film will tend to be poorly cured, and even if a large amount is added, the hiding power and coloring power of the coating film will not improve much. The ultraviolet curable coating composition of the present invention is coated or printed on a coated substrate using a conventional coating means or printing means, and then irradiated with ultraviolet rays to induce a photopolymerization reaction and cure the coating film. Note that as a light source used for irradiating ultraviolet rays, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a xenon lamp, a chemical lamp, etc. are used. Furthermore, the coating can be applied to various base materials such as metal, wood, plastic, gas, ceramics, concrete, and paper. In particular, since a coating film excellent in abrasion resistance, impact resistance, scratch resistance, flame retardance, and sound insulation performance can be obtained, it can be suitably used for architectural interiors. <Effects of the Invention> Since the ultraviolet curable coating composition of the present invention contains specific glass beads, it has a coating composition of several hundred microns (e.g.
Even a film as thick as 500 μ) can be sufficiently cured by UV irradiation, and can be made thicker, providing coatings with hiding and coloring power, which is revolutionary in practical terms. It is. In addition, since glass beads are mixed, the resulting coating film has abrasion resistance, impact resistance, scratch resistance, flame retardancy,
It has excellent sound insulation and adhesion properties, and it also does not easily generate heat when irradiated with ultraviolet rays, so it can be applied to heat-sensitive substrates, and it also has the characteristics of preventing wrinkles in the coating film due to heat. I have it. The present invention will be explained below using examples. In the examples, "parts" and "%" are expressed on a weight basis. Example 1 An ultraviolet curable coating composition consisting of the following formulation was applied to a black hard PVC material using a 3 mil applicator, and ultraviolet rays were irradiated for 2 seconds from a distance of 15 cm using a 120 W/cm Fe/Sn halide lamp to form a coating film. hardened. Table 1 shows the results of a performance test on the resulting coating film. Note that the refractive index N D of the clear coating film obtained by excluding soda glass beads and zinc sulfide pigment from the following formulation was 1.5. <Composition> Acrylic urethane oligomer Note 1) 22 parts N-vinylpyrrolidone 6 parts Acetophenone photoinitiator 1 part Soda glass beads Note 2) 40 parts Zinc sulfide pigment 14 parts N-vinyl acetate 17 parts Note 1) "Unidik V4001" (Product name manufactured by Dainippon Ink and Chemicals Co., Ltd.) Note 2) Transparent spherical beads with a refractive index N D = 1.52 and a center particle size of 60 μm Example 2 An ultraviolet curable coating composition consisting of the following formulation,
The coating film was cured in the same manner as in Example 1 except that it was applied with a 10 mil applicator and irradiated with ultraviolet light for 2 seconds. Table 1 shows the results of a performance test on the resulting coating film. Note that the refractive index N D of the clear coating obtained by excluding soda glass beads and zinc sulfide pigment from the following formulation was 1.5. <Composition> Acrylic urethane oligomer Note 1) 25 parts N-vinylpyrrolidone 7 parts Acetophenone photoinitiator 1 part Soda glass beads Note 2) 65 parts Zinc sulfide pigment 2 parts Comparative example 1 Substituted for soda glass beads in Example 1 It was coated and irradiated with ultraviolet rays under the same conditions as in Example 1, except that transparent spherical lead glass beads with a refractive index N D of 2.2 and a center particle size of 60 μm were used. Only the surface layer of the resulting coating film was cured and wrinkled, and the lower layer of the coating film was sticky and uncured. Comparative Example 2 The coating was applied under the same conditions as in Example 1, except that the amount of soda glass beads in Example 1 was changed to 10 parts, and as a result of irradiation with ultraviolet rays, as in Comparative Example 1, the lower layer of the coating was uncured. Ta. Comparative Example 3 The coating was applied under the same conditions as in Example 1 except that the amount of soda glass beads was changed to 300 parts, and the performance test was performed on the resulting coating film. Table 1 shows the results of performance tests on the resulting coating film. Shown below. Comparative Example 4 Coating was performed under the same conditions as in Example 1 except that soda glass beads with a center particle size of 111 μm were used and a 6 mil applicator was used, and the resulting coating was irradiated with ultraviolet light. Table 1 shows the results of performance tests on the membrane. Comparative Example 5 Coating was carried out under the same conditions as in Example 1 except that calcium carbonate was used as an extender pigment instead of soda glass beads in Example 1, and as a result of irradiation with ultraviolet rays, the lower layer of the coating film was uncured as in Comparative Example 1. It was hot. Comparative Example 6 The coating was applied under the same conditions as in Example 1 except that the zinc sulfide pigment was removed and calcium carbonate was used as an extender pigment instead of the glass beads, and the resulting coating film was irradiated with ultraviolet rays. Table 1 shows the results of the performance tests. However, the coating film obtained was a clear coating film.
【表】
実施例 3
下記配合からなる紫外線硬化型被覆組成物を、
目止め処理した合板に5ミルアプリケータにて塗
布し、80W/cmの水銀ランプで20cmの距離から紫
外線を5秒照射し、塗膜を硬化させた。なお、下
記配合からガラスビーズ及び着色顔料を除いたク
リヤー塗膜の屈折率NDは1.5であつた。
〈組成配合〉
不飽和ポリエステルプレポリマー 25部
トリメチロールプロパントリアクリレート7部
アセトフエノン系光開始剤 1部
ソーダライムガラスビーズ注2)
53部
硫化亜鉛顔料 14部
得られた塗膜は実施例1と同様優れた塗膜性能
を有していた。
比較例 7
実施例3においてガラスビーズの代りに不定形
ソーダライムガラス粉末(屈折率1.51、平均粒径
40μ)を使用する以外は実施例3と同一条件にて
塗布、紫外線を照射した。得られた塗膜は表層の
み硬化し、シワが発生しており、かつ塗膜下層は
未硬化であつた。[Table] Example 3 An ultraviolet curable coating composition consisting of the following formulation,
It was applied to sealed plywood using a 5 mil applicator, and the coating was cured by irradiating it with ultraviolet light for 5 seconds from a distance of 20 cm using an 80 W/cm mercury lamp. Note that the refractive index N D of the clear coating film obtained by excluding the glass beads and colored pigments from the following formulation was 1.5. <Composition> Unsaturated polyester prepolymer 25 parts Trimethylolpropane triacrylate 7 parts Acetophenone photoinitiator 1 part Soda lime glass beads Note 2) 53 parts Zinc sulfide pigment 14 parts The obtained coating film was the same as in Example 1. It had excellent coating performance. Comparative Example 7 In Example 3, amorphous soda lime glass powder (refractive index 1.51, average particle size) was used instead of glass beads.
Coating and irradiation with ultraviolet rays were carried out under the same conditions as in Example 3 except that 40μ) was used. Only the surface layer of the resulting coating film was cured and wrinkled, and the lower layer of the coating film was uncured.
Claims (1)
において、前記着色顔料を除く紫外線硬化型被覆
組成物のクリヤー塗膜との屈折率の差が0.3以内
で、かつ中心粒径100μ以下の透明な球状ガラス
ビーズを全被覆組成物固形分中に20〜80重量%含
有せしめることを特徴とする、耐摩耗性に優れ、
かつ厚膜化可能な塗膜を形成しうる、紫外線硬化
型被覆組成物。 2 ガラスビーズの中心粒径が10〜60μであるこ
とを特徴とする特許請求の範囲第1項記載の紫外
線硬化型被覆組成物。[Scope of Claims] 1. In an ultraviolet curable coating composition containing a colored pigment, the difference in refractive index between the ultraviolet curable coating composition excluding the colored pigment and the clear coating film is within 0.3, and the central particle size is Excellent abrasion resistance, characterized by containing 20 to 80% by weight of transparent spherical glass beads of 100μ or less in the solid content of the total coating composition,
An ultraviolet curable coating composition that can form a thick coating film. 2. The ultraviolet curable coating composition according to claim 1, wherein the glass beads have a central particle size of 10 to 60 μm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60219525A JPS6279275A (en) | 1985-10-02 | 1985-10-02 | Ultraviolet curing coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60219525A JPS6279275A (en) | 1985-10-02 | 1985-10-02 | Ultraviolet curing coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6279275A JPS6279275A (en) | 1987-04-11 |
JPH0220665B2 true JPH0220665B2 (en) | 1990-05-10 |
Family
ID=16736844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60219525A Granted JPS6279275A (en) | 1985-10-02 | 1985-10-02 | Ultraviolet curing coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6279275A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0735693B2 (en) * | 1989-07-24 | 1995-04-19 | 新三郎 ▲吉▼田 | Wall covering |
JPH03174472A (en) * | 1989-11-24 | 1991-07-29 | Dainippon Toryo Co Ltd | Ultraviolet-curable coating composition |
US5013768A (en) * | 1989-12-19 | 1991-05-07 | Dai Nippon Toryo Co., Ltd. | Photopolymerizable coating composition and process for forming a coating having a stereoscopic pattern |
JPH03192163A (en) * | 1989-12-21 | 1991-08-22 | Dainippon Toryo Co Ltd | Ultraviolet-curing coating composition |
JP2006143800A (en) * | 2004-11-17 | 2006-06-08 | Kyowa Sangyo Kk | Coating and coated article |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5738803A (en) * | 1980-08-20 | 1982-03-03 | Toyobo Co Ltd | Ultraviolet-curable resin composition having excellent pigment dispersibility and adhesiveness |
JPS5740505A (en) * | 1980-08-26 | 1982-03-06 | Yokohama Rubber Co Ltd:The | Ultraviolet-curable resin composition, prepreg material impregnated with the same and utilization thereof |
JPS6023462A (en) * | 1983-07-20 | 1985-02-06 | Hitachi Ltd | Abrasion-resistant coating composition |
-
1985
- 1985-10-02 JP JP60219525A patent/JPS6279275A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5738803A (en) * | 1980-08-20 | 1982-03-03 | Toyobo Co Ltd | Ultraviolet-curable resin composition having excellent pigment dispersibility and adhesiveness |
JPS5740505A (en) * | 1980-08-26 | 1982-03-06 | Yokohama Rubber Co Ltd:The | Ultraviolet-curable resin composition, prepreg material impregnated with the same and utilization thereof |
JPS6023462A (en) * | 1983-07-20 | 1985-02-06 | Hitachi Ltd | Abrasion-resistant coating composition |
Also Published As
Publication number | Publication date |
---|---|
JPS6279275A (en) | 1987-04-11 |
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