JP2012219157A - Anti-static agent for active energy ray curing type resin and active energy ray curing type resin containing anti-static agent - Google Patents
Anti-static agent for active energy ray curing type resin and active energy ray curing type resin containing anti-static agent Download PDFInfo
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- JP2012219157A JP2012219157A JP2011085008A JP2011085008A JP2012219157A JP 2012219157 A JP2012219157 A JP 2012219157A JP 2011085008 A JP2011085008 A JP 2011085008A JP 2011085008 A JP2011085008 A JP 2011085008A JP 2012219157 A JP2012219157 A JP 2012219157A
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- 239000002216 antistatic agent Substances 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title description 13
- 229920005989 resin Polymers 0.000 title description 13
- 239000011342 resin composition Substances 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 abstract description 3
- -1 phosphate ester Chemical class 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 2
- 239000008096 xylene Substances 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
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical class CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- OAMHTTBNEJBIKA-UHFFFAOYSA-N 2,2,2-trichloro-1-phenylethanone Chemical compound ClC(Cl)(Cl)C(=O)C1=CC=CC=C1 OAMHTTBNEJBIKA-UHFFFAOYSA-N 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
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-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
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 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
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- BMVWCPGVLSILMU-UHFFFAOYSA-N 5,6-dihydrodibenzo[2,1-b:2',1'-f][7]annulen-11-one Chemical compound C1CC2=CC=CC=C2C(=O)C2=CC=CC=C21 BMVWCPGVLSILMU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-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
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- 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
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- YCIAWJLYAXZODU-UHFFFAOYSA-N diphenylmethanone;2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1.CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 YCIAWJLYAXZODU-UHFFFAOYSA-N 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
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical class CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は活性エネルギー線硬化型樹脂用帯電防止剤、及び該帯電防止剤を含有する活性エネルギー線硬化型樹脂に関するものである。 The present invention relates to an antistatic agent for an active energy ray curable resin and an active energy ray curable resin containing the antistatic agent.
エネルギー線硬化型樹脂組成物は、様々な基材のコーティングや接着等に使用されている。かかるエネルギー線硬化型樹脂組成物においては、帯電し易く、塵や埃が付着しやすいため、用途によっては帯電防止性能が要求される。
そこで、エネルギー線硬化型樹脂組成物の帯電防止性能を向上させるため様々な提案がなされている。例えば、分子中にリン酸エステル、並びにアクリロイルオキシ基及び／又はメタクリロイルオキシ基を含有する単量体を含有する被覆組成物（特許文献１）、４級アンモニウム塩基および（メタ）アクリロイル基を有するモノマーを含む紫外線硬化型樹脂組成物（特許文献２）が開示されている。しかし、これらの組成物は一定の表面抵抗値を下げる効果が認められるが、より優れた帯電防止性能を有するエネルギー線硬化型樹脂組成物用の帯電防止剤が求められている。
Energy ray curable resin compositions are used for coating and adhesion of various substrates. Such an energy beam curable resin composition is easily charged, and dust and dirt are likely to adhere to it, so that antistatic performance is required depending on the application.
Therefore, various proposals have been made to improve the antistatic performance of the energy beam curable resin composition. For example, a coating composition containing a phosphate ester and a monomer containing an acryloyloxy group and / or a methacryloyloxy group in the molecule (Patent Document 1), a monomer having a quaternary ammonium base and a (meth) acryloyl group An ultraviolet curable resin composition (Patent Document 2) is disclosed. However, although these compositions have an effect of lowering a certain surface resistance value, an antistatic agent for an energy ray curable resin composition having more excellent antistatic performance is required.
本発明は上記の実情に鑑みてなされたものであり、その目的は、従来の帯電防止性を有する活性エネルギー線硬化型樹脂組成物より表面抵抗値を低下させることが出来る活性エネルギー線硬化型樹脂組成物用の帯電防止剤および該帯電防止剤を含有する活性エネルギー線硬化型樹脂組成物を提供することにある。 The present invention has been made in view of the above circumstances, and the object thereof is an active energy ray curable resin capable of lowering the surface resistance value compared to the conventional active energy ray curable resin composition having antistatic properties. An object is to provide an antistatic agent for a composition and an active energy ray-curable resin composition containing the antistatic agent.
本発明者らが鋭意研究を重ねた結果、従来の帯電防止性能を有する活性エネルギー線硬化型樹脂組成物においては、帯電防止性能を発揮するリン酸エステル基や４級アンモニウム塩基が樹脂組成物中に分散することにより表面抵抗値が高くなる、すなわち帯電防止性能が低下することに着目し、特定のリン酸エステル化合物の場合は、樹脂組成物表面に局在化し優れた表面抵抗値を示すことを見出し、本発明を完成するに至った。
すなわち、本発明は、下記一般式（１）及び／又は（２）で表されることを特徴とする活性エネルギー線硬化性樹脂組成物用帯電防止剤を第一の要旨とする。
As a result of intensive studies by the present inventors, in the active energy ray-curable resin composition having the conventional antistatic performance, phosphate ester groups and quaternary ammonium bases exhibiting the antistatic performance are contained in the resin composition. Focusing on the fact that the surface resistance value increases, that is, the antistatic performance decreases, by dispersing in the case of a specific phosphate ester compound, it is localized on the resin composition surface and exhibits an excellent surface resistance value. As a result, the present invention has been completed.
That is, this invention makes the 1st summary the antistatic agent for active energy ray-curable resin compositions characterized by being represented by the following general formula (1) and / or (2).
本発明の第二の要旨は、前記活性エネルギー線硬化性樹脂組成物用帯電防止剤を含有することを特徴とする活性エネルギー線硬化型樹脂組成物である。
さらに、本発明は前記活性エネルギー線硬化型樹脂組成物の表面抵抗が１０の１２乗Ω以下である事が好ましい。
The second gist of the present invention is an active energy ray-curable resin composition comprising the antistatic agent for an active energy ray-curable resin composition.
Furthermore, in the present invention, the active energy ray-curable resin composition preferably has a surface resistance of 10 12 Ω or less.
次に、本発明を実施するための形態について説明する。
本発明の活性エネルギー線硬化性樹脂組成物用帯電防止剤（以下、帯電防止剤と称す）は下記一般式（１）及び／又は（２）で示される化合物である。
Next, the form for implementing this invention is demonstrated.
The antistatic agent for active energy ray-curable resin composition of the present invention (hereinafter referred to as an antistatic agent) is a compound represented by the following general formula (1) and / or (2).
一般式（１）及び／又は（２）におけるRは炭素数８〜１３のアルキル基である。これらの置換基はとくに限定されるものではないが、オクチル、ノニレル、デシル、ドデシル、ウンデシル、トリデシル等の直鎖状のアルキレン基或いは、トリメチルヘキシル、メチルヘプチル、ジメチルヘプチル、トリメチルヘプチル、テトラメチルヘプチル、エチルヘプチル、メチルオクチル、メチルノニル、メチルデシル、メチルドデシル、メチルウンデシル、メチルトリデシル等の分岐状のアルキル基を示すことができる。 R in the general formula (1) and / or (2) is an alkyl group having 8 to 13 carbon atoms. These substituents are not particularly limited, but are linear alkylene groups such as octyl, nonenyl, decyl, dodecyl, undecyl, tridecyl, or trimethylhexyl, methylheptyl, dimethylheptyl, trimethylheptyl, tetramethylheptyl And branched alkyl groups such as ethyl heptyl, methyl octyl, methyl nonyl, methyl decyl, methyl dodecyl, methyl undecyl, methyl tridecyl and the like.
一般式(１)及び／又は（２）におけるｎは０以上、６以下である。ｎが６を超える場合は、帯電防止性能が十分でない、すなわち表面抵抗が１０の１３乗Ω以上となる問題が生じる。 N in the general formula (1) and / or (2) is 0 or more and 6 or less. When n exceeds 6, there arises a problem that the antistatic performance is not sufficient, that is, the surface resistance becomes 10 13 Ω or more.
本発明の帯電防止剤は、1種を単独で用いてもよく、又は２種以上を混合して用いても良い。 The antistatic agent of this invention may be used individually by 1 type, or may mix and use 2 or more types.
本発明の帯電防止剤は、市販のアルキル（エーテル）リン酸エステル型界面活性剤を使用することが出来る。例えば、東邦化学株式会社製「フォスファノール（登録商標）シリーズ」、株式会社ＡＤＥＫＡ製「アデカコール（登録商標）PS/CS/TSシリーズ」、第一工業製薬株式会社製「プライサーフ（登録商標）シリーズ」等が挙げられる。 As the antistatic agent of the present invention, a commercially available alkyl (ether) phosphate ester type surfactant can be used. For example, “Phosphanol (registered trademark) series” manufactured by Toho Chemical Co., Ltd., “ADEKA COAL (registered trademark) PS / CS / TS series” manufactured by ADEKA Corporation, “Plisurf® (registered trademark)” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Series "etc. are mentioned.
本発明の帯電防止剤の配合量は特に限定されないが、活性エネルギー線硬化型樹脂１００重量部に対して、３〜１５重量部が好ましく、５〜１０重量部がより好ましい。 ３重量部未満であると十分な導電性能が得られず、１５重量部を超えるとブリードという問題が生じる。 Although the compounding quantity of the antistatic agent of this invention is not specifically limited, 3-15 weight part is preferable with respect to 100 weight part of active energy ray hardening-type resins, and 5-10 weight part is more preferable. If the amount is less than 3 parts by weight, sufficient conductive performance cannot be obtained, and if it exceeds 15 parts by weight, a problem of bleeding occurs.
本発明の活性エネルギー線硬化型樹脂は、本発明の目的とする用途に従来から使用されているものが特に限定無く使用できる。 As the active energy ray-curable resin of the present invention, those conventionally used for the purpose of the present invention can be used without any particular limitation.
前記活性エネルギー線硬化型樹脂の好ましい例としては、炭素数１〜１４のアルキル基を有するアクリレート及び／又はメタクリレートの１種又は２種以上を主成分とするアクリル系ポリマーを含有するものを挙げることができる。 Preferable examples of the active energy ray-curable resin include those containing an acrylic polymer mainly composed of one or more of acrylates and / or methacrylates having an alkyl group having 1 to 14 carbon atoms. Can do.
また、１液タイプや２液タイプのウレタン樹脂、熱重合または放射重合によって重合可能なアクリル樹脂やエポキシ樹脂なども挙げることが出来る。 In addition, one-pack type or two-pack type urethane resin, acrylic resin or epoxy resin that can be polymerized by thermal polymerization or radiation polymerization can be used.
上記放射線としては、例えば、紫外線、レーザー線、α線、β線、γ線、X線、電子線などが挙げられる。なお、放射線として紫外線を用いる場合には光重合開始剤を添加する。光重合開始剤は、放射線反応成分の種類に応じ、その重合反応の引き金となり得る適当な波長の紫外線を照射することにより、ラジカルもしくはカチオンを生成する物質であれば良い。 Examples of the radiation include ultraviolet rays, laser beams, α rays, β rays, γ rays, X rays, and electron beams. In addition, when using an ultraviolet-ray as a radiation, a photoinitiator is added. The photopolymerization initiator may be any substance that generates radicals or cations by irradiating ultraviolet rays having an appropriate wavelength that can trigger the polymerization reaction according to the type of radiation reaction component.
光ラジカル重合開始剤としてはベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、o−ベンゾイル安息香酸メチル−ｐ−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、α−メチルベンゾイン等のベンゾイン類、ベンジルジメチルケタール、トリクロルアセトフェノン、２，２−ジエトキシアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン類、２−ヒドロキシ−２−メチルプロピオフェノン、２−ヒドロキシ−４’−イソプロピル−２−メチルプロピオフェノン等のプロピオフェノン類、ベンゾフェノン、メチルベンゾフェノン、ｐ−クロルベンゾフェノン、ｐ−ジメチルアミノベンゾフニノン等のベンゾフェノン類、２−クロルチオキサントン、２−エチルチオキサントン、２−イソプロピルチオキサントン等のチオキサントン類、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、（２，４，６−トリメチルベンゾイル）−（エトキシ）−フェニルホスフィンオキサイド等のアシルフォスフィンオキサイド類、ベンジル、ジベンゾスベロン、α−アシルオキシムエステルなどが挙げられる。 As radical photopolymerization initiator, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, o-benzoylbenzoic acid methyl-p-benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, benzyldimethyl ketal, trichloroacetophenone, Acetophenones such as 2,2-diethoxyacetophenone and 1-hydroxycyclohexyl phenyl ketone; propiophenones such as 2-hydroxy-2-methylpropiophenone and 2-hydroxy-4'-isopropyl-2-methylpropiophenone Benzophenones such as benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzofuninone, 2-chlorothioxanthone, 2-ethylthioxanthate Thioxanthones such as 2-isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)-( And acylphosphine oxides such as ethoxy) -phenylphosphine oxide, benzyl, dibenzosuberone, α-acyloxime ester and the like.
光カチオン重合開始剤としては、芳香族ジアゾニウム塩、芳香族ヨードニウム塩、芳香族スルホニウム塩等のオニウム塩や、鉄−アレン錯体、チタノセン錯体、アリールシラノール−アルミニウム錯体などの有機金属錯体類、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ−ヒドロキシイミドスルホナートなどが挙げられる。 Photocationic polymerization initiators include onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts, organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes, and nitrobenzyl. Examples thereof include esters, sulfonic acid derivatives, phosphoric acid esters, sulfonic acid derivatives, phosphoric acid esters, phenol sulfonic acid esters, diazonaphthoquinone, and N-hydroxyimide sulfonate.
光重合開始剤は、活性エネルギー線硬化型樹脂１００重量部に対し、通常０．１〜１０重量部、好ましくは０．２〜７重量部の範囲で配合するのが好ましい。 The photopolymerization initiator is usually blended in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin.
さらにアミン類などの光開始重合助剤を併用することも可能である。前記光開始助剤としては、２−ジメチルアミノエチルベンゾエート、ジメチルアミノアセトフェノン、ｐ−ジメチルアミノ安息香酸エチルエステル、ｐ−ジメチルアミノ安息香酸イソアミルエステルなどがあげられる。上記光重合開始助剤については、２種以上併用することも可能である。 It is also possible to use a photoinitiated polymerization aid such as amines in combination. Examples of the photoinitiator include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. Two or more photopolymerization initiation assistants can be used in combination.
本発明の活性エネルギー線硬化型樹脂組成物は前記活性エネルギー線硬化型樹脂に帯電防止剤を所定量配合して常法により混合することにより得られる。 The active energy ray-curable resin composition of the present invention can be obtained by mixing a predetermined amount of an antistatic agent with the active energy ray-curable resin and mixing them in a conventional manner.
本発明の活性エネルギー線硬化型樹脂組成物には、前記重合開始剤や重合開始助剤の他、希釈溶剤、滑剤、レべリング剤、フィラー等を必要に応じて添加することもできる。 In addition to the polymerization initiator and the polymerization initiation assistant, a diluent solvent, a lubricant, a leveling agent, a filler, and the like can be added to the active energy ray-curable resin composition of the present invention as necessary.
本発明の活性エネルギー線硬化型樹脂組成物の表面抵抗値が１０の１２乗Ω以下であることが好ましく、より好ましくは１０の１０乗Ω以下である。表面抵抗値が１０の１２乗Ωを超える場合は帯電による埃の付着等という問題が生じる。 The surface resistance value of the active energy ray-curable resin composition of the present invention is preferably 10 12 Ω or less, more preferably 10 10 Ω or less. When the surface resistance value exceeds 10 12 Ω, there arises a problem of dust adhesion due to charging.
以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明は、これらの実施例に限定されるものではない。なお、実施例、比較例中、部及び％は特に断らない限り重量基準である。
１．活性エネルギー線硬化型樹脂の合成
〔合成例１〕
フラスコにビスフェノールA型グリシジルエーテル(エポキシ当量＝４５０)のアクリル酸エステル３４４５ｇ（３．３モル）、ハイドロキノンモノメチルエーテル１．８１ｇ、キシレンジイソシアネート１８８ｇ(１モル)を仕込み、７０〜８０℃の条件にて残存イソシアネート濃度が０．１％になるまで反応させ、活性エネルギー線硬化型樹脂を得た。
〔合成例２〕
フラスコにビスフェノールA型グリシジルエーテル(エポキシ当量＝４５０)のアクリル酸エステル３４４５ｇ（３．３モル）、ハイドロキノンモノメチルエーテル１．８１ｇ、フェノキシエチルアクリレート２４２２ｇ、キシレンジイソシアネート１８８ｇ(１モル)を仕込み、７０〜８０℃の条件にて残存イソシアネート濃度が０．１％になるまで反応させ、活性エネルギー線硬化型樹脂を得た。
２．活性エネルギー線硬化型樹脂組成物の調整
上記で得られた合成例１又は２に下記表１に示す帯電防止剤を表２に示す割合（重量部）でそれぞれ配合し、更に光重合開始剤であるα−ヒドロキシアルキルフェノン（製品名：イルガキュア１８４、BASF社製）を３重量％、希釈剤として酢酸ブチルを５０重量％を配合し、混合して、活性エネルギー線硬化型樹脂組成物を得た。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In Examples and Comparative Examples, parts and% are based on weight unless otherwise specified.
1. Synthesis of active energy ray-curable resin [Synthesis Example 1]
A flask was charged with 3445 g (3.3 mol) of an acrylate ester of bisphenol A glycidyl ether (epoxy equivalent = 450), 1.81 g of hydroquinone monomethyl ether, and 188 g (1 mol) of xylene diisocyanate, and the conditions were 70 to 80 ° C. The reaction was continued until the residual isocyanate concentration became 0.1% to obtain an active energy ray-curable resin.
[Synthesis Example 2]
A flask was charged with 3445 g (3.3 mol) of acrylate ester of bisphenol A glycidyl ether (epoxy equivalent = 450), 1.81 g of hydroquinone monomethyl ether, 2422 g of phenoxyethyl acrylate, and 188 g (1 mol) of xylene diisocyanate, and 70-80 The reaction was continued under the condition of ° C. until the residual isocyanate concentration became 0.1% to obtain an active energy ray-curable resin.
2. Preparation of active energy ray-curable resin composition In the synthesis example 1 or 2 obtained above, the antistatic agent shown in Table 1 below was blended in the proportions (parts by weight) shown in Table 2, and further a photopolymerization initiator. A certain α-hydroxyalkylphenone (product name: Irgacure 184, manufactured by BASF) was blended with 3% by weight, and 50% by weight of butyl acetate as a diluent, and mixed to obtain an active energy ray-curable resin composition. .
＜評価サンプルの作成＞
上記により得られた活性エネルギー線硬化型樹脂組成物をPETフィルム(東レ製ルミラー)（コロナ処理面）へスピンコート（５００ｒｐｍ，５ｓｅｃ⇒１５００ｒｐｍ、１５ｓｅｃ）し、８０℃で１０分間乾燥後、高圧水銀灯２００ｍｊ／ｃｍ２の紫外線照射により評価サンプルを作成した。
＜表面抵抗測定条件＞
株式会社アドバンテスト製 Ｒ８３４０ ＵＬＴＲＡ ＨＩＧＨ ＲＥＳＩＳＴＡＮＣＥ ＭＥＴＥＲを用いて、温度２０℃、湿度６５％の条件下で測定した。評価結果は上記表１に示した。
The active energy ray-curable resin composition obtained as described above was spin-coated (500 rpm, 5 sec⇒1500 rpm, 15 sec) onto a PET film (Toray Lumirror) (corona-treated surface), dried at 80 ° C. for 10 minutes, and then a high-pressure mercury lamp. An evaluation sample was prepared by ultraviolet irradiation at 200 mj / cm 2.
<Surface resistance measurement conditions>
Measurement was performed under the conditions of a temperature of 20 ° C. and a humidity of 65% using an R8340 ULTRA HIGH RESISTANCE METER manufactured by Advantest Corporation. The evaluation results are shown in Table 1 above.
表２に示された結果から帯電防止剤が、一般式（１）におけるＲ、ｎが所定の範囲から外れた場合（比較例２〜３）、一般式（１）と構造が異なる場合（比較例５〜７）は表面抵抗値が１０の１２乗Ωを超えることが分かる。 From the results shown in Table 2, when R and n in the general formula (1) are out of the predetermined range (Comparative Examples 2-3), the structure is different from the general formula (1) (comparison) It can be seen that Examples 5 to 7) have a surface resistance value exceeding 10 12 Ω.
本発明の帯電防止剤及びこれを用いた活性エネルギー線硬化型樹脂組成物は、光学フィルム用ハードコート、光学フィルム、帯電防止保護フィルムに好適に使用できる。
The antistatic agent of the present invention and the active energy ray-curable resin composition using the same can be suitably used for hard coats for optical films, optical films, and antistatic protective films.
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| TW101106049A TWI492975B (en) | 2011-04-07 | 2012-02-23 | Active energy line hardening resin |
| CN2012100505469A CN102731824A (en) | 2011-04-07 | 2012-02-29 | Anti-static disruptor for activation energy ray curable resin, and activation energy ray curable resin having the same |
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