JP6763564B2 - Photocurable artificial nail composition for self-nail application containing hydrophobic urethane (meth) acrylate oligomer - Google Patents
Photocurable artificial nail composition for self-nail application containing hydrophobic urethane (meth) acrylate oligomer Download PDFInfo
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- JP6763564B2 JP6763564B2 JP2016106350A JP2016106350A JP6763564B2 JP 6763564 B2 JP6763564 B2 JP 6763564B2 JP 2016106350 A JP2016106350 A JP 2016106350A JP 2016106350 A JP2016106350 A JP 2016106350A JP 6763564 B2 JP6763564 B2 JP 6763564B2
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- Prior art keywords
- meth
- nail
- acrylate
- self
- composition
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 88
- 239000000203 mixture Substances 0.000 title claims description 78
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 19
- 230000002209 hydrophobic effect Effects 0.000 title claims description 17
- 239000000178 monomer Substances 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 13
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002270 phosphoric acid ester group Chemical group 0.000 claims description 2
- 210000000282 nail Anatomy 0.000 description 126
- -1 trimethylhexyl Chemical group 0.000 description 42
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 210000000078 claw Anatomy 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 235000019646 color tone Nutrition 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical group 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- PMCOFJGRLDVXQM-UHFFFAOYSA-N CC(=C)C(O)=O.CCCCCC(=O)OCC Chemical compound CC(=C)C(O)=O.CCCCCC(=O)OCC PMCOFJGRLDVXQM-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000000774 hypoallergenic effect Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000001057 purple pigment Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 2
- MJQHDSIEDGPFAM-UHFFFAOYSA-N (3-benzoylphenyl)-phenylmethanone Chemical compound C=1C=CC(C(=O)C=2C=CC=CC=2)=CC=1C(=O)C1=CC=CC=C1 MJQHDSIEDGPFAM-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- OVJHMJJVXOJMBB-UHFFFAOYSA-N 2-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)ethyl prop-2-enoate Chemical compound C1CCCC2C(=O)N(CCOC(=O)C=C)C(=O)C21 OVJHMJJVXOJMBB-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- ODIARNBUHATISP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(CC(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 ODIARNBUHATISP-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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Landscapes
- Cosmetics (AREA)
Description
本発明は光硬化性人工爪組成物に関する。 The present invention relates to a photocurable artificial nail composition.
手や足の自爪に装飾を施したり、人工爪を接着してこれに装飾を施すというネイルアートの人気が高まっている。また、装飾や、外力による爪の割れ・剥がれを防止するための補強の目的で、いわゆるマニキュア、ペディキュア、スカルプチュアと呼ばれる樹脂含有の材料を爪に塗布することもなされている。 Nail art is becoming more and more popular, where you can decorate your own nails on your hands and feet, or glue artificial nails to decorate them. In addition, resin-containing materials such as so-called manicure, pedicure, and sculpture are also applied to the nails for the purpose of decoration and reinforcement to prevent the nails from cracking or peeling due to external force.
ここで、装飾又は補強のために使用される爪装飾材料としては、ニトロセルロース系のラッカーを有機溶剤に溶解し、これに各種色調の顔料を加えたものがある。これらは、爪や人工爪に塗布した後、有機溶剤を揮発させて、光沢に優れた被膜を形成するものである。そして、この被膜はアセトン等の有機溶剤を用いて容易に拭き取ることができる。
特に最近、ウレタンアクリレート系オリゴマーとアクリル系モノマーを含むジェル状の爪被覆材料を爪に塗布し、紫外線を照射して硬化させる、ジェルネイルと呼ばれる光硬化性人工爪組成物が注目を集めている。
これらは、ラジカル重合反応により、架橋した高分子被膜を形成するため、爪から剥がれにくい強靱な被膜を形成できるとされている。
Here, as the nail decoration material used for decoration or reinforcement, there is a material in which a nitrocellulose-based lacquer is dissolved in an organic solvent and pigments of various color tones are added thereto. These are applied to nails and artificial nails and then volatilize an organic solvent to form a film having excellent luster. Then, this film can be easily wiped off with an organic solvent such as acetone.
In particular, recently, a photocurable artificial nail composition called gel nail, in which a gel-like nail coating material containing a urethane acrylate-based oligomer and an acrylic-based monomer is applied to a nail and cured by irradiating with ultraviolet rays, has attracted attention. ..
Since these form a crosslinked polymer film by a radical polymerization reaction, it is said that a tough film that does not easily peel off from the nail can be formed.
このような光硬化性人工爪組成物として、特許文献１に記載されているように、該組成物中に紫外線の照射により重合可能な重量平均分子量３，０００〜５０，０００のポリウレタンアクリレートやモノマー成分を含有する、爪への密着性や除去性に優れた光硬化性人工爪組成物は公知である。
また、特許文献２に記載されているように、ウレタンアクリレートオリゴマー及びヒドロキシエチルアクリレートを含有し、人体に安全なＵＶＡにより短時間で十分に硬化させることができる光硬化性人工爪組成物も公知である。
特許文献３には、ネイル用の除去可能なゲル硬化性の組成物であって、ジ−［ヒドロキシエチルメタクリリック］トリメチルヘキシルジカルバメート、メタクリル酸エステル、２−ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート及び溶剤を含有する組成物であり、さらに配合し得る成分のうちの一種としてポリウレタンアクリレートオリゴマーも例示されている。
これらの文献に加えて、特許文献４に記載されるように、１分子内にラジカル重合性不飽和結合を有するラジカル重合性化合物、およびチオール化合物を含有する光硬化性人工爪原料組成物とすることによって、光を遮蔽した室温下にて保管の問題を発生させず、硬化後においても、人工爪内に未硬化の組成物が残存しないようにすることが記載されている。
As such a photocurable artificial nail composition, as described in Patent Document 1, a polyurethane acrylate or monomer having a weight average molecular weight of 3,000 to 50,000 that can be polymerized by irradiation with ultraviolet rays in the composition. A photocurable artificial nail composition containing an ingredient and having excellent adhesion to nails and removability is known.
Further, as described in Patent Document 2, a photocurable artificial nail composition containing a urethane acrylate oligomer and hydroxyethyl acrylate and capable of being sufficiently cured by UVA which is safe for the human body in a short time is also known. is there.
Patent Document 3 describes a removable gel-curable composition for nails, which is di- [hydroxyethyl methacrylate] trimethylhexyl dicarbamate, methacrylic acid ester, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate and solvent. A polyurethane acrylate oligomer is also exemplified as one of the components that can be further blended.
In addition to these documents, as described in Patent Document 4, a photocurable artificial nail raw material composition containing a radically polymerizable compound having a radically polymerizable unsaturated bond in one molecule and a thiol compound. It is described that this does not cause the problem of storage at room temperature in which light is shielded, and that the uncured composition does not remain in the artificial nail even after curing.
上記のように、公知の自爪塗布用光硬化性人工爪組成物は、硬化性に優れ、かつ塗布し硬化した後の特性に優れるものである。しかしながら、自爪の表面に塗布した後、時間の経過と共に、指先内部から自爪表面、さらに自爪表面から外部にかけて、体内の水分が浸透・蒸発するので、自爪表面に形成された人工爪に対してその水分も浸透する。
自爪表面に対する人工爪組成物の接着性を考慮して、人工爪組成物の主要成分が親水性を有することが通常であるため、上記の体内の水分に由来する水分が該人工爪にも浸透し、その結果、該人工爪組成物も水分を含有し、ひいては膨潤する結果となる。また、そのような人工爪組成物からなる被膜表面に、入浴時等における耐水性を付与する等を目的としてトップコート層を設ける必要があった。
そうすると、人工爪組成物は自爪に対して十分に強い力で密着することができず、何らかの拍子で自爪表面から人工爪組成物が剥離することになりかねない。
本発明は自爪内部及び外部からの水分を人工爪組成物による被膜が十分に吸収することなく、その結果として、自爪表面に形成させた人工爪組成物の被膜を長期的に高い密着性によって密着させること、さらに耐水性を付与することを目的として、さらに被覆層を設ける必要がない人工爪組成物の被膜層を得ることを課題とする。
As described above, the known photocurable artificial nail composition for self-nail application has excellent curability and excellent properties after application and curing. However, after applying to the surface of the nail, the water in the body permeates and evaporates from the inside of the fingernail to the surface of the nail and further from the surface of the nail to the outside with the passage of time, so that the artificial nail formed on the surface of the nail However, the water also penetrates.
Considering the adhesiveness of the artificial nail composition to the surface of the nail, the main component of the artificial nail composition is usually hydrophilic, so that the water derived from the water in the body is also applied to the artificial nail. Penetration results in the artificial nail composition also containing water and thus swelling. Further, it is necessary to provide a top coat layer on the surface of the coating film made of such an artificial nail composition for the purpose of imparting water resistance during bathing or the like.
Then, the artificial nail composition cannot be brought into close contact with the own nail with a sufficiently strong force, and the artificial nail composition may be peeled off from the surface of the own nail with some beat.
In the present invention, the film of the artificial nail composition does not sufficiently absorb the moisture from the inside and the outside of the nail, and as a result, the film of the artificial nail composition formed on the surface of the nail has high long-term adhesion. It is an object of the present invention to obtain a coating layer of an artificial nail composition that does not require a further coating layer for the purpose of bringing the nails into close contact with each other and further imparting water resistance.
本発明者らは、上記課題を解決すべく鋭意検討を行った結果、特定の組成物からなる自爪塗布用光硬化性人工爪組成物とすることで、上記課題が解決できることを見出し、自爪に対する人工爪の密着性を向上させて本発明を完成するに至った。
具体的には以下の通りである。
１．疎水性ウレタン（メタ）アクリレートオリゴマー、（メタ）アクリル系モノマー、及び光重合開始剤を含有する自爪塗布用光硬化性人工爪組成物。
２．疎水性ウレタン（メタ）アクリレートオリゴマーが、分岐を含みＣ５以上の炭素鎖セグメントを分子内に有する１に記載の自爪塗布用光硬化性人工爪組成物。
３．（メタ）アクリル系モノマーが、イソボルニルアクリレートである１又は２に記載の自爪塗布用光硬化性人工爪組成物。
４．（メタ）アクリル系モノマーが、リン酸エステル系（メタ）アクリレートである１又は２に記載の自爪塗布用光硬化性人工爪組成物。
As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by using a photocurable artificial nail composition for applying self-nail, which comprises a specific composition. The present invention has been completed by improving the adhesion of the artificial nail to the nail.
Specifically, it is as follows.
1. 1. A photocurable artificial nail composition for self-nail application containing a hydrophobic urethane (meth) acrylate oligomer, a (meth) acrylic monomer, and a photopolymerization initiator.
2. 2. The photocurable artificial nail composition for self-nail application according to 1, wherein the hydrophobic urethane (meth) acrylate oligomer contains a branch and has a carbon chain segment of C5 or more in the molecule.
3. 3. The photocurable artificial nail composition for self-nail application according to 1 or 2, wherein the (meth) acrylic monomer is isobornyl acrylate.
4. The photocurable artificial nail composition for self-nail application according to 1 or 2, wherein the (meth) acrylic monomer is a phosphoric acid ester-based (meth) acrylate.
本発明によれば、自爪表面に直に塗布した場合において、時間の経過と共に、自爪内部から自爪表面に浸透した水分が、疎水性の光硬化性人工爪組成物からなる被膜中に浸透することがなく、ひいては、自爪表面に対して長期にわたり密着性に優れる自爪塗布用光硬化性人工爪組成物を得ることができる。 According to the present invention, when applied directly to the surface of the nail, the water that has permeated the surface of the nail from the inside of the nail with the passage of time is contained in the film made of the hydrophobic photocurable artificial nail composition. It is possible to obtain a photocurable artificial nail composition for applying a self-nail, which does not permeate and has excellent adhesion to the surface of the self-nail for a long period of time.
本発明の自爪塗布用光硬化性人工爪組成物は、いわゆる一般のマニキュアやペディキュア、ジェルネイルのように、爪の表面に、ベースコート層、中間層であるカラーコート層、あるいはトップコート層として被覆を行うための組成物とすることもできるが、特に自爪の表面に直に塗布して被膜を得るための組成物とすることもできる。
そして、従来の紫外線等により硬化されるラジカル重合性のマニキュア等と同様の設備、紫外線硬化用の設備を用いて爪表面を被覆するものである。
本発明の自爪塗布用光硬化性人工爪組成物は特にジェルネイルとして使用することもできる。その中でも使用者の爪に直接塗布されるベースコート、該ベースコートの上に塗布されるカラーコート、さらにその上に塗布されるトップコートのいずれにも使用され得るものである。
自爪表面に直に塗布するベースコートは、一般的には透明又は僅かに黄色、場合により微量の紫や青の色素を配合して、経時劣化による色調の変化を防止することがある。
カラーコートはソリッドカラーやラメ調、金属光沢調、暗色や明色等多彩に着色されるコートである。
トップコートは、ベースコートと同様に、透明又は僅かに黄色、場合により微量の紫や青の色素を配合して、経時劣化による色調の変化を防止することがある。最上層であるため、ジェルネイルの艶を発揮させる作用を有する。本発明の光硬化性人工爪組成物は被膜表面の光沢度に優れるので、特にトップコート用として使用することが好ましい。
硬化後にも酸素による重合阻害等を原因とする、仮に未重合の光硬化性成分が被膜内に存在するときには、エタノール、イソプロパノール、酢酸エチルやアセトン等の溶剤、特にエタノールを用いて拭き取る工程が必要である。但し、十分な硬化性を備えるときには、このような工程を要しない。
いずれの層に関しても硬化後少なくとも２週間、欠けることなく、剥がれず、また下層や使用者の爪に対して浮きが発生しない。
The photocurable artificial nail composition for self-nail application of the present invention has a base coat layer, an intermediate color coat layer, or a top coat layer on the surface of the nail, like so-called general nail polish, pedicure, and gel nail. It can be used as a composition for coating, but it can also be used as a composition for obtaining a film by applying it directly to the surface of the nail polish.
Then, the nail surface is coated with the same equipment as the conventional radical-polymerizable nail polish that is cured by ultraviolet rays and the like, and equipment for curing ultraviolet rays.
The photocurable artificial nail composition for self-nail application of the present invention can also be used particularly as a gel nail. Among them, it can be used for any of a base coat applied directly to the user's nails, a color coat applied on the base coat, and a top coat applied on the base coat.
The base coat applied directly to the surface of the nail may be generally transparent or slightly yellow, and in some cases, a small amount of purple or blue pigment may be blended to prevent a change in color tone due to deterioration over time.
The color coat is a coat that is colored in various ways such as solid color, glitter, metallic luster, dark color and light color.
Like the base coat, the top coat may contain a transparent or slightly yellow, and in some cases, a trace amount of purple or blue pigment to prevent a change in color tone due to deterioration over time. Since it is the uppermost layer, it has the effect of exerting the luster of gel nails. Since the photocurable artificial nail composition of the present invention has excellent glossiness on the surface of the coating film, it is particularly preferable to use it for a top coat.
If an unpolymerized photocurable component is present in the film due to polymerization inhibition by oxygen even after curing, a step of wiping it off with a solvent such as ethanol, isopropanol, ethyl acetate or acetone, especially ethanol is required. Is. However, such a step is not required when sufficient curability is provided.
For at least 2 weeks after curing, none of the layers is chipped, does not peel off, and does not float on the lower layer or the user's nails.
以下に本発明の自爪塗布用光硬化性人工爪組成物の具体的組成について説明する。
[疎水性ウレタン（メタ）アクリレートオリゴマー]
本発明中の疎水性ウレタン（メタ）アクリレートオリゴマーとしては、イソシアネート基末端ウレタンプレポリマーに、水酸基を有する（メタ）アクリル化合物を加えて、前記ウレタンプレポリマー中のイソシアネート基総数の１０％以上のイソシアネート基に、前記水酸基を有する（メタ）アクリル化合物を付加反応させて得ることができる。なお、ここで、該イソシアネート基末端ウレタンプレポリマーは、イソシアネート基と反応するジオール化合物やジアミン化合物は、炭素鎖セグメントとして、炭素数が５以上のアルキル基、アルキレン基．不飽和結合を有する炭化水素基であって、直鎖構造又は分岐構造を有し、好ましくは炭素数６以上のアルキレン基を有することが必要である。
また、なかでも、平均アクリル当量が４００〜１０，０００の疎水性ウレタン（メタ）アクリレートオリゴマーであることが好ましい。また、平均アクリル当量が４００〜１０，０００の疎水性ウレタン（メタ）アクリレートオリゴマーは、このようにして得られた各種の平均アクリル当量（場合により一部はアクリル当量が４００未満又は１０，０００を超える）を有する複数種の疎水性ウレタン（メタ）アクリレートオリゴマーを合計して、全体として平均アクリル当量が４００〜１０，０００としてもよい。また、アクリロイル基に基づく官能基数は２〜６の範囲であることが好ましい。
なお、アクリル当量は、ゲル浸透クロマトグラフィーにより測定されたポリスチレン換算の重量平均分子量を、疎水性ウレタン（メタ）アクリレートオリゴマーが有するアクリロイル基の数で除した値である。
The specific composition of the photocurable artificial nail composition for self-nail application of the present invention will be described below.
[Hydrophobic urethane (meth) acrylate oligomer]
As the hydrophobic urethane (meth) acrylate oligomer in the present invention, an isocyanate group-terminated urethane prepolymer is added with a (meth) acrylic compound having a hydroxyl group to make an isocyanate of 10% or more of the total number of isocyanate groups in the urethane prepolymer. It can be obtained by subjecting the group to an addition reaction of the (meth) acrylic compound having a hydroxyl group. Here, the isocyanate group-terminated urethane prepolymer includes an alkyl group and an alkylene group having 5 or more carbon atoms as carbon chain segments of the diol compound and the diamine compound that react with the isocyanate group. It is necessary that the hydrocarbon group has an unsaturated bond, has a linear structure or a branched structure, and preferably has an alkylene group having 6 or more carbon atoms.
Further, among them, a hydrophobic urethane (meth) acrylate oligomer having an average acrylic equivalent of 400 to 10,000 is preferable. Further, the hydrophobic urethane (meth) acrylate oligomer having an average acrylic equivalent of 400 to 10,000 has various average acrylic equivalents (in some cases, an acrylic equivalent of less than 400 or 10,000) thus obtained. A plurality of types of hydrophobic urethane (meth) acrylate oligomers having (exceeding) may be summed up to have an average acrylic equivalent of 400 to 10,000 as a whole. The number of functional groups based on the acryloyl group is preferably in the range of 2 to 6.
The acrylic equivalent is a value obtained by dividing the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography by the number of acryloyl groups contained in the hydrophobic urethane (meth) acrylate oligomer.
本発明の自爪塗布用光硬化性人工爪組成物において、疎水性ウレタン（メタ）アクリレートオリゴマーを全自爪塗布用光硬化性人工爪組成物中に１０〜９９重量％、好ましくは３０〜７０重量％となるように含有させることができる。９９重量％よりも多く含有すると硬化時に収縮が発生し、硬化後の被膜にしわが発生する可能性がある。含有する量が１０重量％よりも少ないと、十分な硬度の被膜を形成させることができず、被膜表面に傷が付きやすくなる。
このような疎水性ウレタン（メタ）アクリレートオリゴマーを配合することにより、硬化被膜も疎水性を有することになり、爪表面から被膜に浸透される水によって、該被膜が柔軟化したり、膨潤したりすることがない。また、臭いが少なく伸縮性に優れ、かつ被膜の透明度が高く黄変せず、艶を有する高い硬度に硬化した自爪塗布用光硬化性人工爪組成物の被膜を得ることができる。そのため、場合によっては、トップコート用に適した光硬化性化合物とすることができる。
In the photocurable artificial nail composition for self-nail application of the present invention, the hydrophobic urethane (meth) acrylate oligomer is contained in the photocurable artificial nail composition for self-nail application in an amount of 10 to 99% by weight, preferably 30 to 70% by weight. It can be contained so as to be% by weight. If it is contained in an amount of more than 99% by weight, shrinkage occurs at the time of curing, and the film after curing may be wrinkled. If the content is less than 10% by weight, a film having sufficient hardness cannot be formed, and the surface of the film is easily scratched.
By blending such a hydrophobic urethane (meth) acrylate oligomer, the cured film also has hydrophobicity, and the water permeating the film from the nail surface softens or swells the film. Never. In addition, it is possible to obtain a film of a photocurable artificial nail composition for self-nail application, which has a low odor, is excellent in elasticity, has high transparency of the film, does not turn yellow, and is cured to a high hardness with luster. Therefore, in some cases, a photocurable compound suitable for a top coat can be obtained.
[単官能（メタ）アクリレートモノマー]
本発明の自爪塗布用光硬化性人工爪組成物にさらに含有させることが可能な、（メタ）アクリレートモノマーの中でも単官能（メタ）アクリレートモノマーは、自爪塗布用光硬化性人工爪組成物の臭いを少なくし、透明であって、低刺激性であり、反応性に優れ、黄変しない性質を備えることが必要である。
そのような単官能（メタ）アクリレートモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、シクロヘキシル（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、イソボルニル（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、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、Ｎ−アクリロイルオキシエチルヘキサヒドロフタルイミド等のアルコールと（メタ）アクリル酸とのエステル化物である（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリルアミド、アクリロイルモルフォリン等が挙げられる。
また、グリシジル（メタ）アクリレート、アリルグリシジルエーテル等のグリシジル基含有ラジカル重合性不飽和基含有化合物；スチレン、α−メチルスチレン、ビニルトルエン、α−クロルスチレン等のビニル芳香族化合物；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ−ｔ−ブチルアミノエチル（メタ）アクリレート等の含窒素アルキル（メタ）アクリレートを使用することもできる。
単官能アクリルアミド化合物としては、アクリルアミド、ヒドロキシエチルアクリルアミド、ジメチルアクリルアミド、ジエチルアクリルアミド、メタクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−ヒドロキシエチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド等の重合性アミド化合物等、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、２−カルボキシエチル（メタ）アクリレート、２−カルボキシプロピル（メタ）アクリレート、５−カルボキシペンチル（メタ）アクリレート等のカルボキシル基含有（メタ）アクリレート、２−オキセパノンホモポリマー、２−[(２−メチル−１−オキソ−２−プロペニル)オキシ]エチルエステル等の酸性の重合性モノマーも使用することができる。
また、リン酸メタクリル酸ヘキサン酸エチル、リン酸メタクリル酸プロパン酸ペンチル等の単官能のリン酸エステル系メタクリレートも使用することができる。
この単官能（メタ）アクリレートモノマーを配合しないこともでき、配合するときの配合比率としては、全自爪塗布用光硬化性人工爪組成物中に３０．０重量％以下、好ましくは２０．０重量％以下となるように含有させることができ、さらには含有しないことが好ましい。３０．０重量％を超えて配合すると、硬化速度が減衰し、未硬化樹脂が残存する可能性がある。
なお、２−ヒドロキシエチルメタクリレート及び／又はイソボルニル（メタ）アクリレートを配合することが好ましく、このときに硬化後の被膜の硬度と屈曲性のバランスが良好になる。これらの化合物を配合する場合には、好ましくはその合計の配合量を２０重量％以下とすることが好ましい。
[Monofunctional (meth) acrylate monomer]
Among the (meth) acrylate monomers that can be further contained in the photocurable artificial nail composition for self-nail application of the present invention, the monofunctional (meth) acrylate monomer is a photocurable artificial nail composition for self-nail application. It is necessary to reduce the odor of the nail, be transparent, be hypoallergenic, have excellent reactivity, and have the property of not yellowing.
Examples of such monofunctional (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meta) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenyl (meth) ) Acrylate, benzyl (meth) acrylate, (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, which is an esterified product of alcohol such as N-acryloyloxyethyl hexahydrophthalimide and (meth) acrylic acid. , Hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylamide, acryloylmorpholine and the like.
In addition, glycidyl group-containing radically polymerizable unsaturated group-containing compounds such as glycidyl (meth) acrylate and allyl glycidyl ether; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene; N, N- Nitrogen-containing alkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and Nt-butylaminoethyl (meth) acrylate can also be used.
Examples of monofunctional acrylamide compounds include acrylamide, hydroxyethyl acrylamide, dimethyl acrylamide, diethyl acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-methylol. (Meta) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl Polymerizable amide compounds such as aminoethyl (meth) acrylamide, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, Acidic polymerization of carboxyl group-containing (meth) acrylates such as 5-carboxypentyl (meth) acrylate, 2-oxepanone homopolymer, 2-[(2-methyl-1-oxo-2-propenyl) oxy] ethyl ester, etc. Sexual monomers can also be used.
In addition, monofunctional phosphate ester-based methacrylates such as ethyl hexanenate phosphate and pentyl propanate methacrylate can also be used.
This monofunctional (meth) acrylate monomer may not be blended, and the blending ratio at the time of blending is 30.0% by weight or less, preferably 20.0% by weight or less in the photocurable artificial nail composition for all-self nail application. It can be contained in an amount of% by weight or less, and more preferably it is not contained. If it is blended in excess of 30.0% by weight, the curing rate is attenuated and uncured resin may remain.
It is preferable to add 2-hydroxyethyl methacrylate and / or isobornyl (meth) acrylate, and at this time, the balance between the hardness and flexibility of the film after curing is improved. When these compounds are blended, the total blending amount is preferably 20% by weight or less.
[多官能（メタ）アクリレートモノマー]
本発明の自爪塗布用光硬化性人工爪組成物にさらに含有させることが可能な、上記のモノマー以外の（メタ）アクリレートモノマーの中でも多官能の（メタ）アクリレートモノマーとしては、ラジカル重合しうる不飽和基を１分子中に２以上有する化合物であって、本発明の自爪塗布用光硬化性人工爪組成物に配合できる化合物の１種である。ラジカル重合しうる不飽和基としては、炭素−炭素間二重結合をもつ官能基であり（重合性二重結合ともいう）、例えば、ビニル基、（メタ）アクリロイル基、（メタ）アクリルアミド基、ビニルエーテル基、アリル基等を挙げることができる。
そしてこれらの多官能（メタ）アクリレートモノマーには、自爪塗布用光硬化性人工爪組成物の臭いを少なくし、透明であって、低刺激性であり、反応性に優れ、黄変しない性質を備えることが必要である。
このような多官能（メタ）アクリレートモノマーとしては、エトキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化エトキシ化ビスフェノールＡジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレンジ（メタ）アクリレート、エトキシ化ポリプロピレングリコールジ（メタ）アクリレート、エトキシ化プロピレングリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジアクリレート、１，３−ブタンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド変性ジ（メタ）アクリレート等のジ（メタ）アクリレート化合物、グリセリントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキサイド変性トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイド変性トリ（メタ）アクリレート、等のトリ（メタ）アクリレート化合物、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトール（メタ）アクリレート、トリペンタエリスリトール（メタ）アクリレート、テトラペンタエリスリトール（メタ）アクリレート、エトキシ化イソシアヌル酸トリアクリレート等のエリスリトール類の（メタ）アクリレート類、ε−カプロラクトン変性トリス（アクリロキシエチル）イソシアヌレート、トリメチロールプロパンジ（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、ジトリメチロールプロパンテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレートを使用することができる。
また、リン酸ビス（メタクリル酸ヘキサン酸エチル）、リン酸ビス（メタクリル酸プロパン酸ペンチル）、リン酸トリ（メタクリル酸ヘキサン酸エチル）、リン酸トリ（メタクリル酸プロパン酸ペンチル）等の多官能のリン酸エステル系メタクリレートも使用することができる。
このような多官能（メタ）アクリレートモノマーは被膜の強度を調整するために配合することができ、配合するときの配合比率としては、０〜３０．０重量％、好ましくは０〜２５．０重量％である。３０．０重量％を超えて配合すると、硬化時において被膜の収縮が大きくなる可能性がある。また、多官能（メタ）アクリレートモノマーを含まない場合においても、ウレタン（メタ）アクリレートオリゴマーの比率で補える可能性がある。
[Polyfunctional (meth) acrylate monomer]
Among the (meth) acrylate monomers other than the above-mentioned monomers, which can be further contained in the photocurable artificial nail composition for self-nail coating of the present invention, the polyfunctional (meth) acrylate monomer can be radically polymerized. It is a compound having two or more unsaturated groups in one molecule, and is one of the compounds that can be blended in the photocurable artificial nail composition for self-adhesion coating of the present invention. The unsaturated group capable of radical polymerization is a functional group having a carbon-carbon double bond (also referred to as a polymerizable double bond), for example, a vinyl group, a (meth) acryloyl group, a (meth) acrylamide group, and the like. Examples thereof include a vinyl ether group and an allyl group.
And these polyfunctional (meth) acrylate monomers have the property of reducing the odor of the photocurable artificial nail composition for self-nail application, being transparent, hypoallergenic, excellent in reactivity, and not yellowing. It is necessary to prepare.
Examples of such polyfunctional (meth) acrylate monomers include ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and glycerin di (meth). Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, Polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tricyclodecanedimethanol diacrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, glycerindi (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A ethylene oxide-modified di (meth) ) Di (meth) acrylate compounds such as acrylate, tri (meth) acrylate compounds such as glycerin tri (meth) acrylate, trimethyl propanpropylene oxide modified tri (meth) acrylate, trimethyl propaneethylene oxide modified tri (meth) acrylate, etc. , Pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol (meth) acrylate, tripentaerythritol (meth) acrylate, tetrapentaerythritol (meth) acrylate, ethoxylated isocyanuric acid triacrylate and other erythritol (Meta) acrylates, ε-caprolactone-modified tris (acryloxyethyl) isocyanurate, trimethylpropandi (meth) acrylate, trimethylpropantri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, ethoxylated Pentaerythritol tetra (meth) acrylate can be used.
In addition, polyfunctional bis (ethyl methacrylate), bis (pentyl methacrylate), tri (ethyl methacrylate) phosphate, tri (pentyl methacrylate), etc. Phosphate ester-based methacrylate can also be used.
Such a polyfunctional (meth) acrylate monomer can be blended to adjust the strength of the coating film, and the blending ratio at the time of blending is 0 to 30.0% by weight, preferably 0 to 25.0% by weight. %. If it is blended in excess of 30.0% by weight, the shrinkage of the coating film may increase during curing. Further, even when the polyfunctional (meth) acrylate monomer is not contained, it may be supplemented by the ratio of the urethane (meth) acrylate oligomer.
［多官能チオール化合物］
本発明の自爪塗布用光硬化性人工爪組成物にさらに含有させることが可能な、多官能チオール化合物としては、トリメチロールプロパン、ペンタエリスリトール、及びジペンタエリスリトールが本来有する水酸基に、チオール基又は反応してチオール基になる基を有する化合物が反応して得たものが好ましい。
このような多官能チオール化合物としては、トリメチロールプロパントリス（３−メルカプトプロピオネート）、トリス[（３−メルカプトプロピオニルオキシ）−エチル]−イソシアヌレート、ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３−メルカプトプロピオネート）が挙げられる。
このような多官能チオール化合物を含有させることによって、自爪塗布用光硬化性人工爪組成物の粘度を調節することに加え、硬化した自爪塗布用光硬化性人工爪組成物を拭き取って除去する際の拭き取り性を向上させることができる。
本発明の自爪塗布用光硬化性人工爪組成物において、多官能チオール化合物を全自爪塗布用光硬化性人工爪組成物中に含有させる場合には、好ましくは１．０〜５０．０重量％、さらに好ましくは２．０〜２０．０重量％、より好ましくは７．０〜１８．０重量％となるように含有させることができる。５０．０重量％よりも多く含有すると硬化時の硬化速度が速すぎて、爪表面への塗布や、硬化時の取り扱いが困難になる可能性があり、含有する量が１．０重量％よりも少ないと、硬化速度が低下して、硬化後においても未硬化成分を含有する可能性がある。
[Polyfunctional thiol compound]
Examples of the polyfunctional thiol compound that can be further contained in the photocurable artificial nail composition for self-nail application of the present invention include thiol groups or thiol groups in the hydroxyl groups inherent in trimethylrol propane, pentaerythritol, and dipentaerythritol. A compound obtained by reacting a compound having a group which becomes a thiol group by reaction is preferable.
Examples of such polyfunctional thiol compounds include trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and pentaerythritol tetrakis (3-mercaptopropionate). , Dipentaerythritol hexakis (3-mercaptopropionate).
By containing such a polyfunctional thiol compound, in addition to adjusting the viscosity of the photocurable artificial nail composition for self-nail application, the cured photocurable artificial nail composition for self-nail application is wiped off and removed. It is possible to improve the wiping property at the time of wiping.
In the photocurable artificial nail composition for self-nail application of the present invention, when the polyfunctional thiol compound is contained in the photocurable artificial nail composition for self-nail application, it is preferably 1.0 to 50.0. It can be contained in an amount of% by weight, more preferably 2.0 to 20.0% by weight, and more preferably 7.0 to 18.0% by weight. If it is contained in an amount of more than 50.0% by weight, the curing rate at the time of curing may be too fast, and it may be difficult to apply it to the nail surface or handle it at the time of curing. If it is too small, the curing rate will decrease, and there is a possibility that uncured components will be contained even after curing.
[光重合開始剤]
本発明の自爪塗布用光硬化性人工爪組成物に配合する光重合開始剤は、ＬＥＤを光源とした紫外線や３６５〜４１０ｎｍ付近の波長の光（可視光の一部）によっても十分に硬化することができ、硬化時の発熱量を抑制することができるものが好ましい。
そのような光重合開始剤として、ベンゾインエーテル類、ベンジルケタール類、アシッドエステル類、α−アミノアルキルフェノン類、アシルフォスフィンオキシド類、ベンゾフェノン類、チオキサントン類、チタノセン類、を使用することができる。
これらの光重合開始剤として、具体的には、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキシド、フェニル酢酸、α−オキソ− オキシジ−２，１−エタンジイルエステル、オキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ]−エチルエステル、又はオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ]−エチルエステル、あるいはこれらの化合物の混合物、２，４−ジエチルチオキサントン、２−イソプロピルチオキサントン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１−オン、ビス（２，４，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキシド、ビス(２，４，６−トリメチルベンゾイル) −フェニルフォスフィンオキシド、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン、オリゴ（２−ヒドロキシ−２−メチル−１−（４−(１−メチルビニル)フェニル）プロパノン）、４−ベンゾイル−４’−メチル−ジフェニルスルフィド、１，２−オクタンジオン、１−（４−（フェニルチオ）−２，２−（Ｏ−ベンゾイルオキシム））１−ヒドロキシシクロヘキシルフェニルケトン、ベンゾインエチルエーテル、ベンジルジメチルケタール、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、および１−ヒドロキシシクロヘキシルフェニルケトン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］−フェニル｝−２−メチルプロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン、ベンゾフェノン、４−フェニルベンゾフェノン、イソフタルフェノンなどが好適に用いられる。なかでも、１−ヒドロキシシクロヘキシルフェニルケトンや２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキシドを使用することが好ましい。
[Photopolymerization initiator]
The photopolymerization initiator blended in the photocurable artificial nail composition for self-nail coating of the present invention is sufficiently cured by ultraviolet rays using an LED as a light source and light having a wavelength of around 365 to 410 nm (a part of visible light). It is preferable that the amount of heat generated during curing can be suppressed.
As such photopolymerization initiators, benzoin ethers, benzyl ketals, acid esters, α-aminoalkylphenones, acylphosphine oxides, benzophenones, thioxanthones, titanosenes, etc. can be used.
Specific examples of these photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylacetic acid, α-oxo-oxydi-2,1-ethanediyl ester, and oxy-phenyl-acetylid. 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, or oxy-phenyl-acetylic acid 2- [2-hydroxy-ethoxy] -ethyl ester, or a mixture of these compounds, 2,4 -Diethylthioxanthone, 2-isopropylthioxanthone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, bis (2,4,6-dimethoxybenzoyl) -2,4 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, oligo ( 2-Hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 4-benzoyl-4'-methyl-diphenylsulfide, 1,2-octanedione, 1- (4- (phenylthio) ) -2,2- (O-benzoyloxime)) 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-hydroxycyclohexyl Phenylketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -Phenyl} -2-methylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{ 4- [4- (2-Hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane, benzophenone, 4-phenylbenzophenone, isophthalphenone and the like are preferably used. Of these, it is preferable to use 1-hydroxycyclohexylphenylketone or 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
これらの光重合開始剤は、染料、顔料や重合性化合物の光吸収によってもラジカル生成反応が阻害されず、またラジカル発生効率が高く、自爪塗布用光硬化性人工爪組成物の硬化性を高めることができる点で好ましい。
これらの光重合開始剤は本発明の自爪塗布用光硬化性人工爪組成物中０．５〜２０．０重量％、好ましくは０．５〜５．０重量％となるように配合することができる。２０．０重量％を超えると、過剰な量のラジカルが発生することになるので、ラジカル重合反応が多くの開始点からなされ、その結果、硬化後のポリマーの分子量が小さくなって硬化膜が脆くなり、膜を維持できない可能性がある。また、０．５重量％未満であると十分な量のラジカルが発生できないので、ラジカル重合反応が長時間に及ぶこととなり、硬化不良となる可能性が高い。
These photopolymerization initiators do not inhibit the radical generation reaction even by the light absorption of dyes, pigments and polymerizable compounds, have high radical generation efficiency, and improve the curability of the photocurable artificial nail composition for self-nail application. It is preferable in that it can be enhanced.
These photopolymerization initiators are blended in an amount of 0.5 to 20.0% by weight, preferably 0.5 to 5.0% by weight, in the photocurable artificial nail composition for self-nail application of the present invention. Can be done. If it exceeds 20.0% by weight, an excessive amount of radicals will be generated, so that the radical polymerization reaction is carried out from many starting points, and as a result, the molecular weight of the cured polymer becomes small and the cured film becomes brittle. It may not be possible to maintain the membrane. Further, if it is less than 0.5% by weight, a sufficient amount of radicals cannot be generated, so that the radical polymerization reaction takes a long time, and there is a high possibility that curing failure occurs.
本発明の自爪塗布用光硬化性人工爪組成物には、光沢度、粘度や透明性、硬化性などに悪影響を与えない範囲で各種の添加剤を配合することができる。そのような添加剤としては、例えば、ポリオール類、シリコーン系やフッ素系の消泡剤、γ−グリシドキシプロピルトリメトキシシラン等のシランカップリング剤、充填剤、表面張力調整剤、重合禁止剤、難燃剤、酸化防止剤、イオン吸着体、着色剤、顔料、低応力化剤、抗菌剤、可撓性付与剤、ワックス類、ハロゲントラップ剤、レベリング剤、濡れ改良剤等の各種の添加剤を配合することができる。
なお、本発明の自爪塗布用光硬化性人工爪組成物に重合禁止剤を配合する場合には、重合禁止剤として、メトキノン等のキノン化合物、α−トコフェロール等のトコフェロール化合物、サリチル酸ヒドラジドを採用することが好ましい。
自爪塗布用光硬化性人工爪組成物中の重合禁止剤の含有量としては、重量の割合で５００〜５０００ｐｐｍが好ましく、より好ましくは１０００〜２５００ｐｐｍ、更に好ましくは１３００〜２３００ｐｐｍである。５０００ｐｐｍより含有量が多いときには、自爪塗布用光硬化性人工爪組成物が黄変する可能性があり、５００ｐｐｍよりも少ないときには、自爪塗布用光硬化性人工爪組成物が保管時において不用意に硬化してしまう可能性が高くなる。
また、本発明において、重合禁止剤は光重合開始剤による硬化を抑制する作用を有するので、光重合開始剤の含有量に対する重合禁止剤の含有量の比率を一定範囲とすることもできる。
このため、光重合開始剤１重量部に対して、好ましくは重合禁止剤を０．０３０〜０．１００重量部、より好ましくは０．０３５〜０．０８０重量部の範囲とすることができる。
In the photocurable artificial nail composition for self-nail coating of the present invention, various additives can be blended within a range that does not adversely affect glossiness, viscosity, transparency, curability and the like. Examples of such additives include polyols, silicone-based and fluorine-based defoamers, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, fillers, surface tension modifiers, and polymerization inhibitors. , Flame retardants, antioxidants, ion adsorbents, colorants, pigments, low stress agents, antibacterial agents, flexibility-imparting agents, waxes, halogen trapping agents, leveling agents, wetting improvers, etc. Can be blended.
When a polymerization inhibitor is added to the photocurable artificial nail composition for self-nail application of the present invention, a quinone compound such as methquinone, a tocopherol compound such as α-tocopherol, and hydrazide salicylate are used as the polymerization inhibitor. It is preferable to do so.
The content of the polymerization inhibitor in the photocurable artificial nail composition for applying self-nail is preferably 500 to 5000 ppm by weight, more preferably 1000 to 2500 ppm, and further preferably 1300 to 2300 ppm. When the content is higher than 5000 ppm, the photocurable artificial nail composition for self-nail application may turn yellow, and when the content is lower than 500 ppm, the photocurable artificial nail composition for self-nail application is not suitable for storage. There is a high possibility that it will cure easily.
Further, in the present invention, since the polymerization inhibitor has an action of suppressing curing by the photopolymerization initiator, the ratio of the content of the polymerization inhibitor to the content of the photopolymerization initiator can be set within a certain range.
Therefore, the polymerization inhibitor can be preferably in the range of 0.030 to 0.100 parts by weight, more preferably 0.035 to 0.080 parts by weight, based on 1 part by weight of the photopolymerization initiator.
着色剤としては公知の顔料、光輝材、染料を使用することができ、特に爪被覆用として使用されている無機顔料、光輝材有機顔料や染料を使用することができる。また、これらの着色剤を添加しない場合や透明となる程度の量、若しくは染料を添加することにより透明性がある光硬化性人工爪組成物とすることもできる。また、硬化前の自爪塗布用光硬化性人工爪組成物には、顔料等のみではなく樹脂粒子や、公知の光硬化性人工爪組成物に配合できる装飾用材料等を配合しておくことも可能である。
使用できる顔料及び染料の種類、及びそれらの含有量としては、紫外線の照射による硬化を阻害しない程度のものとすることが必要である。
As the colorant, known pigments, bright materials, and dyes can be used, and in particular, inorganic pigments, bright material organic pigments, and dyes used for nail coating can be used. Further, it is also possible to obtain a transparent photocurable artificial nail composition when these colorants are not added, in an amount that makes the nail transparent, or by adding a dye. In addition, the photocurable artificial nail composition for applying self-nail before curing should contain not only pigments but also resin particles and decorative materials that can be blended with known photocurable artificial nail compositions. Is also possible.
It is necessary that the types of pigments and dyes that can be used and their contents are such that they do not inhibit curing by irradiation with ultraviolet rays.
[自爪塗布用光硬化性人工爪組成物による被覆方法]
本発明の自爪塗布用光硬化性人工爪組成物は、使用者自身の爪の表面にサンディングを施すことなく、爪表面に凹凸を形成させる必要がない他は、公知の紫外線硬化型の光硬化性人工爪組成物と同様の方法により爪表面に塗布することができる。また、爪へのベースコート層（下地層）として、あるいは中間層、さらにトップコート層として使用することができる。
そのため、本発明の自爪塗布用光硬化性人工爪組成物は筆等の塗布具によって十分に塗布することができる程度の粘度を有すればよい。もちろん、爪表面に本発明の自爪塗布用光硬化性人工爪組成物を塗布後、硬化前に小さな飾りや粉体等を被膜表面に付着させることも可能である。
また、シートの片面に本発明の未硬化の自爪塗布用光硬化性人工爪組成物からなり、かつ爪の形状を有する層を設けておき、この層を爪表面に重ねるようにして付着させ、この自爪塗布用光硬化性人工爪組成物からなる層からシートを剥離するか又は剥離せずに、紫外線を照射して硬化することもできる。このようなシート表面に予め自爪塗布用光硬化性人工爪組成物からなる層を設けておけば、使用時に筆等の塗布具を使用することなく、爪の表面に均一かつ正確な模様を被覆することが可能である。そして使用後においても該塗布具を洗浄等する必要がない。
被覆される爪は、人の手の爪と足の爪のいずれでもよく、犬や猫などの動物の爪でも良い。
塗布後の自爪塗布用光硬化性人工爪組成物の硬化に関しても公知の紫外線硬化用の装置を用いて行うことができる。含有される化合物や顔料等の成分によって、硬化に必要な照射エネルギーは異なるものの、その光照射による照射エネルギー（積算光量）は、５ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下であるのが好ましく、１０ｍＪ／ｃｍ２以上８００ｍＪ／ｃｍ２以下であるのがより好ましい。照射エネルギーがこの範囲内であれば、十分な密着性および耐擦性を有するネイルアートが得られる。
光源としては、例えば、水銀ランプ、メタルハライドランプ、紫外線発光ダイオード（ＵＶ−ＬＥＤ）、紫外線レーザーダイオード（ＵＶ−ＬＤ）等の公知の紫外線の光源を用いることができる。
その中でも、小型、高寿命、高効率、低コストの観点から、紫外線発光ダイオード（ＵＶ−ＬＥＤ）および紫外線レーザーダイオード（ＵＶ−ＬＤ）が好ましい。
[Coating method with photo-curable artificial nail composition for self-nail application]
The photocurable artificial nail composition for applying self-nail of the present invention does not require sanding on the surface of the user's own nails and does not need to form irregularities on the surface of the nails. It can be applied to the nail surface by the same method as the curable artificial nail composition. Further, it can be used as a base coat layer (base layer) for nails, an intermediate layer, and a top coat layer.
Therefore, the photocurable artificial nail composition for self-nail application of the present invention may have a viscosity sufficient to be applied with a coating tool such as a brush. Of course, after applying the photocurable artificial nail composition for self-nail application of the present invention to the nail surface, it is also possible to attach a small decoration, powder or the like to the surface of the coating before curing.
Further, a layer made of the uncured photocurable artificial nail composition for self-nail application of the present invention and having a nail shape is provided on one side of the sheet, and this layer is adhered so as to be overlapped on the nail surface. The sheet can be peeled off from the layer made of the photocurable artificial nail composition for applying self-nail, or can be cured by irradiating ultraviolet rays without peeling. If a layer made of a photocurable artificial nail composition for applying self-nail is provided on the surface of such a sheet in advance, a uniform and accurate pattern can be formed on the surface of the nail without using a coating tool such as a brush at the time of use. It is possible to coat. And even after use, it is not necessary to wash the coating tool.
The claws to be covered may be either human hand claws or toenail claws, or may be claws of animals such as dogs and cats.
Curing of the photocurable artificial nail composition for self-nail coating after coating can also be performed using a known ultraviolet curing device. The components of the compounds and pigments to be contained, the irradiation energy although different required for curing, the irradiation by light irradiation energy (integrated light quantity) is preferably at 5 mJ / cm 2 or more 1000 mJ / cm 2 or less, 10 mJ More preferably, it is at least / cm 2 and 800 mJ / cm 2 . When the irradiation energy is within this range, nail art having sufficient adhesion and abrasion resistance can be obtained.
As the light source, for example, a known ultraviolet light source such as a mercury lamp, a metal halide lamp, an ultraviolet light emitting diode (UV-LED), or an ultraviolet laser diode (UV-LD) can be used.
Among them, ultraviolet light emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LD) are preferable from the viewpoints of small size, long life, high efficiency, and low cost.
表１に示す全配合成分（表中数値は重量％）を容器内に投入し、ディゾルバーにより撹拌しつつ５０℃に加温し撹拌した。これらの工程を全て遮光下にて行った。
＜組成物の評価＞
（耐水性）
厚さ１００μｍの自爪塗布用光硬化性人工爪組成物の被膜を硬質塩ビ板上に形成し、この被膜に対して３２ＷＬＥＤ−ＵＶライトで２０秒間紫外線を照射して硬化させた。
次いで、硬化され得られた被膜を常温の水に浸漬し、２０分放置した。
その後、ウッドスティックで被膜を削り、その欠損の程度によって、被膜の耐水性を目視で評価した。なお、市販の自爪塗布用光硬化性人工爪組成物はこのような試験により欠損する。
評価５：被膜に変化がなかった。
３：被膜が僅かに欠損した。
１：被膜が著しく欠損した。
All the compounding components shown in Table 1 (values in the table are% by weight) were put into a container, and the mixture was heated to 50 ° C. and stirred while stirring with a dissolver. All of these steps were performed under shading.
<Evaluation of composition>
(water resistant)
A film of a photocurable artificial nail composition for self-nail application having a thickness of 100 μm was formed on a hard vinyl chloride plate, and the film was cured by irradiating the film with ultraviolet rays for 20 seconds with a 32WLED-UV light.
Then, the cured film was immersed in water at room temperature and left for 20 minutes.
Then, the film was scraped with a wood stick, and the water resistance of the film was visually evaluated based on the degree of the defect. It should be noted that a commercially available photocurable artificial nail composition for applying self-nail is defective by such a test.
Evaluation 5: There was no change in the coating film.
3: The film was slightly missing.
1: The film was significantly damaged.
（密着性）
１８０Ｇのスポンジパフを用いて自爪表面を整え、自爪表面を消毒用エタノールで拭いた後、その自爪表面に自爪塗布用光硬化性人工爪組成物の被膜を形成し、この被膜に対して３２ＷＬＥＤ−ＵＶライトで２０秒間紫外線を照射して硬化させた。
次いで、市販のカラージェル、さらにトップジェルを塗布し、同条件で硬化させたものの、１４日後の状態を観察した。
評価５：被膜に変化がなかった。
４：被膜が１０本の指のうち１本以下で欠損が見られた。
３：被膜が１０本の指のうち３本以下で欠損が見られた。
１：被膜が１０本の指のうち４本以上欠損が見られた。
(Adhesion)
The surface of the nail is prepared using a 180 G sponge puff, the surface of the nail is wiped with ethanol for disinfection, and then a film of a photocurable artificial nail composition for applying the nail is formed on the surface of the nail. On the other hand, it was cured by irradiating it with ultraviolet rays for 20 seconds with a 32W LED-UV light.
Next, a commercially available color gel and a top gel were applied and cured under the same conditions, but the state after 14 days was observed.
Evaluation 5: There was no change in the coating film.
4: Defects were found in one or less of the ten fingers with a coating.
3: Defects were found in 3 or less of the 10 fingers with a coating.
1: The coating was found to be missing in 4 or more of the 10 fingers.
疎水性オリゴマーＡ：ネオペンチルグリコール及びオキセパノン構造を有するウレタンアクリレートオリゴマー（重量平均分子量：５０００、アクリロイル基に基づく官能基数２、アクリル当量：５０００／２＝２５００）
疎水性オリゴマーＢ：ネオペンチルグリコール及びオキセパノン構造を有するウレタンアクリレートオリゴマー（重量平均分子量：１５０００、アクリロイル基に基づく官能基数２、アクリル当量：１５０００／２＝７５００）
親水性オリゴマーＡ：ポリプロピレン構造を有するウレタンアクリレートオリゴマー（重量平均分子量：９０００、アクリロイル基に基づく官能基数２、アクリル当量：９０００／２＝４５００）
親水性オリゴマーＢ：ポリプロピレン構造を有するウレタンアクリレートオリゴマー（重量平均分子量：３５００、アクリロイル基に基づく官能基数２、アクリル当量：３５００／２＝１７５０）
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ＨＰＭＡ：２−ヒドロキシプロピルメタクリレート
ＩＢＸＡ：イソボルニルアクリレート
ＢＩＳＧＭＡ：イソプロピリデンジフェニルビス（メタクリル酸オキシヒドロキシプロピル）
ＰＭＡ：リン酸メタクリル酸ヘキサン酸エチル
ＰＭＡ２：リン酸ビス（メタクリル酸ヘキサン酸エチル）
光重合開始剤Ａ：１−ヒドロキシシクロヘキシルフェニルケトン
光重合開始剤Ｂ：２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキシド
Hydrophobic oligomer A: Neopentyl glycol and urethane acrylate oligomer having an oxepanone structure (weight average molecular weight: 5000, number of functional groups based on acryloyl group 2, acrylic equivalent: 5000/2 = 2500)
Hydrophobic oligomer B: Neopentyl glycol and urethane acrylate oligomer having an oxepanone structure (weight average molecular weight: 15,000, number of functional groups based on acryloyl group 2, acrylic equivalent: 15,000/2 = 7500)
Hydrophilic oligomer A: Urethane acrylate oligomer having a polypropylene structure (weight average molecular weight: 9000, number of functional groups based on acryloyl group 2, acrylic equivalent: 9000/2 = 4500)
Hydrophilic oligomer B: Urethane acrylate oligomer having a polypropylene structure (weight average molecular weight: 3500, number of functional groups based on acryloyl group 2, acrylic equivalent: 3500/2 = 1750)
HEMA: 2-Hydroxyethyl methacrylate
HPMA: 2-Hydroxypropyl methacrylate IBXA: Isobornyl acrylate BISGMA: Isopropyridene diphenylbis (oxyhydroxypropyl methacrylate)
PMA: Ethyl hexanoate methacrylate PMA2: Bis phosphate (ethyl hexanoate methacrylate)
Photopolymerization Initiator A: 1-Hydroxycyclohexylphenylketone Photopolymerization Initiator B: 2,4,6-trimethylbenzoyldiphenylphosphine oxide
上記実施例及び比較例の結果によると、疎水性ウレタン（メタ）アクリレートオリゴマーを用いて本発明に沿った例である実施例１〜６によれば、得られた被膜の耐水性が良好であり、密着性は悪くても被膜がほんの僅かに欠損する程度であった。この結果によれば、本発明によると耐水性と密着性のバランスがとれた被膜を形成できる。
これに対して、親水性ウレタン（メタ）アクリレートオリゴマーを用いた比較例１〜３によれば、被膜の耐水性に劣り、かつ密着性も不良であった。
According to the results of the above Examples and Comparative Examples, according to Examples 1 to 6, which are examples according to the present invention using the hydrophobic urethane (meth) acrylate oligomer, the water resistance of the obtained film is good. Although the adhesion was poor, the film was only slightly lost. According to this result, according to the present invention, a film having a good balance between water resistance and adhesion can be formed.
On the other hand, according to Comparative Examples 1 to 3 using the hydrophilic urethane (meth) acrylate oligomer, the water resistance of the coating film was inferior and the adhesion was also poor.
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