JP6858585B2 - UV curable resin composition and hard coat film - Google Patents
UV curable resin composition and hard coat film Download PDFInfo
- Publication number
- JP6858585B2 JP6858585B2 JP2017026503A JP2017026503A JP6858585B2 JP 6858585 B2 JP6858585 B2 JP 6858585B2 JP 2017026503 A JP2017026503 A JP 2017026503A JP 2017026503 A JP2017026503 A JP 2017026503A JP 6858585 B2 JP6858585 B2 JP 6858585B2
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- film
- resin composition
- curable resin
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- 239000011342 resin composition Substances 0.000 title claims description 17
- 239000010408 film Substances 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 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 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- ONCICIKBSHQJTB-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]propan-1-one Chemical compound CCC(=O)C1=CC=C(N(C)C)C=C1 ONCICIKBSHQJTB-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 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
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-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
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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- Laminated Bodies (AREA)
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- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は紫外線硬化型樹脂組成物及びハードコートフィルムに関する。 The present invention relates to an ultraviolet curable resin composition and a hard coat film.
従来、たとえばポリエチレンテレフタレート（ＰＥＴ）フィルムに蒸着やスパッタ、メッキ法等で意匠性、主に鏡面を実現するための金属を成膜したり、耐久性や導電性、赤外線吸収といった目的で金属酸化物を成膜するケースが増えている。このようなフィルムは金属調フィルムとして自動車の内装パーツなどに用いられたり、また窓貼り用フィルムとして赤外線カット、遮断熱フィルムといった目的で使用されている。しかしながらこのような金属薄膜および金属酸化物薄膜は硬度や耐擦傷性に乏しく、利用できる用途は限定さる。 Conventionally, for example, a polyethylene terephthalate (PET) film is vapor-deposited, sputtered, plated, or the like to form a metal for designability, mainly a mirror surface, or a metal oxide for the purpose of durability, conductivity, and infrared absorption. The number of cases of forming a film is increasing. Such a film is used as a metallic film for interior parts of automobiles and the like, and is also used as a film for attaching windows for purposes such as infrared ray cutting and heat blocking heat film. However, such metal thin films and metal oxide thin films have poor hardness and scratch resistance, and their usable applications are limited.
従来ではこのような基材に対して、金属密着性に優れたフェノール樹脂、エポキシ樹脂、メラミン樹脂等を熱硬化により成膜していた。しかしながら熱硬化プロセスで１０分間以上の硬化時間を必要とするため、生産性が悪くなり、また硬度も十分でなかった。 Conventionally, a phenol resin, an epoxy resin, a melamine resin, or the like having excellent metal adhesion has been formed on such a base material by thermosetting. However, since the thermosetting process requires a curing time of 10 minutes or more, the productivity is deteriorated and the hardness is not sufficient.
一方、紫外線硬化型樹脂組成物は、熱硬化型と比較し、生産性や硬度に優れるが、硬化時の塗膜収縮が大きいため、一般的に金属あるいは金属酸化物への密着性は悪いといった問題があった。そのため種々プライマー処理を施した後、紫外線硬化型ハードコート剤を塗工し、光沢や硬度を実現していた。しかしながら金属密着性や鉛筆硬度は十分なものの、耐擦傷性は決して十分なものではなかった。 On the other hand, the ultraviolet curable resin composition is superior in productivity and hardness to the thermosetting type, but generally has poor adhesion to metals or metal oxides due to the large shrinkage of the coating film during curing. There was a problem. Therefore, after applying various primer treatments, an ultraviolet curable hard coating agent was applied to achieve gloss and hardness. However, although the metal adhesion and the pencil hardness were sufficient, the scratch resistance was by no means sufficient.
市場では、プライマー処理を施すことで紫外線硬化型のメリットである生産性が低下し、コスト高に繋がるため、これら基材に対して密着性および硬度が良好な紫外線硬化型ハードコート樹脂組成物が望まれていた。 In the market, primer treatment reduces productivity, which is an advantage of UV curable type, and leads to high cost. Therefore, UV curable hard coat resin compositions having good adhesion and hardness to these substrates are available. It was desired.
発明者らは上記事由を鑑み、鋭意工夫を重ねた結果、金属密着性と硬化収縮を抑制した紫外線硬化型ハードコート樹脂組成物を開発した。 In view of the above reasons, the inventors have made diligent efforts to develop an ultraviolet curable hard coat resin composition that suppresses metal adhesion and curing shrinkage.
本発明は３個以上の（メタ）アクリロイル基を有する（メタ）アクリレートモノマー／オリゴマーと、リン酸エステル基を有する（メタ）アクリレートモノマーと、金属酸化物ナノ粒子とを必須成分とし、前記ナノ粒子の表面が（メタ）アクリレート基で修飾されていることを特徴とする。 The present invention comprises a (meth) acrylate monomer / oligomer having three or more (meth) acryloyl groups, a (meth) acrylate monomer having a phosphate ester group, and metal oxide nanoparticles as essential components, and said nanoparticles. The surface of the is modified with a (meth) acrylate group.
本発明の紫外線硬化型樹脂組成物からなる層は金属あるいは金属酸化物層への密着性が高く、また鉛筆硬度や耐擦傷性にも優れる紫外線硬化型樹脂組成物となる。 The layer made of the ultraviolet curable resin composition of the present invention is an ultraviolet curable resin composition having high adhesion to a metal or a metal oxide layer and also having excellent pencil hardness and scratch resistance.
３個以上の（メタ）アクリロイル基を有する（メタ）アクリレートモノマー／オリゴマーの具体的例としては、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンテトラ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、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、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テトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、アルキル変性ジペンタエリスリトールトリ（メタ）アクリレート、アルキル変性ジペンタエリスリトールテトラ（メタ）アクリレート、アルキル変性ジペンタエリスリトールペンタ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレートが挙げられ、これらの２種以上の混合物が挙げられる。とりわけ、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、或いはこれらの混合物が、耐摩耗性、硬化性の点からとりわけ好ましい。オリゴマーとして、多官能のウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート、ポリエーテルアクリレート、アクリルアクリレートなどが挙げられる。 Specific examples of the (meth) acrylate monomer / oligomer having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylol propanetri (meth) acrylate, and propylene oxide-modified tri. Methylolpropantri (meth) acrylate, trimethylpropantetra (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate Examples thereof include meta) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and examples thereof include a mixture of two or more of these. In particular, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, or a mixture thereof is particularly preferable from the viewpoint of wear resistance and curability. Examples of the oligomer include polyfunctional urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, acrylic acrylate and the like.
リン酸エステル基を有する（メタ）アクリレートモノマーとしては２−（メタ）アクリロイルオキシエチル−ジヒドロフォスフェート、ジ−（２−（メタ）アクリロイルオキシ）ヒドロゲンフォスフェート、トリス（メタ）アクリロイルオキシエチルフォスフェートなどが挙げられる。リン酸基と金属あるいは金属酸化物表面との反応によって金属あるいは金属酸化物基材への密着性が向上する。 Examples of the (meth) acrylate monomer having a phosphate ester group include 2- (meth) acryloyloxyethyl-dihydrophosphate, di- (2- (meth) acryloyloxy) hydrogen phosphate, and tris (meth) acryloyloxyethyl phos. Examples include fate. The reaction between the phosphoric acid group and the surface of the metal or metal oxide improves the adhesion to the metal or metal oxide base material.
リン酸エステル基を有する（メタ）アクリレートモノマーは前記多官能（メタ）アクリレート１００重量部に対し、１〜３０重量部、特に３〜２０重量部配合されるのが好ましい。１重量部未満では密着性向上効果に寄与せず、３０重量部を超えるとエステル基が加水分解しやすくなり、耐水性が低下する。 The (meth) acrylate monomer having a phosphoric acid ester group is preferably blended in an amount of 1 to 30 parts by weight, particularly 3 to 20 parts by weight, based on 100 parts by weight of the polyfunctional (meth) acrylate. If it is less than 1 part by weight, it does not contribute to the effect of improving adhesion, and if it exceeds 30 parts by weight, the ester group is easily hydrolyzed and the water resistance is lowered.
金属酸化物ナノ粒子としては、粒子表面が（メタ）アクリレート基で修飾された平均粒子径５〜１００ｎｍの（メタ）アクリレート基修飾金属酸化物ナノ粒子を溶媒に分散したものを用いる。未修飾のシリカ、アルミナなどの金属酸化物のナノ粒子を用いると、粒子表面の水酸基による影響で親水性を示し、樹脂中に混合すると凝集してしまい、均一分散が困難である。この粒子表面の水酸基と反応する有機化合物、例えば反応性モノマーやシランカップリング剤などを用いて表面に（メタ）アクリレート基で修飾して疎水化すると樹脂中で均一に分散され、ハードコートフィルムの耐擦傷性、鉛筆硬度を向上させることができる。また硬化収縮を抑制し、金属および金属薄膜への密着性向上にも寄与する。 As the metal oxide nanoparticles, those in which (meth) acrylate group-modified metal oxide nanoparticles having an average particle diameter of 5 to 100 nm whose particle surface is modified with (meth) acrylate groups are dispersed in a solvent are used. When nanoparticles of metal oxides such as unmodified silica and alumina are used, they exhibit hydrophilicity due to the influence of hydroxyl groups on the surface of the particles, and when mixed in a resin, they aggregate and it is difficult to uniformly disperse them. When the surface is modified with a (meth) acrylate group using an organic compound that reacts with the hydroxyl groups on the surface of the particles, for example, a reactive monomer or a silane coupling agent to make it hydrophobic, it is uniformly dispersed in the resin, and the hard coat film Scratch resistance and pencil hardness can be improved. It also suppresses curing shrinkage and contributes to improving adhesion to metals and metal thin films.
当該ナノ粒子の平均粒子径が５ｎｍより小さい場合は、十分な鉛筆硬度、耐擦傷性を得ることが難しく、１００ｎｍを超えると光学特性に劣りやすくなる。尚、平均粒径とはレーザー回折式粒度分布測定装置を用いて得られた値である。また、平均粒子径は、５０％分布粒子径とする。なお、５０％分布粒子径とは粒度分布が５０％のところの粒子径を指す。 When the average particle size of the nanoparticles is smaller than 5 nm, it is difficult to obtain sufficient pencil hardness and scratch resistance, and when it exceeds 100 nm, the optical characteristics tend to be inferior. The average particle size is a value obtained by using a laser diffraction type particle size distribution measuring device. The average particle size is 50% distributed particle size. The 50% distributed particle size refers to the particle size where the particle size distribution is 50%.
前記ナノ粒子としては、耐擦傷性や鉛筆硬度の観点から、シリカあるいはアルミナが好ましい。配合量としては、３個以上の（メタ）アクリロイル基を有する（メタ）アクリレートモノマー／オリゴマー１００重量部に対して、３０〜１５０重量部、特に５０〜１００重量部が好ましい。３０重量部未満では硬度、耐擦傷性の向上効果が不十分であり、１５０重量部を超えると、脆くなり耐久性に懸念が発生しやすくなるとともにコスト高となる。 As the nanoparticles, silica or alumina is preferable from the viewpoint of scratch resistance and pencil hardness. The blending amount is preferably 30 to 150 parts by weight, particularly preferably 50 to 100 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer / oligomer having three or more (meth) acryloyl groups. If it is less than 30 parts by weight, the effect of improving hardness and scratch resistance is insufficient, and if it exceeds 150 parts by weight, it becomes brittle and concerns about durability are likely to occur, and the cost is high.
光重合開始剤としては特に限定されるものではなく、アセトフェノン、２、２−ジエトキシアセトフェノン、ｐ−ジメチルアセトフェノン、ｐ−ジメチルアミノプロピオフェノン、ベンゾフェノン、２−クロロベンゾフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、などのカルボニル化合物、チオキサントン、２−クロロチオキサントン、２−メチルチオキサントン、テトラメチルチウラムジスルフィドなどの硫黄化合物、オキシムエステルなどが挙げられる。中でも硬化性、光安定性、相溶性、低揮発、低臭気という点から、アルキルフェノン系光重合開始剤を主として用いるのが好ましく、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−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−オン等が挙げられる。市販の光開始剤としてはＩｒｇａｃｕｒｅ１１７３、１２７、１８４、３６９、５００、６５１、７５４、２９５９（ＢＡＳＦ製）などを用いることが出来る。 The photopolymerization initiator is not particularly limited, and acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, benzoin, benzoin methyl ether, etc. Examples thereof include carbonyl compounds such as benzoin ethyl ether and benzoin isopropyl ether, sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone and tetramethylthium disulfide, and oxime esters. Among them, it is preferable to mainly use an alkylphenone-based photopolymerization initiator from the viewpoints of curability, photostability, compatibility, low volatility, and low odor, and 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1 are preferable. Examples thereof include −phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one and the like. As a commercially available photoinitiator, Irgacure1173, 127, 184, 369, 500, 651, 754, 2959 (manufactured by BASF) and the like can be used.
また、本発明の紫外線硬化型樹脂組成物には必要に応じて、有機溶剤、酸化防止剤、ブルーイング剤、顔料、レベリング剤、消泡剤、増粘剤、沈澱防止剤、帯電防止剤、防曇剤、スリップ剤、抗菌剤等を添加してもよい。 Further, the ultraviolet curable resin composition of the present invention contains, if necessary, an organic solvent, an antioxidant, a bluing agent, a pigment, a leveling agent, an antifoaming agent, a thickener, an antioxidant, an antistatic agent, and the like. Antifogging agents, slip agents, antibacterial agents and the like may be added.
上記成分は溶剤にて希釈され固形分が３〜８０％に調整される。溶剤としては、例えば、メタノール、エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール、ジアセトンアルコール等のアルコール系溶媒、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、ｎ−プロピルセロソルブ等のセロソルブ系溶剤、アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン、シクロヘキサノン、イソホロン等のケトン系溶剤、ギ酸メチル、ギ酸ブチル、酢酸メチル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテ等のエーテル系溶媒、N，N−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド系溶媒等が挙げられる。 The above components are diluted with a solvent to adjust the solid content to 3 to 80%. Examples of the solvent include alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol and diacetone alcohol, methyl cellosolve and ethyl cellosolve. , Cellosolve solvents such as butyl cellosolve, n-propyl cellosolve, ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, isophorone, ester solvents such as methyl formate, butyl formate, methyl acetate, butyl acetate, etc. Examples thereof include ether solvents such as diethyl ether and diisopropylate, and amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide.
本発明に使用するプラスチック基材上に成膜された金属あるいは金属酸化物としては特に限定されるものではなく、アルミ、銅、ニッケル、クロム、スズ、インジウム、亜鉛、金、銀、白金およびこれらの合金や酸化物が挙げられ、他にスズドープ酸化インジウム、シリカ、酸化チタン、酸化ジルコニウムなどが挙げられる。 The metal or metal oxide formed on the plastic substrate used in the present invention is not particularly limited, and aluminum, copper, nickel, chromium, tin, indium, zinc, gold, silver, platinum and these are not particularly limited. Examples of alloys and oxides include tin-doped indium oxide, silica, titanium oxide, and zirconium oxide.
薄膜を形成する基材となるプラスチック基材も種々公知なものが使用でき、プラスチックフィルムとしては、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレンビニルアルコールフィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルフォンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルフォンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッソ樹脂フィルム、ナイロンフィルム、アクリルフィルム、シクロオレフィン（コ）ポリマーフィルム等を挙げることができる。 Various known plastic substrates can be used as the substrate for forming the thin film, and the plastic films include polyester film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, and acetyl cellulose butyrate film. , Polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, polystyrene film, polycarbonate film, polymethylpentene film, polysulphon film, polyether ether ketone film, polyether sulfone film, polyetherimide film , Polygonic film, fluorine resin film, nylon film, acrylic film, cycloolefin (co) polymer film and the like.
なかでも価格、加工性、寸法安定性などの点から二軸延伸処理されたポリエステルフィルムが好ましく用いられる。フィルムの厚みは概ね２３μｍ〜２５０μｍであればよい。 Among them, a biaxially stretched polyester film is preferably used from the viewpoints of price, workability, dimensional stability and the like. The thickness of the film may be approximately 23 μm to 250 μm.
紫外線硬化型樹脂組成物を塗布する方法は、特に制限はなく、公知のスプレーコート、ロールコート、ダイコート、エアナイフコート、ブレードコート、スピンコート、リバースコート、グラビアコート、ワイヤーバーなどの塗工法またはグラビア印刷、スクリーン印刷、オフセット印刷、インクジェット印刷などの印刷法により形成できる。乾燥膜厚は、０．０５μｍ〜３μｍが好ましいが、５０〜５００ｎｍがより好ましい。膜厚が５０ｎｍ未満だと十分な硬度、耐擦傷性が発現せず、５００ｎｍを超えると硬化収縮で密着性に悪影響が出る。 The method of applying the ultraviolet curable resin composition is not particularly limited, and is a coating method such as a known spray coat, roll coat, die coat, air knife coat, blade coat, spin coat, reverse coat, gravure coat, wire bar, or gravure. It can be formed by printing methods such as printing, screen printing, offset printing, and inkjet printing. The dry film thickness is preferably 0.05 μm to 3 μm, more preferably 50 to 500 nm. If the film thickness is less than 50 nm, sufficient hardness and scratch resistance will not be exhibited, and if it exceeds 500 nm, curing shrinkage will adversely affect the adhesion.
紫外線硬化型樹脂組成物を塗布した後は、６０〜１２０℃で乾燥する。紫外線硬化型樹脂組成物は、紫外線照射機を用いて５００ｍＷ／ｃｍ２〜３０００ｍＷ／ｃｍ２の照射強度で、仕事量が５０〜４００ｍＪ／ｃｍ２の紫外線処理を行い硬化させる。紫外線発生源としては一般的に紫外線ランプが用いられており、具体的には、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、メタルハライドランプなどが挙げられ、照射する場合は空気中でもよいし、窒素、アルゴンなどの不活性ガス中でもよい。 After applying the ultraviolet curable resin composition, it is dried at 60 to 120 ° C. UV-curable resin composition, using an ultraviolet irradiator at an irradiation intensity of 500mW / cm 2 ~3000mW / cm 2 , the amount of work hardening with ultraviolet processing 50~400mJ / cm 2. An ultraviolet lamp is generally used as an ultraviolet source, and specific examples thereof include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, and a metal halide lamp. It may be an inert gas such as nitrogen or argon.
以下、本発明を実施例、比較例に基づき詳細に説明するが、具体例を示すものであって特にこれらに限定するものではない。重量部は固形分重量を示す。表中の配合例は全て固形分重量である。 Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but specific examples are shown and the present invention is not particularly limited thereto. The weight part indicates the solid content weight. The compounding examples in the table are all solid content weights.
ジペンタエリスリトールヘキサアクリレート（商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ、日本化薬株式会社製、固形分１００％）１００重量部、２−（メタ）アクリロイルオキシエチル−ジヒドロフォスフェート（商品名：ＫＡＹＡＭＥＲ ＰＭ−２、日本化薬株式会社製、固形分１００％）５重量部、ナノ分散シリカ微粒子（商品名：ＭＥＫ−ＡＣ−２１４０Ｚ、日産化学株式会社製、平均粒径１５ｎｍ、ＳｉＯ２量４０％、粒子表面メタクリレート基）１２５重量部、開始剤としてＩｒｇａｃｕｒｅ１８４（ＢＡＳＦ社製）を５重量部加え、溶剤として、ＭＥＫ（メチルエチルケトン）を配合して固形分２０重量％の紫外線硬化型樹脂組成物を得た。 Dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., solid content 100%) 100 parts by weight, 2- (meth) acryloyloxyethyl-dihydrophosphate (trade name: KAYAMER PM-2, Japan) Made by Kayaku Co., Ltd., solid content 100%) 5 parts by weight, nano-dispersed silica fine particles (trade name: MEK-AC-2140Z, manufactured by Nissan Chemical Co., Ltd., average particle size 15 nm, SiO 2 amount 40%, particle surface methacrylate group ) 125 parts by weight and 5 parts by weight of Irgacure184 (manufactured by BASF) as an initiator was added, and MEK (methyl ethyl ketone) was blended as a solvent to obtain an ultraviolet curable resin composition having a solid content of 20% by weight.
次いで、得られた紫外線硬化型樹脂組成物をＰＥＴフィルム上にアルミニウム蒸着したフィルムにバーコーターにて硬化後の樹脂膜厚が１５０ｎｍとなるように塗工し、８０℃１分間乾燥させ、窒素雰囲気下において、紫外線照射機（高圧水銀ランプ）を用いて１５００ｍＷ／ｃｍ２の照射強度で、仕事量が１５０ｍＪ／ｃｍ２の紫外線処理を行い、ハードコートフィルムを得た。 Next, the obtained ultraviolet curable resin composition was coated on a PET film on which aluminum was vapor-deposited so that the resin film thickness after curing was 150 nm with a bar coater, and dried at 80 ° C. for 1 minute to create a nitrogen atmosphere. in the lower, at an irradiation intensity of 1500 mW / cm 2 using UV irradiation machine (high-pressure mercury lamp), the amount of work with ultraviolet processing 150 mJ / cm 2, to obtain a hard coat film.
実施例１において、ＰＭ−２を１０重量部とした以外は同様に実施した。 In Example 1, the same procedure was carried out except that PM-2 was 10 parts by weight.
実施例１において、ＰＭ−２を２５重量部とした以外は同様に実施した。 In Example 1, the same procedure was carried out except that PM-2 was 25 parts by weight.
実施例１において、ＭＥＫ−ＡＣ−２１４０Ｚを２５０重量部とした以外は同様に実施した。 In Example 1, the same procedure was carried out except that MEK-AC-2140Z was 250 parts by weight.
実施例１において、ＭＥＫ−ＡＣ−２１４０Ｚを３２５重量部とした以外は同様に実施した。 In Example 1, the same procedure was carried out except that MEK-AC-2140Z was 325 parts by weight.
実施例１において、ＭＥＫ−ＡＣ−２１４０Ｚの代わりにナノ分散アルミナ微粒子（商品名：ＡＬＭＩＢＫ３０ＷＴ％−Ｍ４７、ＣＩＫナノテック株式会社製、アルミナ量３０％、平均粒径３０ｎｍ、粒子表面メタクリレート基）を用い、１６６．６重量部配合した以外は同様に実施した。 In Example 1, nano-dispersed alumina fine particles (trade name: ALMIBK30WT% -M47, manufactured by CIK Nanotech Co., Ltd., alumina amount 30%, average particle size 30 nm, particle surface methacrylate group) were used instead of MEK-AC-2140Z. The same procedure was carried out except that 166.6 parts by weight was blended.
実施例１において、膜厚を４００ｎｍとした以外は同様に実施した。 In Example 1, the same procedure was carried out except that the film thickness was set to 400 nm.
比較例１
実施例１において、ＰＭ−２を０．５重量部とした以外は同様に実施した。
Comparative Example 1
In Example 1, the same procedure was carried out except that PM-2 was 0.5 parts by weight.
比較例２
実施例１において、ＰＭ−２を５０重量部とした以外は同様に実施した。
Comparative Example 2
In Example 1, the same procedure was carried out except that PM-2 was 50 parts by weight.
比較例３
実施例１において、ＭＥＫ−ＡＣ−２１４０Ｚを無くした以外は同様に実施した。
Comparative Example 3
In Example 1, the same procedure was carried out except that MEK-AC-2140Z was eliminated.
比較例４
実施例１において、膜厚を２０ｎｍとした以外は同様に実施した。
Comparative Example 4
In Example 1, the same procedure was carried out except that the film thickness was set to 20 nm.
比較例５
実施例１において、膜厚を５ｕｍとした以外は同様に実施した。
Comparative Example 5
In Example 1, the same procedure was carried out except that the film thickness was set to 5 um.
比較例６
実施例１において、ＭＥＫ−ＡＣ−２１４０Ｚの代わりにナノ分散シリカ微粒子（商品名：ＰＧＭ−ＳＴ、日産化学株式会社製、平均粒径１５ｎｍ、ＳｉＯ２量３０％、粒子表面修飾なし）とした以外は同様に実施した。
Comparative Example 6
In Example 1, nano-dispersed silica fine particles (trade name: PGM-ST, manufactured by Nissan Chemical Industries, Ltd., average particle size 15 nm, SiO2 amount 30%, no particle surface modification) were used instead of MEK-AC-2140Z. It was carried out in the same manner.
評価結果を表１、表２に示す。表中の配合量は全て固形分とした。
評価方法は以下の通りとした。
（１）基材密着性：ＪＩＳ Ｋ５６００に基づき試験し、１００マス目のうち剥離していないマス目の数を記載した。
剥離せず：１００／１００
剥離あり：０／１００〜９９／１００
（２）鉛筆硬度：ＪＩＳ Ｋ５６００−５−４に基づき、７５０ｇ荷重で評価を行った。
（３）耐擦傷性：＃００００のスチールウールに５００ｇ／ｃｍ２の荷重を掛け、１０往復させ、傷の状態を確認し下記の評価をした。
○：傷なし、△：傷１０本以内、×：傷１１本以上
The evaluation method was as follows.
(1) Adhesion to base material: A test was conducted based on JIS K5600, and the number of cells that were not peeled out of the 100 cells was described.
Without peeling: 100/100
With peeling: 0/100 to 99/100
(2) Pencil hardness: Based on JIS K5600-5-4, evaluation was performed with a load of 750 g.
(3) Scratch resistance: A load of 500 g / cm2 was applied to # 0000 steel wool and reciprocated 10 times, the state of scratches was confirmed, and the following evaluation was performed.
○: No scratches, △: Within 10 scratches, ×: 11 or more scratches
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