JP4368385B2 - UV-absorbing composite film - Google Patents
UV-absorbing composite film Download PDFInfo
- Publication number
- JP4368385B2 JP4368385B2 JP2007006273A JP2007006273A JP4368385B2 JP 4368385 B2 JP4368385 B2 JP 4368385B2 JP 2007006273 A JP2007006273 A JP 2007006273A JP 2007006273 A JP2007006273 A JP 2007006273A JP 4368385 B2 JP4368385 B2 JP 4368385B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- ultraviolet
- hydrogen atom
- absorbing
- composite film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002131 composite material Substances 0.000 title claims description 23
- 229920000642 polymer Polymers 0.000 claims description 70
- 239000000178 monomer Substances 0.000 claims description 61
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- -1 isocyanate compound Chemical class 0.000 claims description 24
- 239000002985 plastic film Substances 0.000 claims description 24
- 229920006255 plastic film Polymers 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229920003180 amino resin Polymers 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 238000003851 corona treatment Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical group 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 239000010410 layer Substances 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 238000001723 curing Methods 0.000 description 18
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- 125000001424 substituent group Chemical group 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 10
- 239000000049 pigment Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZKECVHXIVHRIIA-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-1-yl)prop-2-enamide Chemical compound CC1(C)CCCC(C)(C)N1NC(=O)C=C ZKECVHXIVHRIIA-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000005023 xylyl group Chemical group 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 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 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000004634 thermosetting polymer Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 150000001565 benzotriazoles Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
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- 239000003431 cross linking reagent Substances 0.000 description 2
- 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 2
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- GIIUJJXXMYYQQD-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)C=C GIIUJJXXMYYQQD-UHFFFAOYSA-N 0.000 description 1
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- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
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- 239000006078 metal deactivator Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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- 125000001421 myristyl 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])C([H])([H])[H] 0.000 description 1
- HNWDFLSODFEDIT-UHFFFAOYSA-N n-(1,2,2,6,6-pentamethylpiperidin-3-yl)prop-2-enamide Chemical compound CN1C(C)(C)CCC(NC(=O)C=C)C1(C)C HNWDFLSODFEDIT-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- 125000003367 polycyclic group Chemical group 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 229920000307 polymer substrate Polymers 0.000 description 1
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- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、紫外線吸収能を有し、かつ長期耐候性に優れた紫外線吸収性複合フィルムに関するものである。 The present invention relates to a UV-absorbing composite film having UV-absorbing ability and excellent long-term weather resistance.
紫外線を遮断して内部を保護するために、農業用グリーンハウスなどの屋外で使用するフィルム、建物や自動車の窓などに貼着するフィルムとして紫外線吸収性フィルムがこれまでから使用されている。かかる紫外線吸収性フィルムそのものの耐候性を向上させる手段として、これまで種々の技術が提案されている。例えば特許文献１には、フィルム用樹脂に紫外線吸収剤を練り込んだフィルム、特許文献２には、紫外線吸収性モノマーを共重合したアクリル樹脂を使用したフィルム、特許文献３には、プラスチックフィルム表面に紫外線吸収型アクリル系樹脂及びカチオン系ポリマーを主成分とした被覆層を設けた複合フィルムがそれぞれ提案されている。
しかしながら、フィルム用樹脂に紫外線吸収剤を練り込んだフィルムでは、紫外線吸収剤が溶出したり、ブリードアウトするといった問題や耐候性が不十分であるといった問題がある。また紫外線吸収モノマーを共重合したアクリル樹脂を使用したフィルムやプラスチックフィルム表面に紫外線吸収型アクリル系樹脂及びカチオン系ポリマーを主成分とした被覆層を設けた複合フィルムでは、プラスチックフィルムとの密着性に劣り、長期間使用すると層間で劣化を起こす。 However, a film in which an ultraviolet absorbent is kneaded into a resin for film has a problem that the ultraviolet absorbent is eluted or bleeds out and a problem that weather resistance is insufficient. Films using acrylic resins copolymerized with UV-absorbing monomers, and composite films with plastic film surfaces that have UV-absorbing acrylic resins and cationic polymers as the main component, have good adhesion to plastic films. It is inferior and causes deterioration between layers when used for a long time.
本発明は、このような問題を解決するためになされたものであって、優れた紫外線吸収能を有すると共に、プラスチックフィルムとの密着性に優れ、長期耐候性を備えたフィルムを提供することを目的とする。 The present invention has been made to solve such a problem, and provides a film having excellent ultraviolet absorbing ability, excellent adhesion to a plastic film, and having long-term weather resistance. Objective.
本発明によれば、片面又は両面を易接着処理したプラスチックフィルムの処理面上に、下記一般式（１）及び（２）で表される紫外線吸収性単量体から選ばれる少なくとも一種を含む単量体組成物をラジカル重合してなる紫外線吸収性重合体を含有し、かつ硬化された紫外線吸収性重合体層を有することを特徴とする紫外線吸収性複合フィルムが提供される。 According to the present invention, a single surface containing at least one selected from the ultraviolet-absorbing monomers represented by the following general formulas (1) and (2) is provided on the treated surface of a plastic film having one or both surfaces subjected to easy adhesion treatment. An ultraviolet-absorbing composite film comprising an ultraviolet-absorbing polymer obtained by radical polymerization of a monomer composition and having a cured ultraviolet-absorbing polymer layer is provided.
当該重合体は下記一般式（３）、（４）及び（５）で表される単量体から選ばれる少なくとも一種をさらに含む単量体組成物をラジカル重合したものであることが好ましい。 The polymer is preferably a polymer obtained by radical polymerization of a monomer composition further containing at least one selected from monomers represented by the following general formulas (3), (4) and (5).
また紫外線吸収性複合フィルムは、紫外線吸収性重合体が硬化性官能基を有し、紫外線吸収性重合体層が硬化剤を含むものであることがよい。 In the UV-absorbing composite film, the UV-absorbing polymer preferably has a curable functional group, and the UV-absorbing polymer layer preferably contains a curing agent.
このとき硬化性官能基は活性水素を有する基であることが好ましい。また硬化剤は、イソシアネート化合物、エポキシ樹脂又はアミノプラスト樹脂であることが好ましい。 At this time, the curable functional group is preferably a group having active hydrogen. The curing agent is preferably an isocyanate compound, an epoxy resin or an aminoplast resin.
プラスチックフィルムの厚さは、１〜１，０００ミクロンであり、易接着処理面の表面ぬれ指数は、３６ｄｙｎ／ｃｍ以上であることが好ましい。 The thickness of the plastic film is preferably 1 to 1,000 microns, and the surface wetting index of the easy-adhesion treated surface is preferably 36 dyn / cm or more.
本発明の紫外線吸収性複合フィルムは、優れた紫外線吸収能を有すると共に、プラスチックフィルムとの密着性に優れ、長期耐候性を備える。 The ultraviolet-absorbing composite film of the present invention has excellent ultraviolet-absorbing ability, is excellent in adhesion with a plastic film, and has long-term weather resistance.
本発明の紫外線吸収性複合フィルムは、片面又は両面を易接着処理したプラスチックフィルムの処理面上に紫外線吸収性重合体層を有することが大きな特徴の一つである。易接着処理した面上に紫外線吸収性重合体層を形成するので、プラスチックフィルムと当該重合体層の密着がより強くなり、プラスチックフィルムと当該重合体層の間での剥がれや劣化が生じない。またプラスチックフィルム上に紫外線吸収性重合体層を形成しているので、紫外線吸収性重合体のみからなるフィルムに比べ、引っ張り及び折り曲げ強度が強くなる。 One of the major features of the ultraviolet-absorbing composite film of the present invention is that it has an ultraviolet-absorbing polymer layer on the treated surface of a plastic film having one or both surfaces subjected to easy adhesion treatment. Since the ultraviolet-absorbing polymer layer is formed on the surface subjected to the easy adhesion treatment, the adhesion between the plastic film and the polymer layer becomes stronger, and peeling or deterioration between the plastic film and the polymer layer does not occur. In addition, since the UV-absorbing polymer layer is formed on the plastic film, the tensile and bending strength is increased as compared with a film made of only the UV-absorbing polymer.
本発明で使用するプラスチックフィルムとしては、公知のプラスチックフィルムであればいずれも使用することができる。例えば、ポリエチレンフィルム、ポリプロピレンフィルム等のポリオレフィンフィルム；ポリスチレンフィルム；ポリエチレンテレフタレート等のポリエステルフィルム；ポリカーボネートフィルム；トリアセチルセルロースフィルム；セロハンテープフィルム；フッ素フィルム；ポリアミドフィルム；ポリイミドフィルム；ポリフェニレンスルフィドフィルム；ポリエーテルイミドフィルム；ポリエーテルスルフィドフィルム；ポリスルホンフィルム；ポリアクリロニトリルフィルム；ポリ酢酸ビニルフィルム；ポリエーテルエーテルケトン等の単体又は複合体が挙げられる。フィルムとしての機械的、熱的物性面から、ポリエステルフィルム、ポリオレフィンフィルム、ポリフェニレンスルフィドフィルム、フッ素フィルムの単体又は複合体が好ましい。 As the plastic film used in the present invention, any known plastic film can be used. For example, polyolefin film such as polyethylene film and polypropylene film; polystyrene film; polyester film such as polyethylene terephthalate; polycarbonate film; triacetyl cellulose film; cellophane tape film; fluorine film; polyamide film; Examples thereof include a simple substance or a composite such as a film; a polyether sulfide film; a polysulfone film; a polyacrylonitrile film; a polyvinyl acetate film; From the viewpoint of mechanical and thermal properties as a film, a single film or a composite of a polyester film, a polyolefin film, a polyphenylene sulfide film, or a fluorine film is preferable.
また、かかるプラスチックフィルムには、必要に応じて、本発明の効果を損なわない範囲において、公知の添加剤を配合してもよい。添加剤としては、例えば耐熱安定剤、耐酸化安定剤、顔料、染料、無機・有機微粉末、分散剤、カップリング剤、充填剤等が挙げられる。 Moreover, you may mix | blend a well-known additive with this plastic film as needed in the range which does not impair the effect of this invention. Examples of additives include heat stabilizers, oxidation stabilizers, pigments, dyes, inorganic / organic fine powders, dispersants, coupling agents, fillers, and the like.
さらに、プラスチックフィルムは、未配向、一軸配向、二軸配向のいずれでも使用することができるが、機械的強度が要求される場合には配向フィルムが好ましい。 Furthermore, the plastic film can be used in any of unoriented, uniaxial orientation, and biaxial orientation, but the oriented film is preferred when mechanical strength is required.
プラスチックの厚みに特に限定はないが、１〜１，０００ミクロンの範囲が好ましい。また、プラスチックフィルムの光学的特性等についても特に限定はなく、本発明の紫外線吸収性複合フィルムの用途に応じて、所望のものを使用すればよい。 The thickness of the plastic is not particularly limited, but a range of 1 to 1,000 microns is preferable. Moreover, there is no limitation in particular also about the optical characteristic etc. of a plastic film, What is necessary is just to use a desired thing according to the use of the ultraviolet-absorbing composite film of this invention.
本発明の紫外線吸収性複合フィルムでは、上記プラスチックフィルムの片面又は両面を易接着処理する。本発明における易接着処理とは、コロナ放電処理、プラズマ処理、アルカリ金属溶液処理、高周波スパッタエッチング処理等の表面処理及びポリエステル、ポリ（メタ）アクリル酸エステル、ポリウレタン、ハロゲン化ポリオレフィン等又はこれらの混合物もしくは反応物による下塗り処理を言う。かかる易接着処理の強度に特に限定はないが、密着性の点からＪＩＳ−Ｋ−６７６８に基づく表面ぬれ指数が３６ｄｙｎ／ｃｍ以上であることが望ましい。 In the ultraviolet-absorbing composite film of the present invention, one side or both sides of the plastic film is subjected to easy adhesion treatment. The easy adhesion treatment in the present invention refers to surface treatment such as corona discharge treatment, plasma treatment, alkali metal solution treatment, high-frequency sputter etching treatment, polyester, poly (meth) acrylic ester, polyurethane, halogenated polyolefin, etc., or a mixture thereof. Or the undercoating process with a reactant. The strength of such easy adhesion treatment is not particularly limited, but it is desirable that the surface wetting index based on JIS-K-6768 is 36 dyn / cm or more from the viewpoint of adhesion.
本発明における紫外線吸収性重合体は、一般式（１）及び（２）で表される紫外線吸収性単量体から選ばれる少なくとも一種を含む単量体組成物をラジカル重合してなる重合体であり、単量体組成物が一般式（３）、（４）、（５）で表される単量体をさらに含んでいてもよい。 The ultraviolet absorbing polymer in the present invention is a polymer obtained by radical polymerization of a monomer composition containing at least one selected from the ultraviolet absorbing monomers represented by the general formulas (1) and (2). Yes, the monomer composition may further contain monomers represented by the general formulas (3), (4), and (5).
本発明における前記一般式（１）で表される紫外線吸収性単量体は、式中、Ｒ1は水素原子または炭素数１〜８の炭化水素基で構成され、Ｒ2は低級アルキレン基で構成され、Ｒ3は水素原子またはメチル基で構成され、Ｘは水素、ハロゲン、炭素数１〜８の炭化水素基、低級アルコキシ基、シアノ基またはニトロ基で構成されるベンゾトリアゾール類である。 In the ultraviolet absorbent monomer represented by the general formula (1) in the present invention, R 1 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 2 is a lower alkylene group. R 3 is composed of a hydrogen atom or a methyl group, and X is benzotriazoles composed of hydrogen, halogen, a hydrocarbon group having 1 to 8 carbon atoms, a lower alkoxy group, a cyano group or a nitro group.
上記式中、Ｒ1で表される置換基としては、例えば水素原子、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などの鎖式炭化水素基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基などの脂環式炭化水素基；フェニル基、トリル基、キシリル基、ベンジル基、フェネチル基などの芳香族炭化水素基であり、Ｒ2で表される置換基は、具体的には炭素数１〜６のアルキレン基であって、メチレン基、エチレン基、トリメチレン基、テトラメチレン基などの直鎖状アルキレン基及びプロピレン基、２−メチルトリメチレン基、２−メチルテトラメチレン基などの分枝鎖状アルキレン基であり、Ｘで表される置換基は、水素；フッ素、塩素、シュウ素、ヨウ素などのハロゲン；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などの鎖式炭化水素基：シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基などの脂環式炭化水素基：フェニル基、トリル基、キシリル基、ベンジル基、フェネチル基などの芳香族炭化水素基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘプトキシ基など炭素数１〜６の低級アルコキシ基；シアノ基；ニトロ基である。 In the above formula, examples of the substituent represented by R 1 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group. Chain hydrocarbon groups such as octyl group; cycloaliphatic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group The substituent represented by R 2 is specifically an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and the like. Straight chain alkylene group and branched chain alkylene group such as propylene group, 2-methyltrimethylene group and 2-methyltetramethylene group. And a substituent represented by X is hydrogen; halogen such as fluorine, chlorine, sulfur, iodine; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, Chain hydrocarbon group such as hexyl group, heptyl group, octyl group: cycloaliphatic hydrocarbon group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group: phenyl group, tolyl group, xylyl group An aromatic hydrocarbon group such as benzyl group, phenethyl group; a lower alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, heptoxy group; cyano group; nitro group.
前記一般式（１）で表される紫外線吸収性単量体としては、例えば２−［２'−ヒドロキシ−５'−（メタクリロイルオキシメチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−（メタクリロイルオキシエチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−（メタクリロイルオキシプロピル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−（メタクリロイルオキシヘキシル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−３'−ｔｅｒｔ−ブチル−５'−（メタクリロイルオキシエチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−ｔｅｒｔ−ブチル−３'−（メタクリロイルオキシエチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−（メタクリロイルオキシエチル）フェニル］−５−クロロ−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−（メタクリロイルオキシエチル）フェニル］−５−メトキシ−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−（メタクリロイルオキシエチル）フェニル］−５−シアノ−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−（メタクリロイルオキシエチル）フェニル］−５−ｔｅｒｔ−ブチル−２Ｈ−ベンゾトリアゾール、２−［２'−ヒドロキシ−５'−（メタクリロイルオキシエチル）フェニル］−５−ニトロ−２Ｈ−ベンゾトリアゾールなどが挙げられるが、特にこれらに限定されるものではない。一般式（１）で表されるこれら紫外線吸収性単量体は一種類のみを用いてもよく、また二種類以上を適宜混合して用いてもよい。 Examples of the ultraviolet absorbing monomer represented by the general formula (1) include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′- Hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy- 5 ′-(methacryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [ 2′-Hydroxy-5′-tert-butyl-3 ′-(methacryloyloxyethyl) phenyl] -2H-ben Triazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5 -Methoxy-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxy) Ethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like. It is not limited to these. These ultraviolet absorbing monomers represented by the general formula (1) may be used alone or in a suitable mixture of two or more.
また前記一般式（２）で表される紫外線吸収性単量体は、式中、Ｒ4で表される置換基は低級アルキレン基で構成され、Ｒ5で表される水素原子またはメチル基で構成されるベンゾトリアゾール類である。 In the ultraviolet absorbing monomer represented by the general formula (2), the substituent represented by R 4 is composed of a lower alkylene group, and is a hydrogen atom or methyl group represented by R 5. Constituted benzotriazoles.
上記式中、Ｒ4で表される置換基は、具体的には炭素数２または３のアルキレン基であって、エチレン基、トリメチレン基、プロピレン基などを挙げることができる。 In the above formula, the substituent represented by R 4 is specifically an alkylene group having 2 or 3 carbon atoms, and examples thereof include an ethylene group, a trimethylene group, and a propylene group.
前記一般式（２）で表される紫外線吸収性単量体としては、例えば、２−〔２'−ヒドロキシ−５'−（β−メタクリロイルオキシエトキシ）−３'−ｔｅｒｔ−ブチルフェニル〕−４−ｔｅｒｔ−ブチル−２Ｈ−ベンゾトリアゾールが挙げられるが、特にこれに限定されるものではない。一般式（２）で表されるこれら紫外線吸収性単量体は一種類のみを用いてもよく、また二種類以上を適宜混合してもよい。 Examples of the ultraviolet absorbing monomer represented by the general formula (2) include 2- [2′-hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-tert-butylphenyl] -4. Although -tert-butyl-2H-benzotriazole is mentioned, it is not particularly limited to this. These ultraviolet absorbing monomers represented by the general formula (2) may be used alone or in combination of two or more.
本発明で使用する一般式（３）、（４）の紫外線安定性単量体において、式中、Ｒ6で示される置換基は水素原子またはシアノ基で構成され、Ｒ7、Ｒ8、Ｒ7'、Ｒ8'で示される置換基はそれぞれ独立して水素原子またはメチル基で構成され、Ｒ9で示される置換基が水素原子または炭化水素基で構成され、Ｙで示される置換基が酸素原子またはイミノ基で構成されるピペリジン類である。 In the UV-stable monomers of the general formulas (3) and (4) used in the present invention, the substituent represented by R 6 is composed of a hydrogen atom or a cyano group, and R 7 , R 8 , R The substituents represented by 7 ′ and R 8 ′ are each independently composed of a hydrogen atom or a methyl group, the substituent represented by R 9 is composed of a hydrogen atom or a hydrocarbon group, and the substituent represented by Y is Piperidines composed of an oxygen atom or an imino group.
上記Ｒ9で示される置換基としては、具体的には水素原子、炭素数１〜１８の炭化水素基であって、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基など鎖式炭化水素基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基などの脂環式炭化水素基；フェニル基、トリル基、キシリル基、ベンジル基、フェネチル基などの芳香族炭化水素基などが非限定的に例示される。 Specific examples of the substituent represented by R 9 include a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, and include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert group. -Chain hydrocarbons such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl Group: cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other alicyclic hydrocarbon groups; phenyl group, tolyl group, xylyl group, xylyl group, benzyl group, phenethyl group and other aromatic hydrocarbon groups, etc. Is illustrated in a non-limiting manner.
前記一般式（３）で表される紫外線安定性単量体としては、例えば４−（メタ）アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、４−（メタ）アクリロイルオキシ−１，２，２，６，６−ペンタメチルピペリジン、４−（メタ）アクリロイルアミノ−１，２，２，６，６−ペンタメチルピペリジン、４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルアミノ−２，２，６，６−テトラメチルピペリジンなどが挙げられ、これらの一種のみを用いてもよく、また二種以上を適宜混合して用いてもよい。もちろん一般式（３）の紫外線安定性単量体はこれら化合物に限定されるものではない。 Examples of the UV stable monomer represented by the general formula (3) include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2, 2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6- Pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoyl Amino-2,2,6,6-tetramethylpiperidine and the like may be mentioned, and only one of these may be used, or two or more may be used in appropriate mixture. Of course, the ultraviolet-stable monomer of General formula (3) is not limited to these compounds.
前記一般式（４）で表される紫外線安定性単量体としては、例えば１−（メタ）アクリロイル−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−クロトノイル−４−クロトイルオキシ−２，２，６，６−テトラメチルピペリジンなどが挙げられ、これら一種のみを用いてもよく、また二種以上を適宜混合して用いてもよい。なお一般式（４）の紫外線安定性単量体はこれらに限定されるものではない。 Examples of the UV-stable monomer represented by the general formula (4) include 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- ( (Meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine, etc. These may be used alone or in combination of two or more. In addition, the ultraviolet-stable monomer of General formula (4) is not limited to these.
本発明に係る一般式（５）に表される不飽和単量体は、式中、Ｒ10で示される置換基が水素原子またはメチル基で構成され、Ｚで示される置換基が炭素数４以上の炭化水素基で構成される不飽和単量体である。 In the unsaturated monomer represented by the general formula (5) according to the present invention, the substituent represented by R 10 is composed of a hydrogen atom or a methyl group, and the substituent represented by Z has 4 carbon atoms. It is an unsaturated monomer composed of the above hydrocarbon groups.
上記式中、Ｚで表される置換基はシクロヘキシル基、メチルシクロヘキシル基、シクロドデシル基などの炭素数４以上の脂環式炭化水素基；ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、２−エチルヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、ペンタデシル基、オクタデシル基など炭素数４以上の直鎖または分枝鎖のアルキル基；ボルニル基、イソボルニル基などの炭素数４以上の多環式炭化水素基であり、中でも脂環式炭化水素基、分枝鎖のアルキル基、炭素数６以上の直鎖アルキル基が好ましい。 In the above formula, the substituent represented by Z is an alicyclic hydrocarbon group having 4 or more carbon atoms such as a cyclohexyl group, a methylcyclohexyl group, or a cyclododecyl group; a butyl group, an isobutyl group, a tert-butyl group, or 2-ethylhexyl. A linear or branched alkyl group having 4 or more carbon atoms such as a group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group, octadecyl group; carbon number such as bornyl group, isobornyl group It is a polycyclic hydrocarbon group having 4 or more, and among them, an alicyclic hydrocarbon group, a branched alkyl group, and a linear alkyl group having 6 or more carbon atoms are preferable.
本発明に係る一般式（５）に表される不飽和単量体として、例えばシクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、シクロドデシル（メタ）アクリレート、ｔｅｒｔ−ブチルシクロヘキシル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ステアリル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレートなどが挙げられ、これらの一種または二種以上が使用できる。 Examples of the unsaturated monomer represented by the general formula (5) according to the present invention include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, Examples include isobutyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. The above can be used.
また上記単量体以外のその他の共重合可能な不飽和単量体は、紫外線吸収性単量体が繰り返し単位の一部として含まれる重合体に要求される各種物性を損なわないものであればいずれも使用することができる。具体的には、（メタ）アクリル酸、クロトン酸、イタコン酸、マレイン酸、無水マレイン酸等のカルボキシル基含有不飽和単量体；２−（メタ）アクリロイルオキシエチルアシッドホスフェート、２−（メタ）アクリロイルオキシプロピルアシッドホスフェート、２−（メタ）アクリロイルオキシ−３−クロロプロピルアシッドホスフェート、２−メタクリロイルオキシエチルフェニルリン酸等の酸性リン酸エステル系不飽和単量体；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、カプロラクトン変性ヒドロキシ（メタ）アクリレート（例えば、ダイセル化学工業株式会社製；商品名「プラクセルＦＭ」）、フタル酸とプロピレングリコールとから得られるポリエステルジオールのモノ（メタ）アクリレート等の活性水素を有する基を含有する不飽和単量体；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート等の（メタ）アクリル酸低級アルキルエステル；グリシジル（メタ）アクリレート等のエポキシ基含有不飽和単量体；（メタ）アクリルアミド、ウレイドエチルアクリレート、ウレイドエチルビニルエーテル、メタクリロイルジシアンアミド、Ｎ，Ｎ' −ジメチルアミノチル（メタ）アクリレート、ビニルピリジン、ビニルイミダゾール等の含窒素不飽和単量体；β−ビニルオキシエチルメタクリレート、２−ブチン−１−オールアクリレート等の２個の重合性二重結合を有する不飽和単量体；塩化ビニル、塩化ビニリデン等のハロゲン含有不飽和単量体；スチレン、α−メチルスチレン、ビニルトルエン等の芳香族不飽和単量体；酢酸ビニル等のビニルエステル；ビニルエーテルなどが挙げられるが、特にこれらに限定されるものではない。その他単量体は必要に応じて一種類のみを用いてもよく、また二種以上を用いてもよい。 In addition to the above monomers, other copolymerizable unsaturated monomers may be used as long as they do not impair various physical properties required for a polymer in which an ultraviolet absorbing monomer is included as a part of a repeating unit. Either can be used. Specifically, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and other carboxyl group-containing unsaturated monomers; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) Acid phosphate ester unsaturated monomers such as acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2-methacryloyloxyethylphenyl phosphate; hydroxyethyl (meth) acrylate, hydroxy Mono (meth) acrylate of polyester diol obtained from propyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (eg, Daicel Chemical Industries, Ltd .; trade name “Placcel FM”), phthalic acid and propylene glycol Unsaturated monomers containing active hydrogen-containing groups such as methylate; lower alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate Ester; Epoxy group-containing unsaturated monomer such as glycidyl (meth) acrylate; (meth) acrylamide, ureidoethyl acrylate, ureidoethyl vinyl ether, methacryloyl dicyanamide, N, N′-dimethylaminotyl (meth) acrylate, vinyl Nitrogen-containing unsaturated monomers such as pyridine and vinylimidazole; unsaturated monomers having two polymerizable double bonds such as β-vinyloxyethyl methacrylate and 2-butyn-1-ol acrylate; vinyl chloride; Halogen-containing unsaturated monomers such as vinylidene chloride Styrene, alpha-methyl styrene, aromatic unsaturated monomers such as vinyl toluene, vinyl esters such as vinyl acetate; the like vinyl ether, but is not particularly limited thereto. Only one type of other monomer may be used as necessary, or two or more types may be used.
なお、後述する紫外線吸収性重合体層の硬化処理において、紫外線吸収性重合体が単独で硬化する場合には、上記その他単量体として、エポキシ基やイソシアネート基を有する不飽和単量体を含むか、エポキシ基、イソシアネート基、重合性二重結合を持つ化合物を、紫外線共重合体を重合した後にこれらの官能基が残るように付加する必要がある。一方、架橋剤によって架橋硬化する場合には、エポキシ基やカルボキシル基、活性水素を有する基等の硬化性官能基を有する不飽和単量体を含んでいる必要がある。これらの中でも活性水素を有する基が硬化性官能基として好ましい。 In addition, in the curing treatment of the ultraviolet absorbing polymer layer to be described later, when the ultraviolet absorbing polymer is cured alone, the other monomer includes an unsaturated monomer having an epoxy group or an isocyanate group. Alternatively, it is necessary to add a compound having an epoxy group, an isocyanate group, or a polymerizable double bond so that these functional groups remain after the ultraviolet copolymer is polymerized. On the other hand, when crosslinking and curing with a crosslinking agent, it is necessary to include an unsaturated monomer having a curable functional group such as an epoxy group, a carboxyl group, or a group having active hydrogen. Among these, a group having active hydrogen is preferable as the curable functional group.
一般式（１）、（２）で表される紫外線吸収性単量体の使用量は、特に限定されないが、紫外線吸収性重合体に対して０．１〜９９ｗｔ％とすることが望まれる。より好ましい範囲について述べると、下限側として好ましくは１ｗｔ％、さらに好ましくは５ｗｔ％である。他方上限側として好ましくは６０ｗｔ％、さらに好ましくは５０ｗｔ％である。０．１ｗｔ％よりも少ないと得られる紫外線吸収性重合体の紫外線遮断能力が不十分となり、９９ｗｔ％よりも多いと紫外線吸収性重合体の他の樹脂との相溶性が悪くなることがある。 Although the usage-amount of the ultraviolet absorptive monomer represented by General formula (1), (2) is not specifically limited, It is desirable to set it as 0.1-99 wt% with respect to an ultraviolet absorptive polymer. A more preferable range is described. The lower limit is preferably 1 wt%, and more preferably 5 wt%. On the other hand, the upper limit is preferably 60 wt%, more preferably 50 wt%. If the amount is less than 0.1 wt%, the ultraviolet absorbing polymer obtained has insufficient UV blocking ability, and if it exceeds 99 wt%, the compatibility of the ultraviolet absorbing polymer with other resins may be deteriorated.
また、紫外線吸収性重合体層中の紫外線吸収性単量体の使用量は、特に限定されないが、紫外線吸収性重合体層の層厚との関係において、膜厚（μｍ）と紫外線吸収性重合体層１００ｇに対する紫外線吸収性単量体の使用量（ｇ）との積が１〜５，０００の範囲にあるのがよい。より好ましい範囲について述べると、下限側として好ましくは１０、さらに好ましくは１００である。他方上限側として好ましくは２，５００、さらに好ましくは１，５００である。上記積が１より小さいと紫外線遮断能力が不足するおそれがあり、５，０００より大きいと紫外線吸収性重合体層の膜厚が厚くなりすぎたり、紫外線吸収性単量体の量が多くなりすぎフィルム自体の伸びが低下するおそれがある。 The amount of the UV-absorbing monomer used in the UV-absorbing polymer layer is not particularly limited, but the film thickness (μm) and the UV-absorbing weight are related to the layer thickness of the UV-absorbing polymer layer. The product of the amount (g) of the UV-absorbing monomer with respect to 100 g of the combined layer is preferably in the range of 1 to 5,000. A more preferable range is described as follows. The lower limit is preferably 10, and more preferably 100. On the other hand, the upper limit is preferably 2,500, more preferably 1,500. If the product is less than 1, the UV blocking ability may be insufficient. If it is greater than 5,000, the UV-absorbing polymer layer is too thick or the amount of UV-absorbing monomer is too large. There is a possibility that the elongation of the film itself is lowered.
一般式（３）、（４）で表される紫外線安定性単量体の使用量は、特に限定されるものではないが、紫外線吸収性重合体に対して１〜９９．９ｗｔ％とすることが望まれる。より好ましい範囲について述べると、下限側として好ましくは５ｗｔ％、さらに好ましくは１０ｗｔ％である。他方上限側として好ましくは８０ｗｔ％、さらに好ましくは５０ｗｔ％である。紫外線安定性単量体の合計使用量が１ｗｔ％よりも少ないと、紫外線吸収性重合体層の耐久性が悪くなることがあり、９９．９ｗｔ％よりも多いと、紫外線吸収性重合体中の紫外線吸収性単量体の含有量が少なくなりすぎ、得られる紫外線吸収性重合体層の紫外線遮断能力が不十分となることがある。 Although the usage-amount of the ultraviolet-stable monomer represented by General formula (3), (4) is not specifically limited, It shall be 1-99.9 wt% with respect to an ultraviolet absorptive polymer. Is desired. The more preferable range is described. The lower limit is preferably 5 wt%, and more preferably 10 wt%. On the other hand, the upper limit is preferably 80 wt%, more preferably 50 wt%. If the total amount of UV-stable monomers used is less than 1 wt%, the durability of the UV-absorbing polymer layer may deteriorate, and if it exceeds 99.9 wt%, The content of the UV-absorbing monomer may be too small, and the UV-absorbing polymer layer obtained may have insufficient UV blocking ability.
一般式（５）で表される不飽和単量体の使用量は、特に限定されるものではないが、紫外線吸収性重合体に対して１〜９９．９ｗｔ％とすることが望まれる。より好ましい範囲について述べると、下限側として好ましくは５ｗｔ％、さらに好ましくは１０ｗｔ％である。他方上限側として好ましくは８０ｗｔ％、さらに好ましくは５０ｗｔ％である。１ｗｔ％よりも少ないと、得られる紫外線吸収性重合体の他の樹脂との相溶性が悪くなることがあり、９９．９ｗｔ％よりも多いと、紫外線吸収性重合体中の紫外線吸収性単量体の含有量が少なくなりすぎ、得られる紫外線吸収性重合体層の紫外線遮断能力が不十分となることがある。 Although the usage-amount of the unsaturated monomer represented by General formula (5) is not specifically limited, It is desirable to set it as 1-99.9 wt% with respect to an ultraviolet absorptive polymer. The more preferable range is described. The lower limit is preferably 5 wt%, and more preferably 10 wt%. On the other hand, the upper limit is preferably 80 wt%, more preferably 50 wt%. If it is less than 1 wt%, the compatibility of the resulting UV-absorbing polymer with other resins may deteriorate, and if it exceeds 99.9 wt%, the UV-absorbing monomer in the UV-absorbing polymer The content of the body becomes too low, and the ultraviolet ray-absorbing polymer layer obtained may have insufficient ultraviolet blocking ability.
上記単量体の混合方法は、特に限定されるものではなく、従来公知の混合方法が採用され得る。 The method for mixing the monomers is not particularly limited, and a conventionally known mixing method can be adopted.
また単量体組成物を共重合させる際の重合方法は、特に限定されるものではなく、従来公知の重合方法が採用され得る。例えば、溶液重合、分散重合、懸濁重合、乳化重合等の重合方法が使用できる。溶液重合法を用いて単量体組成物を重合させる場合に用いることができる溶媒としては、トルエン、キシレン、その他高沸点の芳香族系溶媒；酢酸ブチル、酢酸エチル、セロソルブアセテート等のエステル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；ジメチルホルムアミドなどが挙げられる。もちろん使用し得る溶媒がこれら溶媒に限定されるものではない。これら溶媒は一種のみを使用してもよいし、二種以上を混合して使用してもよい。なお、溶媒の使用量は生成物の濃度などを考慮し適宜定めればよい。 Moreover, the polymerization method at the time of copolymerizing a monomer composition is not specifically limited, A conventionally well-known polymerization method may be employ | adopted. For example, polymerization methods such as solution polymerization, dispersion polymerization, suspension polymerization, and emulsion polymerization can be used. Solvents that can be used when polymerizing the monomer composition using the solution polymerization method include toluene, xylene, and other high boiling aromatic solvents; ester solvents such as butyl acetate, ethyl acetate, and cellosolve acetate. Ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; dimethylformamide and the like. Of course, the solvent which can be used is not limited to these solvents. These solvents may be used alone or in combination of two or more. Note that the amount of the solvent used may be appropriately determined in consideration of the concentration of the product.
また単量体組成物を共重合させる際には重合開始剤を用いる。重合開始剤としては、たとえば２，２'−アゾビス−（２−メチルブチロニトリル）、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート、２，２'−アゾビスイソブチロニトリル、ベンゾイルパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサイド等の通常のラジカル重合開始剤が挙げられる。重合開始剤の使用量は、要求される重合体の特性値などから適宜決定されるべきものであり、特に限定はない。 A polymerization initiator is used when the monomer composition is copolymerized. Examples of the polymerization initiator include 2,2′-azobis- (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, benzoylper Usual radical polymerization initiators such as oxide and di-tert-butyl peroxide are exemplified. The amount of the polymerization initiator used should be appropriately determined from the required characteristic values of the polymer and is not particularly limited.
反応温度は、特に限定されるものではないが、室温〜２００℃の範囲が好ましく、４０〜１４０℃がより好ましい。なお反応時間は、用いる単量体組成物の組成や重合開始剤の種類などに応じて、重合反応が完結するように適宜設定すればよい。 Although reaction temperature is not specifically limited, The range of room temperature-200 degreeC is preferable, and 40-140 degreeC is more preferable. In addition, what is necessary is just to set reaction time suitably so that a polymerization reaction may be completed according to the composition of the monomer composition to be used, the kind of polymerization initiator, etc.
紫外線吸収性重合体の数平均分子量（Ｍｎ）は、特に限定されないが、２，０００〜５００，０００が好ましく、より好ましくは４，０００〜３００，０００であり、さらに好ましくは５，０００〜２００，０００である。なお数平均分子量は、ポリスチレン標準ＧＰＣで測定した値である。 The number average molecular weight (Mn) of the ultraviolet absorbing polymer is not particularly limited, but is preferably 2,000 to 500,000, more preferably 4,000 to 300,000, and still more preferably 5,000 to 200. , 000. The number average molecular weight is a value measured by polystyrene standard GPC.
次に紫外線吸収性重合体層の形成について説明する。生成された紫外線吸収性重合体を、必要により他の重合体と混合して紫外線吸収性重合体層組成物とし、プラスチックフィルム上に塗布する。当該組成物のプラスチックフィルムへの塗布は、浸漬、吹き付け、刷毛塗り、カーテンフローコータ、グラビアコート、ロールコート、スピンコート、バーコート、静電塗装などの方法により行うことができる。その後に塗布した紫外線吸収性重合体層を加熱したり、紫外線や電子線を照射して硬化させて最終成形物を得る。 Next, formation of the ultraviolet absorbing polymer layer will be described. The produced UV-absorbing polymer is mixed with other polymers as necessary to form an UV-absorbing polymer layer composition and applied onto a plastic film. The composition can be applied to the plastic film by dipping, spraying, brushing, curtain flow coater, gravure coating, roll coating, spin coating, bar coating, electrostatic coating, or the like. Thereafter, the applied UV-absorbing polymer layer is heated or irradiated with UV rays or an electron beam to be cured to obtain a final molded product.
ここで、生成された紫外線吸収性重合体が単独で硬化できない重合体の場合には、硬化剤を添加する必要がある。かかる硬化剤は、紫外線吸収性重合体に存在する硬化性官能基、例えば水酸基やアミノ基、カルボキシル基又はその無水物、エポキシ基、アミド基等と架橋硬化反応する官能基を１分子当たり２個以上含む化合物又はポリマーであって、紫外線吸収性重合体に存在する官能基の種類に応じて選択・使用される。例えば、紫外線吸収性重合体に存在する官能基がカルボキシル基又はその無水物である場合には、ポリイソシアネート化合物又はその変性物、アミノプラスト樹脂、エポキシ樹脂等の架橋硬化剤、当該官能基がエポキシ基である場合には、アミンやカルボン酸、アミド、Ｎ−メチロールアルキルエーテル等を含む化合物からなる架橋硬化剤、当該官能基が水酸基やアミノ基である場合には、ポリイソシアネート化合物又はその変性物、エポキシ樹脂、アミノプラスト樹脂等の架橋硬化剤を挙げることができる。これら硬化剤の中でも、活性水素を有する基との組み合わせにおいて、イソシアネート化合物、エポキシ樹脂、アミノプラスト樹脂が好ましい。 Here, in the case where the produced ultraviolet absorbing polymer is a polymer that cannot be cured alone, it is necessary to add a curing agent. Such a curing agent has two functional groups that crosslink and react with a curable functional group present in the UV-absorbing polymer, such as a hydroxyl group, an amino group, a carboxyl group or its anhydride, an epoxy group, an amide group, and the like per molecule. It is a compound or polymer containing above, and is selected and used according to the type of functional group present in the ultraviolet absorbing polymer. For example, when the functional group present in the UV-absorbing polymer is a carboxyl group or an anhydride thereof, a polyisocyanate compound or a modified product thereof, a crosslinking curing agent such as an aminoplast resin or an epoxy resin, and the functional group is an epoxy. In the case of a group, a crosslinking curing agent comprising a compound containing amine, carboxylic acid, amide, N-methylol alkyl ether, etc. And crosslinking curing agents such as epoxy resins and aminoplast resins. Among these curing agents, an isocyanate compound, an epoxy resin, and an aminoplast resin are preferable in combination with a group having active hydrogen.
これら架橋硬化剤は単独又は２種以上併用してもよい。架橋硬化剤の使用量は、架橋硬化剤の種類等によって適宜決定されるものであるが、一般的には紫外線吸収性重合体１００重量部に対して０．０１〜５０重量部の範囲が好ましい。また架橋反応を促進させるために架橋触媒を添加してもよい。かかる架橋触媒としては例えば、塩類や無機物質、有機物質、酸物質、アルカリ物質等が挙げられる。 These crosslinking curing agents may be used alone or in combination of two or more. The amount of the cross-linking curing agent is appropriately determined depending on the type of the cross-linking curing agent and the like, but is generally preferably in the range of 0.01 to 50 parts by weight with respect to 100 parts by weight of the ultraviolet absorbing polymer. . A crosslinking catalyst may be added to promote the crosslinking reaction. Examples of such a crosslinking catalyst include salts, inorganic substances, organic substances, acid substances, and alkaline substances.
また、紫外線吸収性重合体と混合される上記他の重合体としては、熱可塑性重合体又は単独あるいは架橋剤によって架橋硬化する熱硬化性重合体を使用することができる。本発明の紫外線吸収性複合フィルムの用途・要求される特性によって、当該重合体の種類・使用量を適宜決定すればよい。当該重合体としては、例えばポリ塩化ビニル樹脂、ポリエステル樹脂、アクリル樹脂、シリコン樹脂等の熱可塑性重合体；ウレタン樹脂、アミノプラスト樹脂、シリコン樹脂等の単独硬化する熱硬化性重合体；ポリエステル樹脂、アクリル樹脂等の硬化剤によって硬化する熱硬化性重合体を挙げることができる。 Moreover, as said other polymer mixed with an ultraviolet absorptive polymer, a thermoplastic polymer or the thermosetting polymer which bridge | crosslinks and hardens | cure by a crosslinking agent can be used. What is necessary is just to determine suitably the kind and usage-amount of the said polymer with the use and the characteristic requested | required of the ultraviolet-absorbing composite film of this invention. Examples of the polymer include thermoplastic polymers such as a polyvinyl chloride resin, a polyester resin, an acrylic resin, and a silicon resin; a thermosetting polymer that cures alone such as a urethane resin, an aminoplast resin, and a silicon resin; a polyester resin, The thermosetting polymer hardened | cured with hardening | curing agents, such as an acrylic resin, can be mentioned.
紫外線吸収性重合体層はその他に種々の添加剤を含んでもよい。添加剤としては、例えば、塗料などの層形成用組成物に一般に使用されるレベリング剤；黄鉛、モリブデートオレンジ、紺青、カドミウム系顔料、チタン白、複合酸化物顔料、透明酸化鉄、カーボンブラック、環式高級顔料、溶性アゾ顔料、銅フタロシアニン顔料、染付顔料、顔料中間体などの顔料；顔料分散剤；抗酸化剤；粘性改質剤；耐光安定剤；金属不活性化剤；過酸化物分解剤；充填剤；補強剤；可塑剤；潤滑剤；防食剤；防錆剤；蛍光性増白剤；有機・無機防炎剤；滴下防止剤；溶融流改質剤；静電防止剤などが挙げられる。 The ultraviolet absorbing polymer layer may further contain various additives. Examples of additives include leveling agents commonly used in layer forming compositions such as paints; yellow lead, molybdate orange, bitumen, cadmium pigments, titanium white, complex oxide pigments, transparent iron oxide, carbon black , Cyclic higher pigments, soluble azo pigments, copper phthalocyanine pigments, dyed pigments, pigment intermediates, etc .; pigment dispersants; antioxidants; viscosity modifiers; light stabilizers; metal deactivators; Decomposition agent; Filler; Reinforcing agent; Plasticizer; Lubricant; Anticorrosive agent; Rust inhibitor; Fluorescent whitening agent; Organic / inorganic flameproofing agent; Anti-dripping agent; Melt flow modifier; Etc.
紫外線吸収性重合体層が、加熱によって硬化される場合、硬化温度は架橋性官能基の種類や使用する硬化剤の種類によって異なるが、例えば室温〜２５０℃の温度で硬化するのか好ましい。 When the UV-absorbing polymer layer is cured by heating, the curing temperature varies depending on the type of the crosslinkable functional group and the type of the curing agent to be used, but is preferably cured at a temperature of room temperature to 250 ° C, for example.
紫外線照射によって硬化される場合、その硬化方法は、使用する光重合開始剤、紫外線を発生させる光源の種類、光源と塗布面との距離などの条件によっても異なってくるが、例えば波長１，０００〜８，０００オングストロームの紫外線を通常数秒間、長くとも数十秒間照射する方法を挙げることができる。 When cured by ultraviolet irradiation, the curing method varies depending on conditions such as the photopolymerization initiator used, the type of light source that generates ultraviolet light, the distance between the light source and the coating surface, and the wavelength is, for example, 1,000. A method of irradiating UV light of ˜8,000 angstrom usually for several seconds, at most tens of seconds can be mentioned.
電子線照射によって硬化される場合には、たとえば通常５０〜１０００ｋｅｖ、好ましくは１００〜３００ｋｅｖの加速電圧で、吸収線が１〜２０Ｍｒａｄ程度となるように電子線を照射する方法を挙げることができる。電子線照射は大気中で行ってもよいが、窒素などの不活性ガス中で行うのが好ましい。 In the case of curing by electron beam irradiation, for example, a method of irradiating an electron beam with an accelerating voltage of usually 50 to 1000 kev, preferably 100 to 300 kev so that the absorption line is about 1 to 20 Mrad can be mentioned. The electron beam irradiation may be performed in the air, but is preferably performed in an inert gas such as nitrogen.
また紫外線照射又は電子線照射後、必要に応じて加熱を行い、硬化を一層進行させてもよい。 Moreover, after ultraviolet irradiation or electron beam irradiation, heating may be performed as necessary to further cure.
紫外線吸収性重合体層の厚さは、１〜２００ミクロンが好ましく、より好ましくは２〜１００ミクロン、さらに好ましくは２〜５０ミクロンである。厚さが２００ミクロンより厚いと、塗工速度が遅くなり、またプラスチックフィルム本来の性能が低下することがある。他方厚さが１ミクロンより薄いと、プラスチックフィルム上への均一塗工が困難となり、また紫外線吸収能が不十分となることがある。 The thickness of the ultraviolet absorbing polymer layer is preferably 1 to 200 microns, more preferably 2 to 100 microns, and still more preferably 2 to 50 microns. If the thickness is greater than 200 microns, the coating speed becomes slow, and the original performance of the plastic film may deteriorate. On the other hand, if the thickness is less than 1 micron, uniform coating on the plastic film becomes difficult, and the ultraviolet absorbing ability may be insufficient.
以下、具体例によって本発明をさらに詳細に説明するが、本発明はこれらにより何ら限定されるものではない。なお特に断りのない限り、具体例に記載された「部」は重量部を、「％」は「重量％」を示すものとする。 Hereinafter, more detailed description of the present invention by specific examples, but the present invention should not be construed as being limited thereto. Unless otherwise specified, “parts” described in specific examples indicate parts by weight, and “%” indicates “% by weight”.
（紫外線吸収性重合体の合成）
（合成例１）
攪拌機、滴下口、温度計、冷却管および窒素ガス導入口を備えた５００ミリリットルのフラスコに溶媒としての酢酸ブチル１００部、滴下槽には２−[２'−ヒドロキシ−５'−（メタクリロイルオキシエチル）フェニル]−２Ｈ−ベンゾトリアゾール１０部、ブチルアクリレート３０部、２−ヒドロキシエチルメタクリレート１０部、メチルメタクリレート３０部、ブチルメタクリレート２０部、開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエート４部とを仕込む。滴下槽中の混合物の４０ｗｔ％をまずフラスコに加え、窒素ガスを導入し、撹拌しながら徐々に昇温して１２０℃まで加熱した。昇温後、滴下槽中の残りの混合物を４時間かけて滴下し、滴下後さらに２時間加熱して紫外線吸収性重合体の５０％溶液を得た。なお、この重合体の数平均分子量は５，７００であった。この紫外線吸収性重合体を重合体１とする。表１に単量体組成物の種類と配合量、及び得られた重合体の特性値を示す。
(Synthesis of UV-absorbing polymer)
(Synthesis Example 1)
A 500 ml flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 100 parts of butyl acetate as a solvent, and 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) in the dripping tank ) Phenyl] -2H-benzotriazole 10 parts, butyl acrylate 30 parts, 2-hydroxyethyl methacrylate 10 parts, methyl methacrylate 30 parts, butyl methacrylate 20 parts, t-butylperoxy-2-ethylhexanoate 4 as initiator Prepare the department. First, 40 wt% of the mixture in the dropping tank was added to the flask, nitrogen gas was introduced, the temperature was gradually raised while stirring, and the mixture was heated to 120 ° C. After the temperature rise, the remaining mixture in the dropping tank was dropped over 4 hours, and after the dropping, the mixture was further heated for 2 hours to obtain a 50% solution of an ultraviolet absorbing polymer. The number average molecular weight of this polymer was 5,700. This ultraviolet absorbing polymer is referred to as Polymer 1. Table 1 shows the types and blending amounts of the monomer compositions and the characteristic values of the obtained polymers.
（合成例２〜８）
表１に示す単量体組成物及び配合量で、合成例１と同様にして紫外線吸収性重合体を製造した。製造した重合体をそれぞれ重合体２〜８とする。
(Synthesis Examples 2 to 8)
A UV-absorbing polymer was produced in the same manner as in Synthesis Example 1 with the monomer composition and blending amount shown in Table 1. The produced polymers are referred to as polymers 2 to 8, respectively.
ＵＶＡ１：２−[２'−ヒドロキシ−５'−（メタクリロイルオキシエチル）フェニル]−２Ｈ−ベンゾトリアゾール
ＵＶＡ２：２−[２'−ヒドロキシ−５'−（β−メタクリロイルオキシエトキシ）−３'−ｔｅｒｔ−ブチルフェニル]−４−ｔｅｒｔ−ブチル−２Ｈ−ベンゾトリアゾール
ＨＡＬＳ１：４−メタクリロイルオキシ−２，２，６，６−テトラメチルピペリジン
ＨＡＬＳ２：１−メタクリロイル−４−メタクリロイルアミノ−２，２，６，６−テトラメチルピペリジン
ＣＨＭＡ：シクロヘキシルメタクリレートｎ−ＢＭＡ：ｎ−ブチルメタクリレート
ＢＡ：ブチルアクリレート
ＭＭＡ：メチルメタクリレート
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ＭＡＡ：メタクリル酸開始剤：ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート
UVA1: 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole UVA2: 2- [2′-hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-tert -Butylphenyl] -4-tert-butyl-2H-benzotriazole HALS1: 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine HALS2: 1-methacryloyl-4-methacryloylamino-2,2,6 6-tetramethylpiperidine CHMA: cyclohexyl methacrylate n-BMA: n-butyl methacrylate BA: butyl acrylate MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid initiator: tert-butylperoxy-2-ethylhexa Benzoate
（例１）
合成例１で得られた重合体溶液に、多官能イソシアネート（「スミジュールＮ−３２００」住友バイエルウレタン社製）を溶液中のヒドロキシル基に対するイソシアネート基の当量比が１：１となる量だけ秤取して混合した。さらに、得られた混合物にシンナーを添加して希釈し、混合物の粘度をグラビアコートが可能となる粘度に調整した。
(Example 1)
In the polymer solution obtained in Synthesis Example 1, a polyfunctional isocyanate (“Sumijour N-3200” manufactured by Sumitomo Bayer Urethane Co., Ltd.) is weighed in such an amount that the equivalent ratio of isocyanate groups to hydroxyl groups in the solution is 1: 1. And mixed. Furthermore, thinner was added to the obtained mixture to dilute it, and the viscosity of the mixture was adjusted to a viscosity that enables gravure coating.
コロナ放電処理により表面エネルギーが５０ｄｙｎ／ｃｍになるように処理を行った２軸配向ポリエチレンテレフタレートフィルム（「ルミラーＴ」東レ社製、厚さ１００ミクロン）の処理面に、粘度を調整した上記混合物をグラビアコーターを用いて塗布し、１００℃で２分間熱風乾燥し硬化を行った。その後３０℃雰囲気下で１週間放置した後、下記に示す物性評価を行った。結果を表３に示す。 On the treated surface of a biaxially oriented polyethylene terephthalate film ("Lumirror T" manufactured by Toray Industries, Inc., thickness 100 microns) treated so that the surface energy is 50 dyn / cm by corona discharge treatment, the above-mentioned mixture with adjusted viscosity is used. It apply | coated using the gravure coater and hardened by drying with hot air at 100 degreeC for 2 minute (s). Then, after being left for 1 week in a 30 ° C. atmosphere, the following physical properties were evaluated. The results are shown in Table 3.
（表面ぬれ指数）
ＪＩＳＫ−６７６８ぬれ試験方法に準拠して、ぬれ指数を判定した。
(Surface wetting index)
The wetting index was determined according to the JISK-6768 wetting test method.
（促進耐候性試験）
２７５ｎｍ以下の波長領域を遮断するフィルタを備えた超エネルギー照射試験装置（「ＵＥ−１ＤＥＣ型」スガ試験器社製）を用いて、ＵＶ照射強度が約１００ｍＷ／ｃｍ2、ブラックパネル温度が７０℃、湿度が５０％Ｒｈの状態を約１０時間保持する照射過程と、ブラックパネル温度が５０℃、湿度が９６％Ｒｈの状態を２時間保持する湿潤過程とを１サイクルとして、この照射・湿潤サイクルを１５サイクル繰り返した。
(Accelerated weather resistance test)
Using a super energy irradiation test apparatus (“UE-1DEC type” manufactured by Suga Test Instruments Co., Ltd.) equipped with a filter that cuts off a wavelength region of 275 nm or less, the UV irradiation intensity is about 100 mW / cm 2 , and the black panel temperature is 70 ° C. This irradiation / wetting cycle consists of an irradiation process in which the humidity is maintained at 50% Rh for about 10 hours and a wet process in which the black panel temperature is maintained at 50 ° C. and the humidity is maintained at 96% Rh for 2 hours. Was repeated 15 cycles.
この促進耐候性試験の前後におけるフィルムの密着性、外観、フィルムヘイズを下記条件で測定した。 The film adhesion, appearance, and film haze before and after the accelerated weathering test were measured under the following conditions.
（密着性）
紫外線吸収性重合体層上に「セロテープ（登録商標）ＣＴ４０５−２４」（ニチバン社製）を圧着させた後、セロテープ（登録商標）を１８０度反対方向に強制的に剥離し、剥離度合いを下記のように目視により観察した。
◎：剥離なし
○：わずかに点剥離
△：剥離面積が１０％未満
×：剥離面積が１０％以上
(Adhesion)
After “Cellotape (registered trademark) CT405-24” (manufactured by Nichiban Co., Ltd.) is pressure-bonded on the UV-absorbing polymer layer, the cellophane (registered trademark) is forcibly peeled 180 degrees in the opposite direction. Was observed visually.
◎: No peeling ○: Slight point peeling Δ: Peeling area is less than 10% ×: Peeling area is 10% or more
（外観）
紫外線吸収性複合フィルムの外観を目視により観察した。
(appearance)
The appearance of the ultraviolet absorbing composite film was visually observed.
（フィルムヘイズ）
ＪＩＳＫ７１０５に準拠して、日本電色工業社製の濁度計「ＮＤＨ−３００Ａ」を用いて測定した。
(Film haze)
Based on JISK7105, it measured using the turbidimeter "NDH-300A" by Nippon Denshoku Industries Co., Ltd.
（例２）
例１と同様にして、コロナ放電処理により表面エネルギーが４１ｄｙｎ／ｃｍになるように処理を行った無延伸ポリプロピレンフィルム（「Ｐ−１０１１」東洋紡社製、厚さ５０ミクロン）の処理面上に、表２に示す重合体を所定の塗工機を用いて塗布し紫外線吸収性複合フィルムを作成した。例１と同様にして試験を行った。試験結果を表３に示す。
(Example 2)
In the same manner as in Example 1 , on the treated surface of an unstretched polypropylene film ("P-1011" manufactured by Toyobo Co., Ltd., thickness 50 microns) treated so as to have a surface energy of 41 dyn / cm by corona discharge treatment, The polymers shown in Table 2 were applied using a predetermined coating machine to prepare an ultraviolet absorbing composite film. The test was conducted in the same manner as in Example 1 . The test results are shown in Table 3.
（例３〜５及び例７，８）
例１と同様にして、表２に示す重合体及びプラスチックフィルムを使用して所定の塗工機を用いて紫外線吸収性複合フィルムを作成した。例１と同様にして試験を行った。それぞれの試験結果を表３に示す。
(Examples 3 to 5 and Examples 7 and 8)
In the same manner as in Example 1 , a UV-absorbing composite film was prepared using a polymer and plastic film shown in Table 2 using a predetermined coating machine. The test was conducted in the same manner as in Example 1 . Table 3 shows the test results.
（例６）
合成例６で得られた重合体６の溶液にエポキシ樹脂（「デナコール ＥＸ６２２」）を、溶液中のカルボキシル基に対するエポキシ基の当量比が１：１となる量だけ秤量して混合し、コンマコーターを用いて紫外線吸収性複合フィルムを作成した。例１と同様にして試験を行った。試験結果を表３に示す。
(Example 6)
An epoxy resin (“ Denacol EX622”) was weighed and mixed in an amount of 1: 1 so that the equivalent ratio of the epoxy group to the carboxyl group in the solution was 1: 1 in the solution of the polymer 6 obtained in Synthesis Example 6. A UV-absorbing composite film was prepared using The test was conducted in the same manner as in Example 1 . The test results are shown in Table 3.
Claims (6)
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