JP7465398B1 - Solvent-free hard coat resin composition and optical laminate using the same - Google Patents
Solvent-free hard coat resin composition and optical laminate using the same Download PDFInfo
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- 239000011342 resin composition Substances 0.000 title claims abstract description 24
- 230000003287 optical effect Effects 0.000 title claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 29
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229920000193 polymethacrylate Polymers 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 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 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 24
- 239000011248 coating agent Substances 0.000 abstract description 23
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 15
- 238000001723 curing Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 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 class 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 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 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 3
- 229920002799 BoPET Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical class OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 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
- 239000000178 monomer Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- URQQDYIVGXOEDA-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethyl prop-2-enoate Chemical compound C=COCCOCCOC(=O)C=C URQQDYIVGXOEDA-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 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
- 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
- 238000005299 abrasion Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LOTBYPQQWICYBB-UHFFFAOYSA-N methyl n-hexyl-n-[2-(hexylamino)ethyl]carbamate Chemical compound CCCCCCNCCN(C(=O)OC)CCCCCC LOTBYPQQWICYBB-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
【課題】無溶剤型でありながら塗工外観が安定し、良好な耐擦傷性と共に優れた屈曲性を有するため、ハードコートフィルム等に用いる無溶剤型のハードコート樹脂組成物を提供する。【解決手段】アルキレンオキサイド変性された多官能（メタ）アクリレートと、ビニルエーテル基含有（メタ）アクリレートと、光重合開始剤と、を含み、前記ビニルエーテル基含有（メタ）アクリレートの配合量が固形分全量に対し１５～７０重量％であることを特徴とする無溶剤型ハードコート樹脂組成物である。【選択図】なし[Problem] To provide a solventless hard coat resin composition that has stable coating appearance, good scratch resistance and excellent flexibility, and is used for hard coat films, etc. [Solution] The solventless hard coat resin composition contains an alkylene oxide-modified multifunctional (meth)acrylate, a vinyl ether group-containing (meth)acrylate, and a photopolymerization initiator, and is characterized in that the blending amount of the vinyl ether group-containing (meth)acrylate is 15 to 70% by weight based on the total solid content. [Selected Figures] None
Description
本発明は、希釈溶剤を含まない無溶剤型のハードコート樹脂組成物、及びこれを用いた光学積層体に関する。 The present invention relates to a solvent-free hard coat resin composition that does not contain a diluting solvent, and an optical laminate using the same.
アクリル系の光硬化性樹脂は、プラスチックフィルムやプラスチック成形物表面に機能性を付与するために多くの分野で使用されている。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（以下ＨＣという）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 photocurable resins are used in many fields to impart functionality to the surfaces of plastic films and plastic molded products. For example, hard coat (hereinafter referred to as HC) films, which are applied to PET (polyethylene terephthalate) films to impart high hardness, are used in large quantities as films for touch panels and molding films.
こうしたＨＣ樹脂組成物は一般的に高粘度であることが多く、塗工性を改善するため、溶剤で希釈されて使用される場合が多かった。しかしながら、このような溶剤を含む組成物は、塗工後に溶剤を揮散させるため、環境への負荷が大きく、また乾燥炉では大きなエネルギーを消費していた。更に無溶剤型は溶剤型に比較して、密着性促進のため形成された易接着への浸透、膨潤効果が低く、密着性が不十分になりやすいという傾向もあった。 These HC resin compositions generally tend to be highly viscous, and are often diluted with a solvent to improve coatability. However, compositions that contain such solvents have a large environmental impact because the solvent evaporates after application, and drying ovens consume a large amount of energy. Furthermore, compared to solvent-based types, solventless types have a lower penetration and swelling effect on the easily adhesive layer formed to promote adhesion, and tend to result in insufficient adhesion.
こうした問題に対応する無溶剤型のＨＣ用硬化性組成物として、例えば特定構造のウレタン（メタ）アクリレート構造と、多官能化合物と、単官能化合物と、シリコーン化合物と、光ラジカル開始剤を含む組成物が提案されている（特許文献１）。こうした無溶剤型ＨＣ剤を用いることで、環境への負荷や、乾燥時のエネルギーロスの問題は解決できるようになってきているが、ＨＣフィルムとして要求される外観、硬化性、耐擦傷性等の諸特性については、一長一短があり、これらの物性を平均的にバランスよくクリアできる組成物は殆どなく、特に屈曲性については改善の余地があった。 As a solvent-free HC curable composition that addresses these issues, for example, a composition containing a specific urethane (meth)acrylate structure, a polyfunctional compound, a monofunctional compound, a silicone compound, and a photoradical initiator has been proposed (Patent Document 1). By using such solvent-free HC agents, the problems of environmental burden and energy loss during drying can be solved, but there are pros and cons regarding the various properties required for HC films, such as appearance, curability, and scratch resistance, and there are almost no compositions that can achieve a good balance of these physical properties on average, and there is room for improvement, especially in terms of flexibility.
本発明は、無溶剤型でありながら塗工外観が安定し、良好な耐擦傷性と共に優れた屈曲性を有するＨＣ樹脂組成物、及びその硬化層が形成された光学積層体を提供することにある。 The present invention aims to provide an HC resin composition that is solvent-free, yet has a stable coating appearance, good scratch resistance, and excellent flexibility, as well as an optical laminate in which a cured layer of the composition is formed.
上記課題を解決するため請求項１記載の発明は、アルキレンオキサイド変性された多官能（メタ）アクリレート（Ａ）と、ビニルエーテル基含有（メタ）アクリレート（Ｂ）と、光重合開始剤（Ｃ）と、を含み、前記（Ｂ）の配合量が固形分全量に対し１５～７０重量％であり、前記（Ｃ）がα－ヒドロキシアセトフェノン系であることを特徴とする無溶剤型ハードコート樹脂組成物を提供する。
In order to solve the above problems, the invention described in claim 1 provides a solventless hard coat resin composition comprising an alkylene oxide-modified polyfunctional (meth)acrylate (A), a vinyl ether group-containing (meth)acrylate (B), and a photopolymerization initiator (C), the blending amount of (B) being 15 to 70% by weight based on the total solid content, and (C) being an α-hydroxyacetophenone type .
また請求項２記載の発明は、前記（Ａ）がグリセリンポリ（メタ）アクリレート及びトリメチロールプロパントリ（メタ）アクリレート及びジペンタエリスリトールポリ（メタ）アクリレートからなる群から選択される（メタ）アクリレートの誘導体を含むことを特徴とする請求項１記載の無溶剤型ハードコート樹脂組成物を提供する。
The invention described in claim 2 provides the solventless hard coat resin composition described in claim 1, characterized in that (A) contains a derivative of (meth)acrylate selected from the group consisting of glycerin poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol poly(meth)acrylate.
また請求項３記載の発明は、プラスチック基材の少なくとも片面に、請求項１又は２いずれか記載の無溶剤型ハードコート樹脂組成物の硬化層が形成された光学積層体を提供する。
The present invention provides an optical laminate comprising a plastic substrate and a cured layer of the solventless hard coat resin composition according to the present invention formed on at least one surface of the plastic substrate.
本発明の樹脂組成物は、無溶剤型でありながら塗工外観が安定し、良好な耐擦傷性と共に優れた屈曲性を有するため、ＨＣフィルム等に用いる無溶剤型のＨＣ樹脂組成物として有用である。 The resin composition of the present invention is a solvent-free type, yet has a stable coating appearance, good scratch resistance, and excellent flexibility, making it useful as a solvent-free HC resin composition for use in HC films, etc.
以下本発明について詳細に説明する。 The present invention will be described in detail below.
本発明の組成物の構成は、アルキレンオキサイド変性された多官能（メタ）アクリレート（Ａ）と、ビニルエーテル基含有（メタ）アクリレート（Ｂ）と、光重合開始剤（Ｃ）である。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の双方を包含する。また無溶剤とは、ＨＣ樹脂組成物中に希釈を目的として意図的に溶剤を配合することを除くことであり、ＨＣ樹脂組成物の各成分に微量に含まれる揮発成分までをも除くことは意味せず、その溶剤含有量としては５重量％以下、典型的には１重量％以下を指す。 The composition of the present invention is composed of an alkylene oxide-modified polyfunctional (meth)acrylate (A), a vinyl ether group-containing (meth)acrylate (B), and a photopolymerization initiator (C). In this specification, (meth)acrylate includes both acrylate and methacrylate. Solvent-free means that a solvent is not intentionally blended into the HC resin composition for the purpose of dilution, and does not mean that even the volatile components contained in trace amounts in each component of the HC resin composition are excluded, and refers to a solvent content of 5% by weight or less, typically 1% by weight or less.
本発明で使用されるアルキレンオキサイド変性された多官能（メタ）アクリレート（Ａ）は、骨格中にアルキレンオキサイドのブロック構造を有する、硬化皮膜を構成する主要成分である。アルキレンオキサイド変性しているため低粘度で、反応性官能基であるアクリロイル基同士が一定の距離を保てるため、架橋密度が過度に高くならず、塗膜に残留する内部応力や硬化収縮を低減できる。そのため、基材の密着性と塗膜強度の良好なバランスをとることができ、結果として可撓性も付与された硬化皮膜を形成できる。 The alkylene oxide-modified polyfunctional (meth)acrylate (A) used in the present invention is a main component of the cured coating, which has an alkylene oxide block structure in the skeleton. Because it is alkylene oxide-modified, it has low viscosity, and the reactive functional groups, acryloyl groups, can be kept at a constant distance from each other, so the crosslinking density does not become excessively high, and the internal stress and curing shrinkage remaining in the coating film can be reduced. Therefore, a good balance can be achieved between the adhesion to the substrate and the strength of the coating film, and as a result, a cured coating that is also flexible can be formed.
アルキレンオキサイド変性としては、例えばエチレンオキサイド（以下ＥＯという）変性、プロピレンオキサイド（以下ＰＯという）変性、ブチレンオキサイド（以下ＢＯという）変性が挙げられる。アルキレンオキサイド変性の平均付加数は２～１５が好ましく、３～１２が更に好ましい。２以上とすることで耐擦傷性と屈曲性の向上が期待でき、１５以下とすることで適度な粘度に調整しやすくなる。 Examples of alkylene oxide modifications include ethylene oxide (hereinafter referred to as EO) modifications, propylene oxide (hereinafter referred to as PO) modifications, and butylene oxide (hereinafter referred to as BO) modifications. The average number of alkylene oxide modifications is preferably 2 to 15, and more preferably 3 to 12. By making it 2 or more, it is expected that scratch resistance and flexibility will be improved, and by making it 15 or less, it is easier to adjust the viscosity to an appropriate level.
前記（Ａ）としては、例えばＥＯ変性グリセリンポリ（メタ）アクリレート、ＥＯ変性ジグリセリンポリ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＥＯ変性ペンタエリスリトールポリ（メタ）アクリレート、ＥＯ変性ジペンタエリスリトールポリ（メタ）アクリレート、及びこれらのＰＯ変性物、ＢＯ変性物等が挙げられ、単独あるいは２種類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、粘度、硬化性、入手性の点でＥＯ変性物が好ましい。また屈曲性と耐擦傷性でバランスが取れている点で、ＥＯ変性ジグリセリンテトラアクリレート（以下ＤＧＴＡという）、ＥＯ変性ジペンタエリスリトールヘキサアクリレート（以下ＤＰＨＡという）、ＥＯ変性トリメチロールプロパントリアクリレート（以下ＴＭＰＴＡという）が特に好ましい。 Examples of (A) include EO-modified glycerin poly(meth)acrylate, EO-modified diglycerin poly(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, EO-modified pentaerythritol poly(meth)acrylate, EO-modified dipentaerythritol poly(meth)acrylate, and PO-modified and BO-modified products thereof, which can be used alone or in combination of two or more. Among these, EO-modified products are preferred in terms of viscosity, curing properties, and availability. In addition, EO-modified diglycerin tetraacrylate (hereinafter referred to as DGTA), EO-modified dipentaerythritol hexaacrylate (hereinafter referred to as DPHA), and EO-modified trimethylolpropane triacrylate (hereinafter referred to as TMPTA) are particularly preferred in terms of a good balance between flexibility and scratch resistance.
前記（Ａ）の配合量は、固形分全量に対し２０～８０重量％が好ましく、２５～７０重量％が更に好ましく、３５～６０重量％が特に好ましい。２０重量％以上とすることで十分な屈曲性と耐擦傷性を確保することができ、８０重量％以下とすることで十分な塗工性と安定した外観を確保することができる。 The amount of (A) is preferably 20 to 80% by weight, more preferably 25 to 70% by weight, and particularly preferably 35 to 60% by weight, based on the total solid content. By making it 20% by weight or more, sufficient flexibility and scratch resistance can be ensured, and by making it 80% by weight or less, sufficient coatability and stable appearance can be ensured.
本発明で使用されるビニルエーテル基含有（メタ）アクリレート（Ｂ）は、（Ａ）を希釈する反応性希釈剤として配合する。酸素による重合阻害がなく良好な希釈性を有するカチオン重合性のビニルエーテル基と、（Ａ）との良好な相溶性と反応性を有する（メタ）アクリロイル基を併せ持つモノマーであり、例えば下記一般式（１）で表すことができる。
ＣＨ２＝ＣＲ１－ＣＯ－（ＯＣＨＲ２ＣＨＲ３）ｎ－Ｏ－ＣＨ＝ＣＨＲ４ ・・・（１）
（式中、Ｒ１、Ｒ４は水素原子又はメチル基を表し、Ｒ２、Ｒ３はそれぞれ独立して水素原子又は有機残基を示し、ｎは２以上の整数を表す。）
The vinyl ether group-containing (meth)acrylate (B) used in the present invention is blended as a reactive diluent for diluting (A). It is a monomer having both a cationically polymerizable vinyl ether group having good dilutability without polymerization inhibition by oxygen and a (meth)acryloyl group having good compatibility and reactivity with (A), and can be represented, for example, by the following general formula (1).
CH 2 ═CR 1 —CO—(OCHR 2 CHR 3 )n—O—CH═CHR 4 ... (1)
(In the formula, R1 and R4 represent a hydrogen atom or a methyl group, R2 and R3 each independently represent a hydrogen atom or an organic residue, and n represents an integer of 2 or more.)
前記（Ｂ）としては、例えば（メタ）アクリル酸２－（２－ビニロキシエトキシ）エチル、（メタ）アクリル酸２－（２－ビニロキシイソプロポキシ）エチル、（メタ）アクリル酸２－（２－ビニロキシエトキシ）プロピル、アクリル酸２－（２－ビニロキシイソプロポキシ）プロピル、（メタ）アクリル酸２－（２－ビニロキシエトキシエトキシ）エチル等が挙げられ、単独あるいは２種類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、特に低粘度で希釈能力が高く、硬化性にも優れるアクリル酸２－（２－ビニロキシエトキシ）エチルが好ましい。 Examples of (B) include 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)propyl (meth)acrylate, 2-(2-vinyloxyisopropoxy)propyl acrylate, and 2-(2-vinyloxyethoxyethoxy)ethyl (meth)acrylate, and these may be used alone or in combination of two or more. Among these, 2-(2-vinyloxyethoxy)ethyl acrylate is particularly preferred, as it has low viscosity, high dilution ability, and excellent curing properties.
前記（Ｂ）の配合量は、固形分全量に対し１５～７０重量％であり、２０～６５重量％が好ましく、２５～６０重量％が更に好ましく、３０～５５重量％が特に好ましい。１５重量％未満では塗工性が低下し、外観が安定しない場合があり、７０重量％超では十分な耐擦傷性を確保できない場合がある。 The amount of (B) is 15 to 70% by weight, preferably 20 to 65% by weight, more preferably 25 to 60% by weight, and particularly preferably 30 to 55% by weight, based on the total solid content. If it is less than 15% by weight, the coatability may decrease and the appearance may not be stable, and if it exceeds 70% by weight, sufficient scratch resistance may not be ensured.
本発明で使用される光重合開始剤（Ｃ）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－オン及び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－ヒドロキシフェノン系を配合することが好ましく、酸素による重合阻害を受けにくく表面硬化性に優れる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－オンが更に好ましい。 The photopolymerization initiator (C) used in the present invention generates radicals when irradiated with ultraviolet light or an electron beam, and these radicals trigger the polymerization reaction. General-purpose photopolymerization initiators such as benzyl ketal, acetophenone, and phosphine oxide types can be used. By arbitrarily selecting the light absorption wavelength of the polymerization initiator, it is possible to impart curability over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, the benzyl ketal type includes 2.2-dimethoxy-1.2-diphenylethan-1-one, the α-hydroxyacetophenone type includes 1-hydroxy-cyclohexyl-phenyl-ketone and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, the α-aminoacetophenone type includes 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and the acylphosphine oxide type includes 2.4.6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2.4.6-trimethylbenzoyl)-phenylphosphine oxide, which can be used alone or in combination of two or more. Among these, it is preferable to use an α-hydroxyphenone type that is less prone to yellowing, and even more preferable is 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, which is less susceptible to polymerization inhibition by oxygen and has excellent surface curing properties.
前記（Ｃ）の配合量は、ラジカル重合性成分１００重量部に対して、０．５～１０重量部配合することが好ましく、２～８重量部が更に好ましい。０．５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。市販品としてはＯｍｎｉｒａｄ１２７（商品名：ＩＧＭ Ｒｅｓｉｎｓ社製、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）等が挙げられる。 The amount of (C) is preferably 0.5 to 10 parts by weight, more preferably 2 to 8 parts by weight, per 100 parts by weight of the radically polymerizable component. By adding 0.5 parts by weight or more, sufficient curing properties are exhibited, and by adding 10 parts by weight or less, yellowing of the coating film and deterioration of storage stability can be prevented without excessive addition. Commercially available products include Omnirad 127 (trade name: IGM Resins, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one).
更に加えて本組成物には必要に応じ、性能を損なわない範囲で反応性希釈剤、表面調整剤、光安定剤、重合禁止剤、湿潤剤、酸化防止剤、硬化助剤、シランカップリング剤、可塑剤、増感剤、消泡剤、難燃剤、無機フィラー、有機微粒子、顔料や染料や色素などの着色剤、抗菌、抗ウィルス剤などの添加剤を併用することができる。 Additionally, the composition may contain additives such as reactive diluents, surface conditioners, light stabilizers, polymerization inhibitors, wetting agents, antioxidants, curing aids, silane coupling agents, plasticizers, sensitizers, defoamers, flame retardants, inorganic fillers, organic fine particles, colorants such as pigments, dyes and pigments, antibacterial agents and antiviral agents, as long as the additives do not impair the properties of the composition.
前記反応性希釈剤は、組成物の粘度低減と共に硬化性を向上させる目的で配合する。低粘度で（Ａ）及び（Ｂ）との相溶性に優れる点で、多官能（メタ）アクリレートを用いることが好ましい。例えば４官能では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、ジグリセリンテトラ（メタ）アクリレートが、５官能ではジペンタエリスリトールペンタ（メタ）アクリレートが、６官能ではジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられ、単独あるいは２種類以上を組み合わせて使用することができる。これらの中では硬化性の向上により良好な耐擦傷性を得られる点でＤＰＨＡが好ましい。 The reactive diluent is blended for the purpose of reducing the viscosity of the composition and improving its curability. It is preferable to use a multifunctional (meth)acrylate, which has low viscosity and excellent compatibility with (A) and (B). For example, tetrafunctional diluents include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and diglycerin tetra(meth)acrylate, pentafunctional dipentaerythritol penta(meth)acrylate, and hexafunctional dipentaerythritol hexa(meth)acrylate, and these can be used alone or in combination of two or more types. Of these, DPHA is preferable, since it can provide good scratch resistance due to its improved curability.
前記反応性希釈剤の配合量としては、固形分全量に対し２５重量％以下が好ましく、２０重量部以下が更に好ましく、１５重量％以下が特に好ましい。２５重量％以下とすることで、十分な屈曲性を確保しつつ、耐擦傷性を向上させることが可能となる。 The amount of the reactive diluent is preferably 25% by weight or less, more preferably 20 parts by weight or less, and particularly preferably 15% by weight or less, based on the total solid content. By making the amount 25% by weight or less, it is possible to improve scratch resistance while ensuring sufficient flexibility.
前記表面調整剤は、塗工後のレベリング性向上や防汚性（防指紋性）と撥水性を付与する目的で配合する。硬化後の皮膜から経時的に欠落することがなく、効果を長期的に持続させることが可能である点で、（Ａ）や（Ｂ）と重合反応する反応性官能基を有しているフッ素系、シリコーン系、フッ素シリコーン系であることが好ましい。 The surface conditioner is blended for the purpose of improving the leveling properties after coating and imparting anti-fouling properties (anti-fingerprint properties) and water repellency. In that it will not be lost over time from the cured coating and its effect can be sustained for a long period of time, it is preferable that the surface conditioner is a fluorine-based, silicone-based, or fluorine silicone-based agent having a reactive functional group that undergoes a polymerization reaction with (A) or (B).
本発明のＨＣ樹脂組成物を塗布するプラスチック基材としては、トリアセチルセルロースフィルム、ＰＥＴフィルム、ポリイミドフィルム、ポリエチレンナフタレートフィルム、ポリ塩化ビニルフィルム、ポリスチレンフィルム、アクリルフィルム、ポリカーボネートフィルム、シクロオレフィン（コ）ポリマーフィルム、ポリオレフィンフィルム（ＰＰ、ＰＥ等）及びこれらの複合フィルムが例示できる。これらの中では価格、加工性、寸法安定性などの全体的なバランスが良好な点から二軸延伸処理されたＰＥＴフィルムが好ましく用いられる。 Examples of plastic substrates onto which the HC resin composition of the present invention is applied include triacetyl cellulose film, PET film, polyimide film, polyethylene naphthalate film, polyvinyl chloride film, polystyrene film, acrylic film, polycarbonate film, cycloolefin (co)polymer film, polyolefin film (PP, PE, etc.), and composite films of these. Among these, biaxially oriented PET film is preferably used because of its good overall balance of price, processability, dimensional stability, etc.
本発明のＨＣ樹脂組成物を塗工する方法は、特に制限はなく、フィルムやシートの様な平面形状のものには、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、成形物のように平面形状ではなく凹凸面があるものに対してはスプレー塗布方法が有用である。またこの方法は平面形状に対しても、大きな設備投資をする事なく広い面積を塗布することができる方法として優れている。 There are no particular limitations on the method for coating the HC resin composition of the present invention. For flat surfaces such as films and sheets, known coating methods such as spray coating, roll coating, die coating, air knife coating, blade coating, spin coating, reverse coating, gravure coating, and wire bar, or gravure printing, screen printing, offset printing, and inkjet printing can be used. For objects that are not flat but have an uneven surface such as molded products, spray coating methods are useful. This method is also excellent for flat surfaces as it can coat a large area without requiring large capital investment.
本発明のＨＣ樹脂組成物の塗工膜厚としては、乾燥時で０．５μｍ～５０μｍを例示できるが、これに限定されるものではない。但しプラスチック基材へ塗工する場合は、硬化収縮による反りを防ぐ目的で１～１０μｍであることが好ましい。 The coating thickness of the HC resin composition of the present invention can be, for example, 0.5 μm to 50 μm when dry, but is not limited to this. However, when coating a plastic substrate, it is preferable that the thickness is 1 to 10 μm in order to prevent warping due to cure shrinkage.
本発明のＨＣ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１００ｍＷ／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。 After the HC resin composition of the present invention is applied, it is cured using an ultraviolet irradiator. Examples of light sources for irradiating ultraviolet rays 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, and examples of curing conditions include an irradiation intensity of 100 mW/cm 2 to 3000 mW/cm 2 and an integrated light quantity of 50 to 2,000 mJ/cm 2. The atmosphere for irradiation may be air or an inert gas such as nitrogen or argon, but curing in an inert gas is preferred to prevent curing inhibition by oxygen.
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。なお配合量は重量部を示し、表記が無い場合は、室温２５℃相対湿度６５％の条件下で測定した。 The present invention will be described in detail below based on examples and comparative examples, but these are specific examples and are not intended to be limiting. The amounts in the formula are in parts by weight, and unless otherwise stated, measurements were taken at room temperature of 25°C and relative humidity of 65%.
実施例１
前記（Ａ）としてＭ－４６０（商品名：東亞合成社製、ＥＯ変性（変性数４）ＤＧＴＡ）を、（Ｂ）としてＶＥＥＡ（商品名：日本触媒社製、アクリル酸２－（２－ビニロキシエトキシ）エチル）を、（Ｃ）としてＯｍｎｉｒａｄ１２７（商品名：ＩＧＭ Ｒｅｓｉｎｓ社製、α－ヒドロキシフェノン系）を用い、表１記載の配合で均一に溶解するまで撹拌し実施例１のＨＣ樹脂組成物を調製した。
Example 1
The HC resin composition of Example 1 was prepared by mixing the above-mentioned (A) M-460 (product name: Toagosei Co., Ltd., EO-modified (modification number 4) DGTA), (B) VEEA (product name: Nippon Shokubai Co., Ltd., 2-(2-vinyloxyethoxy)ethyl acrylate), and (C) Omnirad 127 (product name: IGM Resins, α-hydroxyphenone type) in the formulation shown in Table 1 until uniformly dissolved.
実施例２～８
前記（Ａ）としてＡ－ＤＰＨ－１２Ｅ（商品名：新中村化学工業社製、ＥＯ変性（変性数１２）ＤＰＨＡ）及びＳＲ４５４ＮＳ（商品名：ＳＡＲＴＯＭＥＲ社製、ＥＯ変性（変性数３）ＴＭＰＴＡ）を、反応性希釈剤としてＭ－９４０（商品名：東亞合成社製、ＤＰＨＡ）を用い、表１記載の配合で均一に溶解するまで撹拌し実施例２～８のＨＣ樹脂組成物を調製した。
Examples 2 to 8
The HC resin compositions of Examples 2 to 8 were prepared by using A-DPH-12E (product name: Shin-Nakamura Chemical Co., Ltd., EO-modified (number of modifications: 12) DPHA) and SR454NS (product name: SARTOMER Co., Ltd., EO-modified (number of modifications: 3) TMPTA) as the (A) and M-940 (product name: Toagosei Co., Ltd., DPHA) as a reactive diluent in the formulation shown in Table 1 and stirring until uniformly dissolved.
比較例１～５
実施例で用いた材料の他、（Ａ）に代わるモノマーとしてＡ－ＴＭＭＴ（商品名：新中村化学工業社製、ペンタエリスリトールテトラアクリレート）及びＭ－３０９（商品名：東亞合成社製、ＴＭＰＴＡ）を用い、表２記載の配合で均一に溶解するまで撹拌し比較例１～５のＨＣ樹脂組成物を調製した。
Comparative Examples 1 to 5
In addition to the materials used in the examples, A-TMMT (product name: pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) and M-309 (product name: TMPTA, manufactured by Toagosei Co., Ltd.) were used as monomers in place of (A), and the mixture was stirred until uniformly dissolved in the formulation shown in Table 2 to prepare the HC resin compositions of Comparative Examples 1 to 5.
表１
Table 1
表２
Table 2
評価方法は以下の通りとした。 The evaluation method was as follows:
評価用ＨＣフィルムの作成
上記で調製したＨＣ樹脂組成物を用い、Ａ４３００（商品名：東洋紡社製、厚さ５０μｍのＰＥＴフィルム）に乾燥膜厚が４μｍとなるように塗工し、ＦＵＳＩＯＮ社製の無電極ＵＶランプを用いＨバルブで出力６００ｍＷ／ｃｍ２、積算光量が１５０ｍＪ／ｃｍ２（３６５ｎｍ）となる様に紫外線照射し、評価用ＨＣフィルムを作成した。
Preparation of HC film for evaluation <br/>The HC resin composition prepared above was used to coat A4300 (product name: Toyobo Co., Ltd., 50 μm thick PET film) so that the dry film thickness was 4 μm, and ultraviolet light was irradiated using an electrodeless UV lamp manufactured by FUSION Co., Ltd., with an H bulb output of 600 mW/cm2 and an accumulated light amount of 150 mJ/cm2 (365 nm) to prepare an HC film for evaluation.
粘度：東機産業製のブルックフィールド型粘度計ＴＶＢ－１０を用い、２５±１℃で、ローターＮｏがＭ１、回転数は６０ｒｐｍにより１分後の粘度を測定した。 Viscosity: Using a Brookfield viscometer TVB-10 manufactured by Toki Sangyo, the viscosity was measured after 1 minute at 25±1°C, rotor No. M1, and a rotation speed of 60 rpm.
塗工性：上記評価用ＨＣフィルムの作成時において、外観を目視で確認し、高粘度による塗工ムラや塗工スジが無い場合を◎、レベリング性が完全ではないもののほぼ良好な場合を〇、レベリング性が完全でなく塗工スジが若干判る場合を△、塗工スジがはっきりと判りレベリング性が悪い場合を×とした。 Coating properties: When preparing the HC film for evaluation, the appearance was visually checked, and a ◎ was given if there were no coating unevenness or coating streaks due to high viscosity, a 〇 if the leveling was almost good but not perfect, a △ if the leveling was not perfect and some coating streaks were visible, and an × if the coating streaks were clearly visible and the leveling was poor.
硬化性：上記評価用ＨＣフィルムの作成時において、紫外線硬化直後の塗膜表面の指触タックを確認し、タックが完全になく硬化している場合を○、タックがあり硬化していない場合を×とした。 Curability: When preparing the HC film for evaluation, the tackiness of the coating surface immediately after UV curing was checked. If the coating was completely cured and had no tackiness, it was marked as ○, and if it was tacky but not cured, it was marked as ×.
耐擦傷性：東洋精機社製の摩耗試験機を用い、接触面積が直径２５ｍｍφのスチールウール＃００００の上に荷重を載せ、往復速度３０回／分で１０往復させた後、ＨＣフィルムを黒打ちして目視による観察を行い、傷が確認されない荷重量が３００ｇ超の場合を◎、２００～３００ｇの場合を○、２００ｇ未満のを×とした。 Scratch resistance: Using an abrasion tester manufactured by Toyo Seiki Co., Ltd., a load was placed on steel wool #0000 with a contact area of 25 mm in diameter, and the material was moved back and forth 10 times at a reciprocating speed of 30 times per minute. The HC film was then blackened and visually observed. When the load was more than 300 g and no scratches were observed, it was marked with ◎, when it was 200 to 300 g, it was marked with ○, and when it was less than 200 g, it was marked with ×.
耐屈曲性：ビック・ガードナー社製の円筒形マンドレルテスタＰＦ－５７１０を用い、上記ＨＣフィルムを１２０ｍｍ×３０ｍｍにカットし、１８０°の折り曲げ（外曲げ）を１回行い、クラックが入らない最小曲げ半径（Ｒｍｍ）を測定し、１Ｒの場合を◎、１．５Ｒの場合を〇、１．５Ｒ超の場合を×とした。 Bending resistance: Using a cylindrical mandrel tester PF-5710 manufactured by BYK Gardner, the above HC film was cut to 120 mm x 30 mm and bent once at 180° (outward bending) to measure the minimum bending radius (Rmm) at which cracks did not occur. 1R was marked with ◎, 1.5R with ◯, and over 1.5R with ×.
評価結果
表３
Evaluation results <br/> Table 3
表４
Table 4
実施例の各配合は、粘度、塗工性、硬化性、耐擦傷性及び屈曲性、全ての面で問題は無く良好であった。 The formulations in the examples were excellent with no problems in any aspect, including viscosity, coatability, curability, scratch resistance and flexibility.
一方、（Ｂ）の配合量が上限を超えている比較例１は耐擦傷性が劣り、（Ｂ）の配合量が下限未満の比較例２は塗工性が劣っていた。また（Ａ）の代わりにＥＯ変性をしていないモノマーを使用した比較例３及び４は屈曲性が劣り、比較例５は耐擦傷性が劣り、いずれの配合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 blending amount of (B) exceeded the upper limit, exhibited poor scratch resistance, and Comparative Example 2, in which the blending amount of (B) was below the lower limit, exhibited poor coatability. Comparative Examples 3 and 4, in which a non-EO-modified monomer was used instead of (A), exhibited poor flexibility, and Comparative Example 5 exhibited poor scratch resistance, and none of the blends were suitable for the present invention.
Claims (3)
3. An optical laminate comprising a plastic substrate and a cured layer of the solventless hard coat resin composition according to claim 1 or 2 formed on at least one surface of the substrate.
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