JP2023000961A - Solventless photocurable resin composition - Google Patents
Solventless photocurable resin composition Download PDFInfo
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- 239000011342 resin composition Substances 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 150000002222 fluorine compounds Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000003550 marker Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- -1 polysiloxane skeleton Polymers 0.000 description 3
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-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
- 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
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 230000004927 fusion Effects 0.000 description 2
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- 229920002223 polystyrene Polymers 0.000 description 2
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- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XQAVYBWWWZMURF-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO XQAVYBWWWZMURF-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 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 1
- 230000000740 bleeding effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
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- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 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 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229920006393 polyether sulfone Polymers 0.000 description 1
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- 239000003505 polymerization initiator Substances 0.000 description 1
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- 229920000306 polymethylpentene Polymers 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、撥水撥油性を有する無溶剤の光硬化型樹脂組成物に関する。 TECHNICAL FIELD The present invention relates to a solventless photocurable resin composition having water and oil repellency.
アクリル系の光硬化型樹脂は、プラスチックフィルムやプラスチック成形物表面に特別な性能を 付与するために多くの分野で用いられており、例えばＰＥＴ（ポリエチレンテレフタレート）フィルム上に塗布して高硬度を付与したハードコートフィルムは、タッチパネル用フィルムや成形用フィルムとして大量に使用されている。 Acrylic light-curing resins are used in many fields to impart special performance to the surface of plastic films and plastic moldings. The resulting hard coat film is used in large quantities as a film for touch panels and a film for molding.
これらの中でタッチパネル用フィルムは、スマートフォンに代表される情報端末の入力装置表面部材として、広範に用いられており、特に近年では高い透明性や硬度に加え、防汚性を求められることも多くなっている。そのため撥水性、撥油性を高めた硬化膜として、例えばアルコキシシリル基を有する化合物成分と２個以上の（メタ）アクリロイルを有するアクリレートを含む樹脂組成物が提案されている（特許文献１）。 Among them, touch panel films are widely used as input device surface materials for information terminals represented by smartphones, and in recent years, in addition to high transparency and hardness, there are many demands for antifouling properties. It's becoming Therefore, as a cured film with improved water repellency and oil repellency, for example, a resin composition containing a compound component having an alkoxysilyl group and an acrylate having two or more (meth)acryloyl groups has been proposed (Patent Document 1).
こうしたハードコート樹脂は、良好な塗工性を得るため溶剤を含むことが一般的であるが、溶剤を揮発させるための装置やプロセスが必須となり、またそこから放出される溶剤は環境面でも大きな負荷となっていた。一方、ハードコート樹脂を無溶剤化した場合は、溶剤が揮発する際に表面調整剤が塗工表面に浮き上がり、密集することで塗膜外観や物性を変化させることができる、いわゆるリフティング効果が期待できなくなるため、安定した外観形成や、撥水性や撥油性等の特性を安定して付与することが難しくなるという課題があった。そのため、無溶剤でありながら塗工性や外観が良好で、かつ硬化膜が安定した撥水撥油特性を有するハードコート樹脂とするには改善の余地があった。 Such hard coat resins generally contain a solvent in order to obtain good coating properties. was a load. On the other hand, when the hard coat resin is made solventless, the so-called lifting effect can be expected, in which the surface control agent floats on the coating surface when the solvent evaporates. Therefore, there is a problem that it becomes difficult to form a stable appearance and to stably impart properties such as water repellency and oil repellency. Therefore, there is room for improvement in obtaining a hard coat resin that is solvent-free, has good coatability and appearance, and has stable water and oil repellency as a cured film.
本発明の課題は、無溶剤でありながら塗工性が良好であると共に、硬化膜が良好な撥水性及び撥油性を有する光硬化型の樹脂組成物を提供することにある。 An object of the present invention is to provide a photocurable resin composition which is solvent-free, has good coatability, and gives a cured film having good water repellency and oil repellency.
上記課題を解決するため本出願に係る請求項１の発明は、骨格にＳｉ原子に有する３官能以上のウレタン（メタ）アクリレートオリゴマー（Ａ）と、反応性希釈剤（Ｂ）と、表面調整剤（Ｃ）と、光重合開始剤（Ｄ）とを含み、前記（Ａ）の重量平均分子量が８００～１０，０００であり、前記（Ｂ）の配合量が固形分全量に対し６５重量％以下であることを特徴とする無溶剤光硬化型樹脂組成物を提供する。 In order to solve the above problems, the invention of claim 1 according to the present application provides a trifunctional or higher urethane (meth)acrylate oligomer (A) having Si atoms in the skeleton, a reactive diluent (B), and a surface conditioner (C) and a photopolymerization initiator (D), wherein the weight average molecular weight of (A) is 800 to 10,000, and the amount of (B) is 65% by weight or less based on the total solid content. To provide a solventless photocurable resin composition characterized by:
また請求項２の発明は、前記（Ａ）単独の硬化物の水接触角が８５°以上であることを特徴とする請求項１記載の無溶剤光硬化型樹脂組成物を提供する。 The invention according to claim 2 provides the solventless photocurable resin composition according to claim 1, wherein the water contact angle of the single cured product of (A) is 85° or more.
また請求項３の発明は、前記（Ｃ）が反応性官能基を有するフッ素系化合物であることを特徴とする請求項１又は２記載の無溶剤光硬化型樹脂組成物を提供する。 The invention of claim 3 provides the solventless photocurable resin composition of claim 1 or 2, wherein the (C) is a fluorine compound having a reactive functional group.
また請求項４の発明は、前記（Ｂ）が３～４官能の（メタ）アクリレートであることを特徴とする請求項１～３いずれか記載の無溶剤光硬化型樹脂組成物を提供する。 The invention according to claim 4 provides the solventless photocurable resin composition according to any one of claims 1 to 3, wherein the (B) is a tri- to tetra-functional (meth)acrylate.
本発明の光硬化型樹脂組成物は、無溶剤でありながら塗工性が良好であると共に、硬化膜が十分な撥水性及び撥油性を有するため、防汚性を求められるハードコートフィルムに用いるハードコート（以下ＨＣ）樹脂として有用である。 The photocurable resin composition of the present invention has good coatability while being solvent-free, and the cured film has sufficient water repellency and oil repellency, so it is used for hard coat films that require antifouling properties. It is useful as a hard coat (hereinafter HC) resin.
本発明について詳細に説明する。 The present invention will be described in detail.
本発明のＨＣ樹脂組成物は、骨格にＳｉ原子に有する３官能以上のウレタン（メタ）アクリレート（Ａ）と、反応性希釈剤（Ｂ）と、表面調整剤（Ｃ）と、光重合開始剤（Ｄ）を含む。なお、本明細書において（メタ）アクリレートとは、アクリレートとメタクリレートとの双方を包含する。 The HC resin composition of the present invention comprises a trifunctional or higher urethane (meth)acrylate (A) having Si atoms in the skeleton, a reactive diluent (B), a surface conditioner (C), and a photopolymerization initiator. including (D). In this specification, (meth)acrylate includes both acrylate and methacrylate.
本発明で使用する骨格にＳｉ原子に有する３官能以上のウレタン（メタ）アクリレート（以下ウレアク）（Ａ）は、骨格にＳｉ原子を有し、それ自体で撥水性及び撥油性を有する、ハードコート皮膜を構成する主成分である。１分子中に３個以上の（メタ）アクリロイル基を有し、ウレタン結合に由来する水素結合の凝集力により優れた耐擦傷性を有する樹脂であり、（Ｃ）との組合せにより、硬化皮膜に安定した撥水性及び撥油性を付与することができる。 A tri- or more functional urethane (meth)acrylate (hereinafter referred to as ureac) (A) having Si atoms in the skeleton used in the present invention has Si atoms in the skeleton and itself has water repellency and oil repellency. It is the main component that constitutes the film. It is a resin that has three or more (meth)acryloyl groups in one molecule and has excellent scratch resistance due to the cohesion of hydrogen bonds derived from urethane bonds. Stable water repellency and oil repellency can be imparted.
前記（Ａ）は、従来公知の方法により調整することができ、例えば特開２００４－１６０９３２や特許第６０３５３２５号に記載される方法が例示できる。すなわち、ヘキサメチレンジイソシアネート（以下ＨＤＩ）のようなイソシアネート成分とポリシロキサン骨格を有する多価アルコール、水酸基と（メタ）アクリロイル基を有する化合物を、ジブチル錫ラウリレートやジブチル錫アセテート等の触媒を用いて、適当なモル比にて反応させるといった一般的なウレタン化反応により調整することが可能である。 The above (A) can be adjusted by a conventionally known method, for example, methods described in JP-A-2004-160932 and Japanese Patent No. 6035325 can be exemplified. That is, an isocyanate component such as hexamethylene diisocyanate (hereinafter HDI), a polyhydric alcohol having a polysiloxane skeleton, and a compound having a hydroxyl group and a (meth)acryloyl group are mixed with a catalyst such as dibutyltin laurate or dibutyltin acetate. It can be adjusted by a general urethanization reaction such as reacting at an appropriate molar ratio.
前記（Ａ）を単独で硬化させた時の水接触角としては８５°以上が好ましく、９０°以上が更に好ましい。この範囲とすることで、（Ｃ）と組み合わせて組成物としたときに、安定した撥水性及び撥油性を確保することができる。（Ａ）を単独で硬化させる際には、（Ａ）１００重量部に対し（Ｄ）５重量部を配合し、ＰＥＴフィルム上に膜厚１５μｍで塗布し、フュージョンＵＶシステムジャパン製の無電極ＵＶ照射装置Ｆ３００Ｓ／ＬＣ－６Ｂを用い、Ｈバルブで出力１２００ｍＷ／ｃｍ２、積算光量２００ｍＪ／ｃｍ２の条件で硬化させるものとする。 The water contact angle when (A) is cured alone is preferably 85° or more, more preferably 90° or more. Within this range, stable water repellency and oil repellency can be ensured when the composition is formed in combination with (C). When (A) is cured alone, 5 parts by weight of (D) is blended with 100 parts by weight of (A), applied to a film thickness of 15 μm on a PET film, and an electrodeless UV produced by Fusion UV System Japan. Curing is performed under the conditions of an irradiation device F300S/LC-6B, an H bulb output of 1200 mW/cm2, and an integrated light quantity of 200 mJ/cm2.
前記（Ａ）の重量平均分子量（以下Ｍｗ）は８００～１０，０００であり、１，０００～８，０００が好ましく、１，２００～６，５００が更に好ましい。８００未満では硬化収縮が大きくなるため反りやすくなり、１０，０００以上では組成物としての粘度が高くなりすぎ、安定した塗工が難しくなる。（Ａ）の官能基数としては３～１５官能が好ましく、４～１２官能が更に好ましい。３官能以上とすることで、十分な硬化反応性と皮膜凝集力を確保でき、１５官能以下とすることで、硬化収縮を大きくすることなく十分な耐擦傷性を確保することができる。なおＭｗは、ゲル浸透クロマトグラフィーにより、スチレンジビニルベンゼン基材の充填剤を用いたカラムでテトラハイドロフラン溶離液を用いて、標準ポリスチレン換算の分子量を測定、算出した。 The weight average molecular weight (hereinafter referred to as Mw) of (A) is 800 to 10,000, preferably 1,000 to 8,000, more preferably 1,200 to 6,500. If it is less than 800, curing shrinkage becomes large, and warping tends to occur. The number of functional groups of (A) is preferably 3-15, more preferably 4-12. By making it trifunctional or more, sufficient curing reactivity and film cohesion can be ensured, and by making it 15 or less, sufficient scratch resistance can be ensured without increasing cure shrinkage. The Mw was calculated by measuring the molecular weight in terms of standard polystyrene by gel permeation chromatography using a column using a styrene-divinylbenzene-based packing material and using a tetrahydrofuran eluent.
前記（Ａ）の固形分全量に対する配合比率は３０～９５重量％が好ましく、４０～９０重量％が更に好ましく、５０～８０重量％が特に好ましい。３０重量％以上とすることで十分な撥水撥油性を確保することができ、９５重量％以下とすることで十分安定した塗工特性を確保することができる。 The mixing ratio of (A) to the total solid content is preferably 30 to 95% by weight, more preferably 40 to 90% by weight, and particularly preferably 50 to 80% by weight. Sufficient water and oil repellency can be ensured by making it 30% by weight or more, and sufficiently stable coating properties can be ensured by making it 95% by weight or less.
本発明で使用する反応性希釈剤（Ｂ）は、組成物の粘度を塗工しやすい粘度に希釈すると共に、硬化皮膜の耐摩耗性を向上させる目的で配合する。官能基数としては２～６官能が好ましく、３～４官能が更に好ましい。２官能以上とすることで硬化物の分子量が十分な凝集力を有するレベルに大きくでき、６官能以下とすることで硬化収縮を大きくすることなく十分な耐擦傷性を確保することができる。 The reactive diluent (B) used in the present invention is blended for the purpose of diluting the viscosity of the composition to a viscosity that facilitates coating and improving the abrasion resistance of the cured film. The number of functional groups is preferably 2-6, more preferably 3-4. By making it bifunctional or more, the molecular weight of the cured product can be increased to a level having sufficient cohesive strength, and by making it hexafunctional or less, sufficient scratch resistance can be ensured without increasing cure shrinkage.
前記（Ｂ）としては、例えば２官能では１．４－ブタンジオールジ（メタ）アクリレート、４，６－ヘキサンジオール（メタ）アクリレート、ジメチロールトリシクロデカンジアクリレート、ペンタエリスリトールジ（メタ）アクリレートが、３官能ではトリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、グリセリントリ（メタ）アクリレートが、４官能でジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスルトールテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジグリセリンテトラ（メタ）アクリレート等が挙げられ、単独あるいは２種以上を組み合わせて使用することができる。これらの中では、（Ａ）との相溶性が高く、また硬化反応性が高い点でグリセリントリアクリレート、ペンタエリスリトールトリアクリレート（以下ＰＥ３Ａ）、ペンタエリスリトールテトラアクリレート（以下ＰＥ４Ａ）が好ましい。 Examples of the above (B) include difunctional 1.4-butanediol di(meth)acrylate, 4,6-hexanediol (meth)acrylate, dimethyloltricyclodecane diacrylate, and pentaerythritol di(meth)acrylate. , trifunctional trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and glycerin tri(meth)acrylate; tetrafunctional ditrimethylolpropane tetra(meth)acrylate; Pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, diglycerin tetra(meth)acrylate, etc., can be used alone or in combination of two or more. Among these, glycerin triacrylate, pentaerythritol triacrylate (hereinafter referred to as PE3A), and pentaerythritol tetraacrylate (hereinafter referred to as PE4A) are preferred because of their high compatibility with (A) and high curing reactivity.
前期（Ｂ）の固形分全量に対する配合比率は６５重量％以下であり、１０～６０重量％が好ましく、２０～５０重量％が更に好ましく、３０～４０重量％が特に好ましい。６５重量％以上では硬化皮膜に十分に安定した撥水性及び撥油性を付与することが難しく不可である。 The mixing ratio of the former term (B) to the total solid content is 65% by weight or less, preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and particularly preferably 30 to 40% by weight. If it exceeds 65% by weight, it is difficult and impossible to impart sufficiently stable water repellency and oil repellency to the cured film.
本発明で使用する表面調整剤（Ｃ）は、硬化皮膜の撥水撥油性を上げて防汚性を向上させる目的で配合する。例えばシリコーン系、フッ素系、アクリル系等が挙げられるが、硬化後の皮膜からブリード等により経時的に欠落することが無く効果を長期的に持続できる点で、バインダー樹脂と重合して硬化塗膜を形成できる反応性官能基を有することが好ましい。特にフッ素系化合物が、低い表面自由エネルギーにより、塗工後に塗膜表面に偏析しやすく、耐摩耗性及び防汚性を長期にわたり安定化させることができる点で好ましい。 The surface conditioner (C) used in the present invention is blended for the purpose of increasing the water and oil repellency of the cured film and improving the antifouling property. For example, silicone-based, fluorine-based, acrylic-based, etc. can be mentioned, but since the effect can be maintained for a long time without bleeding from the film after curing, it can be polymerized with a binder resin to form a cured coating film. It is preferred to have a reactive functional group capable of forming In particular, fluorine-based compounds are preferred because they tend to segregate on the coating film surface after coating due to their low surface free energy, and can stabilize wear resistance and antifouling properties over a long period of time.
前記（Ｃ）の固形分全量に対する配合比率は０．５～１０重量％が好ましく、１～５重量％が更に好ましい。０．５重量％以上とすることで十分な撥水撥油性を確保することができ、１０重量％以下とすることで十分な鉛筆硬度を確保することができる。 The mixing ratio of (C) to the total solid content is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight. A content of 0.5% by weight or more can ensure sufficient water and oil repellency, and a content of 10% by weight or less can ensure sufficient pencil hardness.
本発明で使用される光重合開始剤（Ｄ）は、紫外線や電子線などの照射でラジカルを生じ、そのラジカルが重合反応のきっかけとなるもので、ベンジルケタール系、アセトフェノン系、フォスフィンオキサイド系等汎用の光重合開始剤が使用できる。重合開始剤の光吸収波長を任意に選択することによって、紫外線領域から可視光領域にいたる広い波長範囲にわたって硬化性を付与することができる。具体的にはベンジルケタール系として２．２-ジメトキシ-１．２-ジフェニルエタン-1-オンが、α－ヒドロキシアセトフェノン系として１－ヒドロキシ－シクロヘキシル－フェニル－ケトン及び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－オンが、α-アミノアセトフェノン系として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-オンが、アシルフォスフィンオキサイド系として２．４．６-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド及びビス（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サイド等があり、単独または２種以上を組み合わせて使用できる。これらの中では、黄変しにくいα－ヒドロキシアセトフェノン系を含むことが好ましく、市販品としてはＯｍｎｉｒａｄ１８４及び同２９５９（商品名：ｉＧＭ社製、α－ヒドロキシアセトフェノン系）などがある。 The photopolymerization initiator (D) used in the present invention produces radicals when irradiated with ultraviolet rays, electron beams, or the like, and the radicals trigger a polymerization reaction. general-purpose photopolymerization initiators such as Curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region by arbitrarily selecting the light absorption wavelength of the polymerization initiator. Specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one is a benzyl ketal system, and 1-hydroxy-cyclohexyl-phenyl-ketone and 1-[4-(2- hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one is 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 as α-aminoacetophenone -on includes acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, either singly or in combination of two or more can be used in combination. Among these, it is preferable to contain an α-hydroxyacetophenone type that is resistant to yellowing.
前記（Ｄ）の光硬化樹脂成分１００重量部に対する比率は、１～１０重量部が好ましく、３～８重量部が更に好ましい。１重量部以上とすることで充分な硬化性が発現し、１０重量部以下とすることで過剰添加とならず塗膜の黄変や保存性低下を防ぐことができる。 The ratio of (D) to 100 parts by weight of the photocurable resin component is preferably 1 to 10 parts by weight, more preferably 3 to 8 parts by weight. When the amount is 1 part by weight or more, sufficient curability is exhibited, and when the amount is 10 parts by weight or less, excessive addition can be avoided, and yellowing of the coating film and deterioration of storage stability can be prevented.
また、本発明の光硬化性樹脂組成物には必要に応じて紫外線吸収剤、酸化防止剤、着色剤、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、抗ウイルス剤、抗菌剤、有機微粒子、無機フィラー等を添加してもよい。 In addition, the photocurable resin composition of the present invention may optionally contain an ultraviolet absorber, an antioxidant, a coloring agent, a leveling agent, an antifoaming agent, a thickener, an anti-settling agent, an antistatic agent, and an anti-fogging agent. , slip agents, antiviral agents, antibacterial agents, organic fine particles, inorganic fillers, and the like may be added.
本組成物の粘度は３００～２５，０００ｍＰａ・ｓが好ましく、５００～１０，０００ｍＰａ・ｓが更に好ましい。この範囲とすることで、安定した塗工性が可能となり、良好な外観と膜厚均一性を確保することができる。なお粘度の測定は、東機産業製のＥ型粘度計ＲＥ－２１５Ｒを用い、コーン角３°Ｒ１７．６５で２５±１℃、回転数は粘度範囲５００ｍＰａ・ｓ以下は５０ｒｐｍ、５００～２０００ｍＰａ・ｓは２０ｒｐｍ、２０００～５０００ｍＰａ・ｓは１０ｒｐｍ、５０００～１００００ｍＰａ・ｓは５ｒｐｍ、１００００ｍＰａ・ｓ以上は１ｒｐｍで測定した。 The viscosity of the composition is preferably 300 to 25,000 mPa·s, more preferably 500 to 10,000 mPa·s. Within this range, stable coatability becomes possible, and good appearance and film thickness uniformity can be ensured. The viscosity was measured using an E-type viscometer RE-215R manufactured by Toki Sangyo Co., Ltd., with a cone angle of 3°R17.65, 25±1°C, and a rotation speed of 50 rpm for a viscosity range of 500 mPa s or less, and 500 to 2000 mPa s. s was measured at 20 rpm, 2000 to 5000 mPa·s at 10 rpm, 5000 to 10000 mPa·s at 5 rpm, and 10000 mPa·s or more at 1 rpm.
本発明の光硬化性樹脂組成物が塗工される基材としては、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、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例示することができる。 Substrates to which the photocurable resin composition of the present invention is applied include polyester film, polyethylene film, polypropylene film, diacetylcellulose film, triacetylcellulose film, acetylcellulose butyrate film, polyvinyl chloride film, and polyvinyl chloride. Vinylidene film, polyvinyl alcohol film, ethylene vinyl alcohol film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluorine resin film, Examples include nylon films, acrylic films, cycloolefin (co)polymer films, and the like.
本発明の光硬化性樹脂組成物を塗工する方法は、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を利用できる。また塗工膜厚は、１μｍ～３０μｍが例示できる。 The method of applying the photocurable resin composition of the present invention is not particularly limited, and known spray coating, roll coating, die coating, air knife coating, blade coating, spin coating, reverse coating, gravure coating, wire bar coating, etc. A coating method or gravure printing, screen printing, offset printing, inkjet printing, or the like can be used. Further, the coating film thickness can be exemplified from 1 μm to 30 μm.
本発明の光硬化性樹脂組成物を塗工した後は、紫外線照射機を用いて硬化させる。紫外線を照射する場合の光源としては例えば、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、カーボンアーク灯、キセノンランプ、メタルハライドランプ、無電極紫外線ランプ、ＬＥＤランプなどがあげられ、硬化条件としては５００ｍＷ／ｃｍ２～３０００ｍＷ／ｃｍ２の照射強度で、積算光量として５０～２，０００ｍＪ／ｃｍ２が例示される。また照射する雰囲気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が、酸素による硬化阻害を防ぐためには不活性ガス中での硬化が好ましい。不活性ガス雰囲気の環境設定が難しい場合は、塗布直後に剥離フィルムを貼り合わせ、塗膜面と空気との接触を遮断した状態で硬化させても良い。 After coating the photocurable resin composition of the present invention, it is cured using an ultraviolet irradiation machine. Examples of light sources for ultraviolet irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, electrodeless ultraviolet lamps, and LED lamps. An irradiation intensity of 500 mW/cm 2 to 3000 mW/cm 2 and an integrated light amount of 50 to 2,000 mJ/cm 2 are exemplified. The atmosphere for irradiation may be air or an inert gas such as nitrogen or argon, but curing in an inert gas is preferred in order to prevent curing inhibition due to oxygen. If it is difficult to set the environment in an inert gas atmosphere, a release film may be attached immediately after coating to block contact between the coating surface and the air before curing.
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。また表記が無い場合は、室温は２５℃、相対湿度６５％の条件下で測定を行った。なお配合量は重量部を示す。 Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but these are specific examples and are not particularly limited to these. Unless otherwise specified, measurements were performed under the conditions of a room temperature of 25° C. and a relative humidity of 65%. In addition, a compounding quantity shows a weight part.
実施例１
（Ａ）としてウレアクＡ（骨格にＳｉ原子に有する６官能、Ｍｗ１５５０、固形分１００％、単独の水接触角９３°）を、（Ｂ）としてＭＴ－９３３（商品名：東亞合成社製、グリセリントリアクリレート）を、（Ｃ）としてＲＳ－７５ＮＳ（商品名：ＤＩＣ社製、反応性官能基有り、固形分１００％、フッ素系）を、（Ｄ）としてＯｍｎｉｒａｄ１８４（商品名：ＩＧＭ社製、αヒドロキシアセトフェノン系）を用い、表１記載の配合で均一に溶解分散するまで撹拌して光硬化型樹脂組成物である実施例１を調整した。
Example 1
(A) Ureac A (hexafunctional having Si atoms in the skeleton, Mw 1550, solid content 100%, single water contact angle 93 °) as (B) MT-933 (trade name: manufactured by Toagosei Co., Ltd., glycerin triacrylate) as (C), RS-75NS (trade name: manufactured by DIC, with a reactive functional group, solid content 100%, fluorine-based) as (D) Omnirad184 (trade name: manufactured by IGM, α Example 1, which is a photocurable resin composition, was prepared by using a hydroxyacetophenone system) and stirring until the composition shown in Table 1 was uniformly dissolved and dispersed.
実施例２～８
実施例１で用いた材料の他、（Ａ）としてウレアクＢ（骨格にＳｉ原子に有する１０官能、Ｍｗ５１００、固形分１００％、単独の９２°）及びウレアクＣ（骨格にＳｉ原子に有する１０官能、Ｍｗ２１００、固形分１００％、単独の水接触角９４°）を、（Ｂ）としてＰＥＴ－３０（商品名：日本化薬社製、ＰＥ３ＡとＰＥ４Ａの混合物）を用い、表１記載の配合で均一に溶解分散するまで撹拌して光硬化型樹脂組成物である実施例２～８を調整した。
Examples 2-8
In addition to the materials used in Example 1, Ureac B (10 functional Si atoms in the skeleton, Mw 5100, solid content 100%, 92 ° alone) and Ureac C (10 functional Si atoms in the skeleton) are used as (A). , Mw 2100, solid content 100%, single water contact angle 94 °), PET-30 (trade name: Nippon Kayaku Co., Ltd., a mixture of PE3A and PE4A) as (B), with the formulation shown in Table 1 Examples 2 to 8, which are photocurable resin compositions, were prepared by stirring until they were uniformly dissolved and dispersed.
比較例１～３
実施例で用いた材料の他、オリゴマーとしてウレアク１（ＨＤＩヌレート（３量体）とＰＥ３Ａの反応物、固形分１００％、９官能、単独の水接触角７１°）とウレアク２（ＨＤＩとジペンタエリスリトールペンタアクリレートの反応物、固形分１００％、１０官能、単独の水接触角７２°）を用い、表１記載の配合で均一に溶解分散するまで撹拌して光硬化型樹脂組成物である比較例１～３を調整した。
Comparative Examples 1-3
In addition to the materials used in the examples, ureac 1 (reaction product of HDI nurate (trimer) and PE3A, solid content 100%, 9-functionality, single water contact angle 71°) and ureac 2 (HDI and A reaction product of pentaerythritol pentaacrylate, solid content 100%, 10-functionality, single water contact angle 72°) is used, and the composition shown in Table 1 is stirred until it is uniformly dissolved and dispersed to obtain a photocurable resin composition. Comparative Examples 1-3 were prepared.
ＨＣフィルムの調整
Ａ４サイズで厚み１８８μｍのＰＥＴフィルムルミラーＵ３４（商品名：東レ社製、両面易接着層有り）に、光硬化型樹脂組成物を膜厚１５μｍで塗工し、その上に厚み７５μｍの剥離フィルムＥ７００６（商品名：東洋紡社製、片面シリコーン剥離層有り）を貼り合わせ、その上からフュージョンＵＶシステムジャパン製の無電極ＵＶ照射装置Ｆ３００Ｓ／ＬＣ－６Ｂを用い、Ｈバルブで出力１２００ｍＷ／ｃｍ２、積算光量２００ｍＪ／ｃｍ２で光硬化させた。
Preparation of HC film A photocurable resin composition was coated on an A4 size, 188 μm thick PET film Lumirror U34 (trade name: manufactured by Toray Industries, with easy adhesion layers on both sides) to a thickness of 15 μm, and a thickness of 75 μm was applied thereon. The release film E7006 (trade name: manufactured by Toyobo Co., Ltd., with a silicone release layer on one side) is pasted together, and an electrodeless UV irradiation device F300S / LC-6B manufactured by Fusion UV System Japan is used from above, with an H bulb output of 1200 mW / It was photo-cured at 200 mJ/cm 2 with an integrated light intensity of 200 mJ/cm 2 .
表１
Table 1
評価方法は以下の通りとした。 The evaluation method was as follows.
塗工性：塗工直後にレベリングして良好な外観を得られる場合を◎、塗工して数秒後にレベリングして良好な外観を得られる場合を〇、レベリングするのに１０秒以上かかる場合を×とした。 Coatability: ◎ indicates that a good appearance can be obtained by leveling immediately after coating, ◯ indicates that a good appearance can be obtained by leveling several seconds after coating, and ◯ indicates that it takes 10 seconds or more to level. x.
塗膜ヘイズ：ＪＩＳ Ｋ７３６１－１に準拠し、東洋精機製作所社製のＨａｚｅ－ＧＡＲＤ２を用い測定し、１．０％以下を〇、１．０％超を×とした。 Coating film haze: Measured using Haze-GARD2 manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with JIS K7361-1.
水接触角：ＪＩＳ Ｒ ３２５７：１９９９の静滴法に準じ、協和界面科学社製のＤＭｓ－４００を用い、室温で水を滴下し３０秒静置後の接触角を測定し、常態については９５°～１００°を○、１００～１０５°を◎、これらの範囲から外れる場合を×とした。 Water contact angle: According to the static drop method of JIS R 3257: 1999, using DMs-400 manufactured by Kyowa Interface Science Co., Ltd., water is dropped at room temperature and the contact angle is measured after standing for 30 seconds. ° to 100° is indicated by ◯, 100 to 105° is indicated by ⊚, and cases outside these ranges are indicated by x.
油性マーカーはじき性：油性マーカーのマジック（商品名：寺西化学工業社製）を用い連続した円弧を描き、インキをはじく場合を○、はじかない場合を×とした。 Permanent marker repellency: Continuous circular arcs were drawn using a permanent marker marker (trade name: manufactured by Teranishi Kagaku Kogyo Co., Ltd.).
鉛筆硬度：ＪＩＳ Ｋ５６００－５－４（１９９９年版）に準拠し、東洋精機製作所製の鉛筆引掻塗膜硬さ試験機（形式Ｐ）を用いて７５０ｇ荷重で測定し、２Ｈ以上を○、２Ｈ未満を×とした。 Pencil hardness: in accordance with JIS K5600-5-4 (1999 version), measured with a load of 750 g using a pencil scratch coating film hardness tester (type P) manufactured by Toyo Seiki Seisakusho, 2H or more is ○, 2H Less than x was defined as x.
耐摩耗性：スチールウール＃００００の上に５００ｇ／ｃｍ２の荷重を載せて１０往復させ、目視による観察で傷が付かないものを○、傷が付くものを×とした。 Abrasion resistance: A load of 500 g/cm 2 was placed on #0000 steel wool and reciprocated 10 times.
粘度：東機産業製のＥ型粘度計ＲＥ－２１５Ｒを用い、コーン角３°Ｒ１７．６５で測定し、２００～１０００ｍＰａ・ｓを〇、それを外れる場合を×とした。なお回転数は粘度範囲５００ｍＰａ・ｓ以下は５０ｒｐｍ、５００～２０００ｍＰａ・ｓは２０ｒｐｍ、２０００～５０００ｍＰａ・ｓは１０ｒｐｍ、５０００～１００００ｍＰａ・ｓは５ｒｐｍ、１００００ｍＰａ・ｓ以上は１ｒｐｍで測定した。 Viscosity: Measured using an E-type viscometer RE-215R manufactured by Toki Sangyo Co., Ltd., with a cone angle of 3°R17.65. The number of revolutions was 50 rpm for viscosity ranges of 500 mPa·s or less, 20 rpm for 500 to 2000 mPa·s, 10 rpm for 2000 to 5000 mPa·s, 5 rpm for 5000 to 10000 mPa·s, and 1 rpm for 10000 mPa·s or more.
評価結果
実施例は塗工性、塗膜ヘイズ、水接触角、油性マーカーハジキ性、鉛筆硬度、耐摩耗性、粘度すべての面で問題はなく良好であった。 The examples had no problems in all aspects of coatability, coating film haze, water contact angle, oil-based marker repellency, pencil hardness, abrasion resistance, and viscosity.
一方、（Ｂ）の配合量が３５重量％超である比較例１は、水接触角及び油性マーカーハジキ性が劣り、骨格にＳｉ原子を有さないオリゴマーを用いた比較例２及び３は、水接触角が低く、また油性マーカーはじき性が劣り、いずれも本願発明に適さないものであった。
On the other hand, Comparative Example 1, in which the amount of (B) was more than 35% by weight, was inferior in water contact angle and oil-based marker repellency. The water contact angle was low, and the repellency of the oil-based marker was poor.
Claims (4)
4. The solventless photocurable resin composition according to any one of claims 1 to 3, wherein the (B) is a tri- to tetra-functional (meth)acrylate.
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