JP2021178935A - 活性エネルギー線硬化性組成物、硬化物、レンズ及びカメラモジュール - Google Patents
活性エネルギー線硬化性組成物、硬化物、レンズ及びカメラモジュール Download PDFInfo
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- JP2021178935A JP2021178935A JP2020085744A JP2020085744A JP2021178935A JP 2021178935 A JP2021178935 A JP 2021178935A JP 2020085744 A JP2020085744 A JP 2020085744A JP 2020085744 A JP2020085744 A JP 2020085744A JP 2021178935 A JP2021178935 A JP 2021178935A
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- meth
- acrylate
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- 239000000203 mixture Substances 0.000 title claims abstract description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 144
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 19
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- 239000004417 polycarbonate Substances 0.000 claims abstract description 17
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 17
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002430 hydrocarbons Chemical group 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 150000002484 inorganic compounds Chemical class 0.000 claims description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
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- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
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- 238000012360 testing method Methods 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 16
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
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- 230000001678 irradiating effect Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000005240 physical vapour deposition Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
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Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
(A)成分としてポリカーボネートジオールジアクリレート(宇部興産株式会社製「UM−90(1/3)DA」:一般式(1)におけるR1が水素原子であり、R2がそれぞれ独立して、炭素原子数6の直鎖状炭化水素基とシクロヘキサン構造をランダムに有するものであり、nが4〜5のものである。);70質量部、(B)成分として2−ヒドロキシエチルアクリレート(大阪有機化学工業株式会社製「HEA」);10質量部、(C)成分としてトリシクロデカンジメタノールジメタクリレート(共栄社化学株式会社製「DCP−M」);20質量部、(D)成分として1−ヒドロキシシクロヘキシルフェニルケトン(BASF製「I−184」);1質量部を混合し、50℃に加温後、ホモディスパ―を使用して回転数1,000rpmで10分間撹拌混合して活性エネルギー線硬化性組成物を調製した。
(A)、(B)、(C)及び(E)の種類及び/又は量を表1〜3に示す通りに変更した以外は、実施例1と同様にして活性エネルギー線硬化性組成物を調製した。
実施例及び比較例で得られた活性エネルギー線硬化性組成物を三角プリズム型(厚さ5mm、1辺の長さ10mm)に流し込み、アイグラフィックス株式会社製ベルトコンベアー式紫外線照射装置(120Wメタルハライドランプ)を使用して、3,000mJ/cm2の紫外線を照射して三角プリズムを作製した。得られた三角プリズムを株式会社島津製作所製カルニュー精密屈折計「KPR−3000」を使用して25℃におけるd線、F線、C線、各々の屈折率を測定した。なお、硬化物の屈折率(nd)に最も近い屈折率(nd)を有するマッチング液を適宜選択して用いた。
上述の[屈折率の測定方法]にて測定したd線、F線、C線、各々の屈折率を用いて下記式によりアッベ数(νd)を算出した。
オクタデシルトリクロロシランにより離型処理を施したガラス板上に、実施例及び比較例で得られた活性エネルギー線硬化性組成物を滴下し、厚み1mmのシムプレートをスペーサーとして油滴の左右に配置後、同様にオクタデシルトリクロロシランにより離型処理を施したガラス板により油滴を挟み込んだ。2枚のガラス板で挟みこまれた活性エネルギー線硬化性組成物の油滴を、岩崎電気株子会社製UV−LED照射装置「LHPUV365/2501」にて照射強度50mW/cm2、積算光量8000mJ/cm2を照射し、約1mm厚のコイン状硬化物を得た。得られたコイン状硬化物を送風式オーブンにより100℃で20分間加熱した後、日本分光株式会社製紫外可視近赤外分光光度計「V−770」を用いて波長410nmにおける初期透過率を測定した。
前記透過率の測定方法において測定したコイン状硬化物を、送風式オーブンにより(1)175℃で10分間加熱、乃至(2)260℃で6分間加熱した後、日本分光株式会社製紫外可視近赤外分光光度計「V−770」を用いて波長410nmにおける透過率を、各々耐熱試験後透過率1及び耐熱試験後透過率2として測定した。なお、加熱温度は低温溶融半田と通常溶融半田のリフロー工程に準じた温度設定として175℃と260℃を用いた。
厚み0.2mmのシムプレートとガラス棒を用いて、アクリル板上に実施例及び比較例で得られた活性エネルギー線硬化性組成物を塗工後、アイグラフィックス株式会社製ベルトコンベアー式紫外線照射装置(120Wメタルハライドランプ)にて積算光量3,000mJ/cm2の紫外線照射により膜厚0.2mmのシート状硬化物を得た。得られたシート状硬化物をダンベルカッターを用いて長さ5cm×幅5cmに裁断することで吸水率測定用試験片を作製した。作製した前記試験片を送風式オーブンにより50℃で24時間乾燥後、試験片の重量測定を行い初期重量m1とした。初期重量測定後、23℃の純水300mlに24時間浸漬させた。純水から引き上げた試験片に残った水分を旭化成株式会社製不織布「ベンコット」にて拭き取った後、試験片の重量測定を行い浸漬後重量m2とした。浸漬後重量測定後、送風式オーブンにより50℃で24時間乾燥させ、試験片の重量測定を行い乾燥重量m3とした。上記m1〜m3を用いて、下記式により吸水率を算出した。
実施例及び比較例で得られた活性エネルギー線硬化性組成物を、信越化学工業株式会社製シランカップリング剤「KBM−5103」により密着処理を施したカバーガラス上に滴下し、レンズレプリカにより賦形した後、岩崎電気株式会社製UV−LED照射装置「LHPUV365/2501」にて照射強度50mW/cm2、積算光量450mJ/cm2の照射により仮硬化させた。レンズレプリカを離型後、プロピレングリコールモノメチルエーテルにより現像処理を行い、未硬化の樹脂組成物を除去した。さらに、積算光量7,550mJ/cm2による本硬化を行った後、送風式オーブンを用いて100℃で90分間のポストベークを行うことで、ウェハレベルレンズを得た。得られたウェハレベルレンズを環境試験機(エスペック製SH−222)を用いて温度85℃、相対湿度85%、で1000時間の耐湿熱試験を行った。試験後レンズを株式会社キーエンス製マイクロスコープ「VHX900」及びオリンパス株式会社製レーザー顕微鏡「OLS5000」を用いて観察し、下記の基準に従い評価した。
〇:ハガレ、界面欠陥は見られないが内部欠陥が1〜10個程度。
△:ハガレ、界面異常、内部欠陥の程度が中程度。
×:ハガレ、界面異常、内部欠陥が重度。
「R−604」;
ジオキサングリコールジ(メタ)アクリレート(日本化薬株式会社製)
「HBPE−4」;
EO変性水添ビスフェノールAジアクリレート(第一工業製薬株式会社製)
「HPA」;
2−ヒドロキシプロピルアクリレート(大阪有機化学工業株式会社製)
「4−HBA」;
4−ヒドロキシブチルアクリレート(大阪有機化学工業株式会社製)
「CHDMMA」;
シクロヘキサンジメタノールモノアクリレート(三菱ケミカル株式会社製)
「M−926」;
EO変性ソルビトールジアクリレート(東亜合成株式会社製)
「PE−1」;
ペンタエリスリトールテトラキス(3−メルカプトブチレート)(昭和電工株式会社製)
Claims (11)
- 下記一般式(1)で表されるポリカーボネートジオールジ(メタ)アクリレート(A)と、
前記ポリカーボネートジオールジ(メタ)アクリレート(A)以外の一分子中に1又は2個の(メタ)アクリロイル基及び一分子中に1個以上の水酸基を有する化合物(B)と、
前記ポリカーボネートジオールジ(メタ)アクリレート(A)及び前記化合物(B)以外の一分子中に1又は2個の(メタ)アクリロイル基及び環状構造を有する化合物(C)と、
を含有することを特徴とする活性エネルギー線硬化性組成物。
(式中、R1は、それぞれ独立して、水素原子又はメチル基を示し、R2は、それぞれ独立して、炭素原子数1〜10の炭化水素基を示す。nは1〜10の整数である。) - 前記一般式(1)中のR2が、それぞれ独立して、炭素原子数5〜6の直鎖状炭化水素基、シクロヘキサン構造、又はイソソルバイド構造を有するものである、請求項1に記載の活性エネルギー線硬化性組成物。
- 前記環状構造が、シクロヘキサン構造、トリシクロデカン構造及び1,3−ジオキサン構造からなる群より選ばれる1種以上である、請求項1又は2に記載の活性エネルギー線硬化性組成物。
- 前記化合物(B)が、2−ヒドロキシエチル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート、シクロヘキサンジメタノールモノ(メタ)アクリレート及びソルビトールエチレンオキサイド変性ジ(メタ)アクリレートからなる群より選ばれる1種以上である、請求項1〜3のいずれか1項に記載の活性エネルギー線硬化性組成物。
- 請求項1〜4のいずれか1項に記載の活性エネルギー線硬化性組成物の硬化物。
- JIS試験方法(K7209:2000)のC法を用いて測定した吸水率が、0.1〜4.0%の範囲である、請求項5に記載の硬化物。
- 請求項5記載の硬化物を有することを特徴とするレンズ。
- 請求項5記載の硬化物を有することを特徴とするウェハレベルレンズ。
- その少なくとも片面に無機化合物層が設けられた請求項5記載の硬化物を有することを特徴とするレンズ。
- 前記無機化合物層が、反射防止層である、請求項9に記載のレンズ。
- 請求項7〜10記載のいずれか1項に記載のレンズを有することを特徴とするカメラモジュール。
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