JPH07118564A - Ultraviolet-absorber-containing curing composition and curing of ultraviolet-curing coating material containing same - Google Patents
Ultraviolet-absorber-containing curing composition and curing of ultraviolet-curing coating material containing sameInfo
- Publication number
- JPH07118564A JPH07118564A JP5266299A JP26629993A JPH07118564A JP H07118564 A JPH07118564 A JP H07118564A JP 5266299 A JP5266299 A JP 5266299A JP 26629993 A JP26629993 A JP 26629993A JP H07118564 A JPH07118564 A JP H07118564A
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet
- curing
- composition
- coating material
- absorber
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000006097 ultraviolet radiation absorber Substances 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 12
- 230000005284 excitation Effects 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- -1 benzotriazole compound Chemical class 0.000 claims description 3
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001723 curing Methods 0.000 description 30
- 239000008199 coating composition Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 1
- FSAONUPVUVBQHL-UHFFFAOYSA-N 1,3-bis(4-azidophenyl)prop-2-en-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=CC(=O)C1=CC=C(N=[N+]=[N-])C=C1 FSAONUPVUVBQHL-UHFFFAOYSA-N 0.000 description 1
- YQPDFPOALLAYGO-UHFFFAOYSA-N 1,5-bis(4-azidophenyl)penta-1,4-dien-3-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=CC(=O)C=CC1=CC=C(N=[N+]=[N-])C=C1 YQPDFPOALLAYGO-UHFFFAOYSA-N 0.000 description 1
- BMNGOGRNWBJJKB-UHFFFAOYSA-N 1-azidopyrene Chemical compound C1=C2C(N=[N+]=[N-])=CC=C(C=C3)C2=C2C3=CC=CC2=C1 BMNGOGRNWBJJKB-UHFFFAOYSA-N 0.000 description 1
- ALRLPDGCPYIVHP-UHFFFAOYSA-N 1-nitropyrene Chemical compound C1=C2C([N+](=O)[O-])=CC=C(C=C3)C2=C2C3=CC=CC2=C1 ALRLPDGCPYIVHP-UHFFFAOYSA-N 0.000 description 1
- KKLBPVXKMBLCQX-UHFFFAOYSA-N 2,5-bis[[4-(diethylamino)phenyl]methylidene]cyclopentan-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CC1)C(=O)C1=CC1=CC=C(N(CC)CC)C=C1 KKLBPVXKMBLCQX-UHFFFAOYSA-N 0.000 description 1
- MLIWQXBKMZNZNF-UHFFFAOYSA-N 2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1C(=CC=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-UHFFFAOYSA-N 0.000 description 1
- UZNOMHUYXSAUPB-UHFFFAOYSA-N 2,6-bis[(4-azidophenyl)methylidene]cyclohexan-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=C(CCC1)C(=O)C1=CC1=CC=C(N=[N+]=[N-])C=C1 UZNOMHUYXSAUPB-UHFFFAOYSA-N 0.000 description 1
- ZQQHQCZUIMXHDW-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C=2C=3N=NNC=3C=CC=2)=C1 ZQQHQCZUIMXHDW-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- ITLDHFORLZTRJI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1N1N=C2C=CC=CC2=N1 ITLDHFORLZTRJI-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- XDTJGDUBFUEJKF-UHFFFAOYSA-N 2-phenylpyrylium Chemical class C1=CC=CC=C1C1=CC=CC=[O+]1 XDTJGDUBFUEJKF-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- CUARLQDWYSRQDF-UHFFFAOYSA-N 5-Nitroacenaphthene Chemical compound C1CC2=CC=CC3=C2C1=CC=C3[N+](=O)[O-] CUARLQDWYSRQDF-UHFFFAOYSA-N 0.000 description 1
- AIPOHLONMUADOM-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.C(CCC)OC1=CC=C(C=C1)C=1C(=[O+]C(=CC1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound Cl(=O)(=O)(=O)O.C(CCC)OC1=CC=C(C=C1)C=1C(=[O+]C(=CC1)C1=CC=CC=C1)C1=CC=CC=C1 AIPOHLONMUADOM-UHFFFAOYSA-N 0.000 description 1
- YINWHXCCEDJPQW-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.C1(=CC=CC=C1)C1=C(C(=[O+]C=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound Cl(=O)(=O)(=O)O.C1(=CC=CC=C1)C1=C(C(=[O+]C=C1)C1=CC=CC=C1)C1=CC=CC=C1 YINWHXCCEDJPQW-UHFFFAOYSA-N 0.000 description 1
- MPGNFQVKAIYSLQ-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.C1(=CC=CC=C1)C=1C(=C([CH+]SC1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound Cl(=O)(=O)(=O)O.C1(=CC=CC=C1)C=1C(=C([CH+]SC1)C1=CC=CC=C1)C1=CC=CC=C1 MPGNFQVKAIYSLQ-UHFFFAOYSA-N 0.000 description 1
- AOPMEEMVFDPQHQ-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.COC1=CC=C(C=C1)C=1C(=[O+]C(=CC1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound Cl(=O)(=O)(=O)O.COC1=CC=C(C=C1)C=1C(=[O+]C(=CC1)C1=CC=CC=C1)C1=CC=CC=C1 AOPMEEMVFDPQHQ-UHFFFAOYSA-N 0.000 description 1
- UHQQNJUYQCLUHN-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.COC1=CC=C(C=C1)C=1[C+](SC(=CC1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound Cl(=O)(=O)(=O)O.COC1=CC=C(C=C1)C=1[C+](SC(=CC1)C1=CC=CC=C1)C1=CC=CC=C1 UHQQNJUYQCLUHN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WNDDODBAIXQYJZ-UHFFFAOYSA-N OC(=O)C1=C(N=[N+]=[N-])CC(=S(=O)=O)C=C1 Chemical compound OC(=O)C1=C(N=[N+]=[N-])CC(=S(=O)=O)C=C1 WNDDODBAIXQYJZ-UHFFFAOYSA-N 0.000 description 1
- PAIRLXWGRGDESR-UHFFFAOYSA-N OC(=O)C1=CC=CC(=S(=O)=O)C1N=[N+]=[N-] Chemical compound OC(=O)C1=CC=CC(=S(=O)=O)C1N=[N+]=[N-] PAIRLXWGRGDESR-UHFFFAOYSA-N 0.000 description 1
- MVQCKZYPQJNPDN-UHFFFAOYSA-N [2,3-bis(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N(C)C MVQCKZYPQJNPDN-UHFFFAOYSA-N 0.000 description 1
- XHPWRTXYJFNZAW-UHFFFAOYSA-N [[4-[2-(4-diazonioimino-2-sulfocyclohexa-2,5-dien-1-ylidene)ethylidene]-3-sulfocyclohexa-2,5-dien-1-ylidene]hydrazinylidene]azanide Chemical compound OS(=O)(=O)C1=CC(N=[N+]=[N-])=CC=C1C=CC1=CC=C(N=[N+]=[N-])C=C1S(O)(=O)=O XHPWRTXYJFNZAW-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 238000002156 mixing Methods 0.000 description 1
- SKACCCDFHQZGIA-UHFFFAOYSA-N n-(4-nitronaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C([N+]([O-])=O)C2=C1 SKACCCDFHQZGIA-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、紫外線硬化型塗料を硬
化するための紫外線吸収剤含有硬化剤組成物及び該組成
物を配合した紫外線硬化型塗料の硬化方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curing agent composition containing an ultraviolet absorber for curing an ultraviolet curable coating material and a method for curing an ultraviolet curable coating material containing the composition.
【０００２】[0002]
【従来技術】紫外線硬化型塗料としては、例えばポリエ
ステルアクリレート、ウレタンアクリレート、エポキシ
アクリレート等が従来より知られている。しかし、かか
る紫外線硬化型塗料は充分満足できる耐候性を有してい
ない。通常、屋外暴露年数１〜５年で塗膜が劣化し基材
のチョーキングやクラッキング、黄変現象が発生する。2. Description of the Related Art Polyester acrylates, urethane acrylates, epoxy acrylates and the like have been conventionally known as ultraviolet curable coatings. However, such UV-curable coatings do not have sufficient weather resistance. Usually, after 1 to 5 years of outdoor exposure, the coating film deteriorates, causing chalking, cracking, and yellowing of the substrate.
【０００３】従来技術では塗膜に紫外線吸収遮断機能を
もたせることが不可能であったため、基材の紫外線によ
る劣化を防止できなかった。その理由は、塗膜に紫外線
吸収遮断機能をもたせるため紫外線硬化型塗料に紫外線
吸収剤を配合すると、塗料中の紫外線吸収剤の吸収波長
域と光重合開始剤・光増感剤の励起波長域が重複し、紫
外線ランプのパワーを減じることになり該塗料の塗膜を
硬化させることが不可能であったためである。In the prior art, it was impossible to give the coating film a function of blocking the absorption of ultraviolet rays, so that it was not possible to prevent the deterioration of the substrate due to ultraviolet rays. The reason for this is that if an ultraviolet curing agent is added to the ultraviolet curable coating in order to give the coating film an ultraviolet absorption blocking function, the absorption wavelength range of the ultraviolet absorber in the coating and the excitation wavelength range of the photopolymerization initiator / photosensitizer This is because it was impossible to cure the coating film of the paint because the power of the ultraviolet lamp was reduced.
【０００４】[0004]
【発明が解決しようとする課題】したがって、本発明の
目的は、紫外線硬化型塗料に充分な硬化速度を与え、且
つ硬化塗膜に紫外線吸収遮断機能をもたせるための、紫
外線吸収剤含有硬化剤組成物を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a curing agent composition containing an ultraviolet absorber for imparting a sufficient curing rate to an ultraviolet curable coating composition and for imparting an ultraviolet absorption blocking function to a cured coating film. To provide things.
【０００５】さらなる本発明の目的は、紫外線硬化型塗
料に充分な硬化速度を与え、且つ硬化塗膜に紫外線吸収
遮断機能を与える紫外線硬化型塗料の硬化方法を提供す
ることにある。A further object of the present invention is to provide a method for curing an ultraviolet curable coating which gives a sufficient curing speed to the ultraviolet curable coating and also provides the cured coating film with an ultraviolet absorption blocking function.
【０００６】[0006]
【課題を解決するための手段】上記の課題を解決するた
めに種々の検討を行なった結果、紫外線吸収剤の有効吸
収波長域と光重合開始剤・光増感剤の有効励起波長ピー
クをずらすことにより本発明の目的を達成できることが
判明した。[Means for Solving the Problems] As a result of various studies to solve the above problems, the effective absorption wavelength region of the ultraviolet absorber and the effective excitation wavelength peak of the photopolymerization initiator / photosensitizer are shifted. Therefore, it was found that the object of the present invention can be achieved.
【０００７】すなわち、本発明の紫外線硬化型塗料用の
紫外線吸収剤含有硬化剤組成物は、有効吸収波長が２７
０〜３８０ｎｍである紫外線吸収剤及び有効励起波長ピ
ークが３８０ｎｍ以上である光重合開始剤・光増感剤よ
りなる。That is, the ultraviolet absorbent-containing curing agent composition for ultraviolet curable coating material of the present invention has an effective absorption wavelength of 27.
It comprises an ultraviolet absorber having a wavelength of 0 to 380 nm and a photopolymerization initiator / photosensitizer having an effective excitation wavelength peak of 380 nm or more.
【０００８】本発明において「紫外線硬化型塗料」なる
用語は、紫外線により塗膜の主成分たる高分子化合物が
硬化乾燥する塗料を示し、幅広い概念で使用され得る。
紫外線硬化型塗料としては、例えばポリエステルアクリ
レート、ウレタンアクリレート、エポキシアクリレー
ト、シリコーンアクリレート等があげられる。In the present invention, the term "ultraviolet curable coating material" refers to a coating material in which a polymer compound as a main component of a coating film is cured and dried by ultraviolet rays, and can be used in a wide range of concepts.
Examples of the ultraviolet curable coating material include polyester acrylate, urethane acrylate, epoxy acrylate, and silicone acrylate.
【０００９】本発明における紫外線吸収剤としては有効
吸収波長が２７０〜３８０ｎｍである有機又は無機の紫
外線吸収剤が使用できる。有機紫外線吸収剤としてはベ
ンゾトリアゾール系化合物が好ましい。ベンゾトリアゾ
ール系紫外線吸収剤としては、２−（２′−ヒドロキシ
−５′−メチルフェニル）ベンゾトリアゾール、２−
（２′−ヒドロキシ−５′−ｔ−ブチルフェニル）ベン
ゾトリアゾール、２−（２′−ヒドロキシ−３′，５′
−ジ−ｔ−ブチルフェニル）ベンゾトリアゾール、２−
（２′−ヒドロキシ−３′−ｔ−ブチル−５′−メチル
フェニル）−５−クロロベンゾトリアゾール、２−
（２′−ヒドロキシ−３′，５′−ジ−ｔ−ブチルフェ
ニル）−５−クロロベンゾトリアゾール、２−（２′−
ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベ
ンゾトリアゾール、２−（２′−ヒドロキシ−４′−オ
クトキシフェニル）ベンゾトリアゾール、２−｛２′−
ヒドロキシ−３′−（３”，４”，５”，６”−テトラ
ヒドロフタルイミドメチル）−５′−メチルフェニル｝
ベンゾトリアゾール等があげられる。無機紫外線吸収剤
としては酸化亜鉛、酸化チタン（チタニア）、酸化セリ
ウム等が挙げられる。As the ultraviolet absorber in the present invention, an organic or inorganic ultraviolet absorber having an effective absorption wavelength of 270 to 380 nm can be used. Benzotriazole compounds are preferred as the organic ultraviolet absorber. Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole.
(2'-Hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2'-Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- {2'-
Hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl}
Examples thereof include benzotriazole. Examples of the inorganic ultraviolet absorber include zinc oxide, titanium oxide (titania), cerium oxide and the like.
【００１０】本発明の硬化剤組成物における光重合開始
剤・光増感剤は有効励起波長ピークが３８０ｎｍ以上で
ある光重合開始剤・光増感剤であれば特に限定されな
い。The photopolymerization initiator / photosensitizer in the curing agent composition of the present invention is not particularly limited as long as it is a photopolymerization initiator / photosensitizer having an effective excitation wavelength peak of 380 nm or more.
【００１１】光重合開始剤・光増感剤としては、例え
ば、チオキサンソン系化合物（２−クロロチオキサンソ
ン、２−メチルチオキサンソン、２−イソプロピルチオ
キサンソン等）、ベンゾフェノン系化合物（４−４′−
ビス（ジメチルアミノ）ベンゾフェノン、４，４′−ビ
ス（ジエチルアミノ）ベンゾフェノン等）、アジド系化
合物（４，４′−ジアジドカルコン、１，３−ビス
（４′−アジドベンザル）アセトン、２，６−ビス
（４′−アジドベンザル）シクロヘキサノン、２，６−
ビス（４′−アジドベンザル）−４−メチルシクロヘキ
サノン、ナフトキノン（１，２）ジアジド（２）−５−
スルホン酸の塩又はエステル、ジアゾ樹脂、４，４′−
ジアジドスチルベン−２，２′−ジスルホン酸、１，３
−ビス（４′−アジドベンザル）−２−プロパノン−
２′−スルホン酸、１，３−ビス（４′−アジドベンザ
ル）−２−プロパノン−２，２′−ジスルホン酸ナトリ
ウム、１，３−ビス（４′−アジドシンナシリデン）−
２−プロパノン、アジドピレン、３−スルホニルアジド
安息香酸、４−スルホニルアジド安息香酸、２，６−ビ
ス（４′−アジドベンザル）−シクロヘキサノン−２，
２′−ジスルホン酸及びそのナトリウム塩、２，６−ビ
ス（４′−アジドベンザル）−メチル−シクロヘキサノ
ン−２，２′−ジスルホン酸及びそのナトリウム塩
等）、フェニルピリリウム系化合物（トリフェニルピリ
リウム過塩素酸、４−メトキシフェニル−２，６−ジフ
ェニルピリリウム過塩素酸、４−ブトキシフェニル−
２，６−ジフェニルピリリウム過塩素酸、トリフェニル
チオピリリウム過塩素酸、４−メトキシフェニル−２，
６−ジフェニルチオピリリウム過塩素酸等）、２，５−
ビス（４′−ジエチルアミノベンザル）シクロペンタノ
ン、１−アセチルアミノ−４−ニトロナフタレン、５−
ニトロアセナフテン、１−ニトロピレン等が好ましい。
特に好ましくは２−クロロチオキサンソン、４−４′−
ビス（ジメチルアミノ）ベンゾフェノン等である。Examples of the photopolymerization initiator / photosensitizer include thioxanthone compounds (2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc.) and benzophenone compounds (4-4). ′-
Bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc., azide compound (4,4'-diazidochalcone, 1,3-bis (4'-azidobenzal) acetone, 2,6- Bis (4'-azidobenzal) cyclohexanone, 2,6-
Bis (4'-azidobenzal) -4-methylcyclohexanone, naphthoquinone (1,2) diazide (2) -5-
Sulfonic acid salts or esters, diazo resins, 4,4'-
Diazidostilbene-2,2'-disulfonic acid, 1,3
-Bis (4'-azidobenzal) -2-propanone-
2'-sulfonic acid, 1,3-bis (4'-azidobenzal) -2-propanone-2,2'-disulfonic acid sodium salt, 1,3-bis (4'-azidocinnalidene)-
2-propanone, azidopyrene, 3-sulfonylazidobenzoic acid, 4-sulfonylazidobenzoic acid, 2,6-bis (4'-azidobenzal) -cyclohexanone-2,
2'-disulfonic acid and its sodium salt, 2,6-bis (4'-azidobenzal) -methyl-cyclohexanone-2,2'-disulfonic acid and its sodium salt, and phenylpyrylium compounds (triphenylpyrylium) Perchloric acid, 4-methoxyphenyl-2,6-diphenylpyrylium perchloric acid, 4-butoxyphenyl-
2,6-diphenylpyrylium perchloric acid, triphenylthiopyrylium perchloric acid, 4-methoxyphenyl-2,
6-diphenylthiopyrylium perchloric acid, etc.), 2,5-
Bis (4'-diethylaminobenzal) cyclopentanone, 1-acetylamino-4-nitronaphthalene, 5-
Nitroacenaphthene, 1-nitropyrene and the like are preferable.
Particularly preferred is 2-chlorothioxanthone, 4-4'-
Examples include bis (dimethylamino) benzophenone.
【００１２】光重合開始剤・光増感剤は一種又は二種以
上の上記化合物を含有することができる。The photopolymerization initiator / photosensitizer may contain one kind or two or more kinds of the above compounds.
【００１３】本発明の硬化剤組成物における紫外線吸収
剤：光重合開始剤・光増感剤の重量比は１：０．０２〜
５０が好ましく、１：０．１〜１０がより好ましく、
１：０．５〜２が最も好ましい。The weight ratio of the ultraviolet absorber: photopolymerization initiator / photosensitizer in the curing agent composition of the present invention is 1: 0.02.
50 is preferable, 1: 0.1-10 is more preferable,
1: 0.5-2 is the most preferable.
【００１４】本発明の硬化剤組成物は、例えば、各成分
を混合、撹拌して均質化することにより製造できる。The hardener composition of the present invention can be produced, for example, by mixing the respective components, stirring and homogenizing.
【００１５】更に、本発明は、前記硬化剤組成物を配合
した紫外線硬化型塗料を紫外線発光体により硬化する紫
外線硬化型塗料の硬化方法にも関する。Furthermore, the present invention also relates to a method for curing an ultraviolet-curable coating composition in which the ultraviolet-curable coating composition containing the above-mentioned curing agent composition is cured with an ultraviolet luminescent material.
【００１６】本発明の硬化剤組成物を配合すべき紫外線
硬化型塗料としては、例えばポリエステルアクリレー
ト、ウレタンアクリレート、エポキシアクリレート、シ
リコーンアクリレート等を主硬化成分として含有するも
のがあげられる。Examples of the ultraviolet-curable coating material to which the curing agent composition of the present invention should be added include those containing polyester acrylate, urethane acrylate, epoxy acrylate, silicone acrylate, etc. as main curing components.
【００１７】紫外線硬化型塗料に該硬化剤組成物を１〜
１０重量％配合するのが好ましく、３〜８重量％配合す
るのがより好ましい。1 to 1 of the curing agent composition in an ultraviolet curable coating composition
The amount is preferably 10% by weight, more preferably 3 to 8% by weight.
【００１８】本発明における紫外線発光体としては、メ
タルハライドランプ、水銀ランプ、キセノンランプ等が
使用できる。特に好ましいのはメタルハライドランプで
ある。A metal halide lamp, a mercury lamp, a xenon lamp or the like can be used as the ultraviolet light emitter in the present invention. Particularly preferred are metal halide lamps.
【００１９】[0019]
【実施例】以下、実施例にて本発明を説明するが、本発
明を限定するものではない。The present invention will be described below with reference to examples, but the present invention is not limited thereto.
【００２０】実施例１ 下記の各成分を混合して本発明
の硬化剤組成物を調製した。Example 1 The following components were mixed to prepare a curing agent composition of the present invention.
【００２１】 ベンゾトリアゾール ２．５重量部 ２−クロロチオキサンソン ０．２重量部 ４−４′−ビス（ジメチルアミノ）ベンゾフェノン ２．０重量部 計４．７重量部 実施例２ 紫外線硬化型塗料の調製及び塗料の硬化 下記の配合（重量部）で、実施例１の硬化剤組成物と各
種塗料用紫外線硬化型樹脂を混合し紫外線硬化型塗料を
調製した。比較のため市販の紫外線硬化型ハードコート
も使用した。Benzotriazole 2.5 parts by weight 2-chlorothioxanthone 0.2 parts by weight 4-4′-bis (dimethylamino) benzophenone 2.0 parts by weight Total 4.7 parts by weight Example 2 UV curable coating composition And the curing of the coating composition The following composition (parts by weight) was mixed with the curing agent composition of Example 1 and the ultraviolet curing resin for various coating compositions to prepare an ultraviolet curing coating composition. A commercially available UV-curable hard coat was also used for comparison.
【００２２】（Ａ）シリコーンアクリレート：実施例１
の硬化剤組成物＝９５．３：４．７ （Ｂ）ウレタンアクリレート：実施例１の硬化剤組成物
＝９５．３：４．７ （Ｃ）ポリエステルアクリレート：実施例１の硬化剤組
成物＝９５．３：４．７ （Ｄ）エポキシアクリレート：実施例１の硬化剤組成物
＝９５．３：４．７ （Ｅ）ウレタンアクリレート（市販品） （Ｆ）ポリエステルアクリレート（市販品） （Ｇ）エポキシアクリレート（市販品） （Ｈ）ブランク（塗料未塗布） 上記の紫外線硬化型塗料から以下の作成条件でテストピ
ースを調製した。(A) Silicone acrylate: Example 1
Curing agent composition = 95.3: 4.7 (B) Urethane acrylate: Curing agent composition of Example 1 = 95.3: 4.7 (C) Polyester acrylate: Curing agent composition of Example 1 = 95.3: 4.7 (D) Epoxy acrylate: Curing agent composition of Example 1 = 95.3: 4.7 (E) Urethane acrylate (commercially available product) (F) Polyester acrylate (commercially available product) (G) Epoxy acrylate (commercial item) (H) blank (paint not applied) A test piece was prepared from the above ultraviolet curable paint under the following preparation conditions.
【００２３】塗布基板：１００×１００×５ｍｍ厚ポリ
カーボネート板（帝人化成製） 塗布方法：バーコーター 塗布膜厚：それぞれ乾燥膜厚が１０μｍになるように塗
布した。Coating substrate: 100 × 100 × 5 mm thick polycarbonate plate (manufactured by Teijin Kasei) Coating method: Bar coater Coating film thickness: Coating was performed so that the dry film thickness was 10 μm.
【００２４】硬化条件：メタルハライドランプ出力１２
０Ｗ／ｃｍ、照射距離１５０ｃｍ 露光時間：２秒 硬化装置：ＥＹＥ ＧＲＡＮＤＡＧＥ アイグラフィッ
クス株式会社製試験例１ 塗膜性能の評価 性能評価はプラスチック及び塗膜に関するＪＩＳ規定の
評価方法で評価した。主な評価項目と評価目的は次の通
りである。Curing conditions: Metal halide lamp output 12
0 W / cm, irradiation distance 150 cm Exposure time: 2 seconds Curing device: EYE GRANDAGE Eye Graphics Co., Ltd. Test Example 1 Evaluation of coating film performance The performance evaluation was evaluated by a JIS-specified evaluation method for plastics and coating films. The main evaluation items and evaluation objectives are as follows.
【００２５】塗膜硬度：表面が硬ければ擦り傷抵抗性が
高く傷が付き難いので初期の透明性が維持できる。塗膜
硬度の比較評価をした。Coating hardness: If the surface is hard, scratch resistance is high and scratches are less likely to occur, so initial transparency can be maintained. Comparative evaluation of coating film hardness was performed.
【００２６】屋外耐候性：一般に透明プラスチック板を
屋外で使用した場合、５年以内に黄変、黒変、クラッキ
ング、白濁、チョーキング現象が現れるので本発明品が
既に上市されている塗料との比較でそれらの劣化現象を
どこまで阻止できるかを見た。試験装置で促進試験を行
った。Outdoor weather resistance: In general, when a transparent plastic plate is used outdoors, yellowing, blackening, cracking, clouding, and chalking phenomena appear within 5 years, so that the product of the present invention is compared with the commercially available paints. I saw how far these deterioration phenomena can be prevented. An accelerated test was conducted with a test device.
【００２７】耐薬品性：屋外では降雨にさらされる。現
在ｐＨ４程度の強い酸性雨が降ることがあるので、硫
酸、硝酸等の耐薬品性を行った。Chemical resistance: exposed outdoors to rainfall. At present, strong acid rain with a pH of about 4 may fall, so chemical resistance against sulfuric acid, nitric acid, etc. was performed.
【００２８】その他：ＪＩＳに基づき塗膜一般物性試験
を行った。Others: A general coating film physical property test was conducted based on JIS.
【００２９】作成したテストピースの評価結果を次に示
す。The evaluation results of the prepared test piece are shown below.
【００３０】ａ．塗膜硬度 シェアスクラッチテスターにて傷つき荷重を測定した。
荷重の大きいほど塗膜が硬く傷が付き難い。A. Coating hardness The scratch load was measured with a shear scratch tester.
The larger the load, the harder the coating is and the less likely it is to get scratched.
【００３１】[0031]
【表１】 [Table 1]
【００３２】ｂ．屋外耐候性 サンシャインウェザオメーター（ＷＯＭ）により促進耐
候性を試験した。B. Outdoor weather resistance Accelerated weather resistance was tested with a Sunshine Weatherometer (WOM).
【００３３】ｂ−１．初期光沢保持率（％） （Ａ）はサンシャインウェザオメーター４０００時間
（屋外暴露相当で２０年間）、（Ｂ）〜（Ｄ）は２００
０時間まで初期の光沢を保持したが、（Ｅ）〜（Ｈ）は
サンシャインウェザオメーター１０００時間（屋外暴露
相当で５年）以内にすべてチョーキング現象が発生し初
期の光沢を失なった。B-1. Initial gloss retention rate (%) (A) is sunshine weatherometer 4000 hours (20 years corresponding to outdoor exposure), (B) to (D) is 200
Although the initial gloss was maintained up to 0 hours, all of (E) to (H) lost the initial gloss due to the occurrence of a chalking phenomenon within 1000 hours of the sunshine weatherometer (5 years corresponding to outdoor exposure).
【００３４】ｂ−２．初期〜経過時間後の黄変度（イエ
ローインデックス；△ＹＩ） （Ａ）〜（Ｄ）はサンシャインウェザオメーター２００
０時間（屋外暴露相当で１０年間）までは黄変がほとん
ど発生しないが、（Ｅ）〜（Ｈ）はサンシャインウェザ
オメーター１０００時間（屋外暴露相当で５年）以内に
すべて激しく黄変することが分かった。尚、目視で判断
できる黄変は△ＹＩが約２前後である。B-2. The degree of yellowing (yellow index; ΔYI) from the initial stage to the elapsed time (A) to (D) is the sunshine weatherometer 200.
Almost no yellowing occurs until 0 hours (equivalent to outdoor exposure for 10 years), but in (E) to (H), all of them turn yellow severely within 1000 hours of sunshine weatherometer (5 years corresponding to outdoor exposure). I understood. In addition, the yellowing that can be visually judged is ΔYI of about 2.
【００３５】ｃ．耐薬品性 硫酸及び硝酸の５％水溶液にテストピースを２４時間浸
漬し、その後水洗し乾燥させて塗膜の状態を目視で評価
した。C. Chemical resistance The test piece was immersed in a 5% aqueous solution of sulfuric acid and nitric acid for 24 hours, then washed with water and dried to visually evaluate the state of the coating film.
【００３６】[0036]
【表２】 [Table 2]
【００３７】ｄ．耐溶剤性 トルエンをしたしたガーゼで表面を１００回摩擦し、塗
膜の状態を目視で評価した。D. Solvent resistance The surface of the coating was rubbed 100 times with gauze coated with toluene, and the state of the coating film was visually evaluated.
【００３８】[0038]
【表３】 [Table 3]
【００３９】[0039]
【発明の効果】本発明の紫外線吸収剤含有硬化剤組成物
及び硬化方法によれば、紫外線硬化型塗料に充分な硬化
速度を与え、且つ硬化塗膜に紫外線吸収遮断機能をもた
せることにより耐候性を著しく改善できる。EFFECTS OF THE INVENTION According to the curing agent composition containing ultraviolet absorber and the curing method of the present invention, it is possible to impart a sufficient curing speed to the ultraviolet curable coating material and to impart a ultraviolet absorption blocking function to the cured coating film to improve the weather resistance. Can be significantly improved.
Claims (3)
る紫外線吸収剤及び有効励起波長ピークが３８０ｎｍ以
上である光重合開始剤・光増感剤よりなる紫外線硬化型
塗料用の紫外線吸収剤含有硬化剤組成物。1. A curing agent containing an ultraviolet absorber for an ultraviolet curable coating material, which comprises an ultraviolet absorber having an effective absorption wavelength of 270 to 380 nm and a photopolymerization initiator / photosensitizer having an effective excitation wavelength peak of 380 nm or more. Composition.
合物、光重合開始剤・光増感剤が２−クロロチオキサン
ソン及び／又は４−４′−ビス（ジメチルアミノ）ベン
ゾフェノンである請求項１に記載の硬化剤組成物。2. The ultraviolet absorber is a benzotriazole compound, and the photopolymerization initiator / photosensitizer is 2-chlorothioxanthone and / or 4-4′-bis (dimethylamino) benzophenone. A curing agent composition as described.
る紫外線吸収剤及び有効励起波長ピークが３８０ｎｍ以
上である光重合開始剤・光増感剤よりなる紫外線吸収剤
含有硬化剤組成物を配合した紫外線硬化型塗料を紫外線
発光体を使用し硬化することを特徴とする紫外線硬化型
塗料の硬化方法。3. An ultraviolet ray containing a curing agent composition containing an ultraviolet absorber having an effective absorption wavelength of 270 to 380 nm and a photopolymerization initiator / photosensitizer having an effective excitation wavelength peak of 380 nm or more. A method for curing an ultraviolet-curable coating material, which comprises curing the curable coating material using an ultraviolet luminescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5266299A JPH07118564A (en) | 1993-10-25 | 1993-10-25 | Ultraviolet-absorber-containing curing composition and curing of ultraviolet-curing coating material containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5266299A JPH07118564A (en) | 1993-10-25 | 1993-10-25 | Ultraviolet-absorber-containing curing composition and curing of ultraviolet-curing coating material containing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07118564A true JPH07118564A (en) | 1995-05-09 |
Family
ID=17429015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5266299A Pending JPH07118564A (en) | 1993-10-25 | 1993-10-25 | Ultraviolet-absorber-containing curing composition and curing of ultraviolet-curing coating material containing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118564A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008266409A (en) * | 2007-04-18 | 2008-11-06 | Goyo Paper Working Co Ltd | Ultraviolet ray-curable resin composition and composite sheet using this |
| JP2009067827A (en) * | 2007-09-10 | 2009-04-02 | Toyoda Gosei Co Ltd | Light curable colored paints and painted resin products |
| CN103146239A (en) * | 2012-12-26 | 2013-06-12 | 王娟 | Ultraviolet curable coating |
| US20140113082A1 (en) * | 2012-10-24 | 2014-04-24 | Mimaki Engineering Co., Ltd. | Ink-jet printing ink and printing method |
| JP2015155542A (en) * | 2015-03-13 | 2015-08-27 | セイコーエプソン株式会社 | Inkjet recording method and recorded matter |
-
1993
- 1993-10-25 JP JP5266299A patent/JPH07118564A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008266409A (en) * | 2007-04-18 | 2008-11-06 | Goyo Paper Working Co Ltd | Ultraviolet ray-curable resin composition and composite sheet using this |
| JP2009067827A (en) * | 2007-09-10 | 2009-04-02 | Toyoda Gosei Co Ltd | Light curable colored paints and painted resin products |
| US20140113082A1 (en) * | 2012-10-24 | 2014-04-24 | Mimaki Engineering Co., Ltd. | Ink-jet printing ink and printing method |
| CN103146239A (en) * | 2012-12-26 | 2013-06-12 | 王娟 | Ultraviolet curable coating |
| JP2015155542A (en) * | 2015-03-13 | 2015-08-27 | セイコーエプソン株式会社 | Inkjet recording method and recorded matter |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2002177C (en) | Methacrylate protective coating containing a uv-absorber for polycarbonate | |
| DE69735466T2 (en) | Radiation-curable coatings | |
| CA1100679A (en) | Ultraviolet light-curable diacrylate hydantoin adhesive compositions | |
| EP2738188B1 (en) | Monolayer film and hydrophilic material comprising same | |
| EP2599799B1 (en) | Single-layer film and hydrophilic material comprising same | |
| KR101646815B1 (en) | Surface protection film | |
| JPH08151415A (en) | Weather-resistant composition | |
| JP2000281935A (en) | Ultraviolet curable coating resin composition | |
| JPWO2015087810A1 (en) | Composition for hydrophilic cured product | |
| JPH07113095B2 (en) | Paint containing titanium oxide | |
| JP2011500905A (en) | UV protection composition | |
| JP5959764B2 (en) | Hydrophilic monolayer | |
| JPH07118564A (en) | Ultraviolet-absorber-containing curing composition and curing of ultraviolet-curing coating material containing same | |
| JP5948297B2 (en) | UV curable coating composition excellent in weather resistance, coating film forming method, coated article | |
| JPH07118563A (en) | New ultraviolet-curing cyclic silicone oligomer and ultraviolet-curing polysiloxane coating composition containing same | |
| US7504450B2 (en) | Resin compositions | |
| JP2007313872A (en) | Laminated hard coat film or sheet | |
| JPH09157581A (en) | Method for reinforcement of plate glass and coating material for preventing broken glass piece from scattering | |
| JP2009046526A (en) | Resin film for improving resistance | |
| JPH07247306A (en) | Ultraviolet-curable composition | |
| JPH0788491B2 (en) | Paint containing titanium oxide | |
| JPH0372302A (en) | Coating composition | |
| EP0331087A2 (en) | Ultraviolet-curing coating composition and production process of molded plastic article having hardened coating of modified surface characteristics | |
| JPH0726177A (en) | Ultraviolet-screening coating and ultravioletscreening transparent body | |
| JP2013023648A (en) | Method for producing monolayer film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20060221 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070815 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070821 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071019 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Effective date: 20071120 Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20071127 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 3 Free format text: PAYMENT UNTIL: 20101207 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101207 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101207 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111207 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111207 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 5 Free format text: PAYMENT UNTIL: 20121207 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 5 Free format text: PAYMENT UNTIL: 20121207 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131207 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |