JP2009079156A - Uv absorbing polymer composition - Google Patents
Uv absorbing polymer composition Download PDFInfo
- Publication number
- JP2009079156A JP2009079156A JP2007250193A JP2007250193A JP2009079156A JP 2009079156 A JP2009079156 A JP 2009079156A JP 2007250193 A JP2007250193 A JP 2007250193A JP 2007250193 A JP2007250193 A JP 2007250193A JP 2009079156 A JP2009079156 A JP 2009079156A
- Authority
- JP
- Japan
- Prior art keywords
- group
- ultraviolet
- monomer
- absorbing polymer
- ultraviolet absorbing
- 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.)
- Withdrawn
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- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 101
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- 239000011347 resin Substances 0.000 claims abstract description 30
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000012964 benzotriazole Substances 0.000 claims description 10
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- 125000003545 alkoxy group Chemical group 0.000 description 5
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- RFWYJPXOKLPVND-UHFFFAOYSA-N (2-ethoxyphenyl)-phenylmethanone Chemical compound CCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 RFWYJPXOKLPVND-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
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- 238000004383 yellowing Methods 0.000 description 3
- FISZAKVDTCHVGC-UHFFFAOYSA-N (2-butoxyphenyl)-phenylmethanone Chemical compound CCCCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 FISZAKVDTCHVGC-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical group CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 2
- 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 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
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- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
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- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 2
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
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- 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 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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Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
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Abstract
Description
本発明は、可塑剤が含まれている樹脂製のフィルム、板等の成形体等に耐候性を付与するために形成される紫外線吸収層用の一液型紫外線吸収性ポリマー組成物に関するものであり、特に、耐可塑剤移行性や耐指紋性に優れる紫外線吸収層を形成することのできる紫外線吸収性ポリマー組成物に関するものである。 The present invention relates to a one-pack type UV-absorbing polymer composition for an UV-absorbing layer formed for imparting weather resistance to a molded body such as a resin film or plate containing a plasticizer. In particular, the present invention relates to an ultraviolet-absorbing polymer composition capable of forming an ultraviolet-absorbing layer excellent in plasticizer migration resistance and fingerprint resistance.
ポリ塩化ビニルは、燃焼によって腐食性の塩化水素ガスを発するという短所はあるものの、透明性、強度、防湿性、耐薬品性、電気絶縁性等の各種特性に優れているため、依然として国内プラスチック生産量が第３位と上位にある。ポリ塩化ビニルは、農業用シートや、電線被覆材料等、紫外線による劣化を受けやすい屋外での用途も多い。 Although polyvinyl chloride has the disadvantage of generating corrosive hydrogen chloride gas by combustion, it still has excellent plastic properties such as transparency, strength, moisture resistance, chemical resistance, and electrical insulation. The amount is third and higher. Polyvinyl chloride is often used outdoors such as agricultural sheets and wire coating materials that are susceptible to deterioration by ultraviolet rays.
一般的に、プラスチックの紫外線劣化を防止するには、プラスチックの表面に紫外線を吸収することのできる皮膜（紫外線吸収層）を設ければよいことが知られている（例えば、特許文献１、特許文献２）が、ポリ塩化ビニルには、無可塑タイプを除き、可塑剤が含まれていることから、紫外線吸収層をポリ塩化ビニル製成形体表面に設けると、紫外線吸収層内へ可塑剤が移行して来て、ポリ塩化ビニル製成形体が脆くなってしまうという問題があった。また、紫外線吸収層がポリ塩化ビニル製成形体表面に設けられていない場合でも、紫外線吸収層を有する部材とポリ塩化ビニル製成形体が接したときに、紫外線吸収層内へ可塑剤が移行して、両者が融着して容易に剥がすことができなくなるといった不具合が発生していた。 In general, it is known that a plastic film (ultraviolet absorption layer) capable of absorbing ultraviolet light may be provided on the surface of the plastic in order to prevent the ultraviolet deterioration of the plastic (for example, Patent Document 1, Patent Reference 2) shows that polyvinyl chloride contains a plasticizer except for the non-plastic type. Therefore, when an ultraviolet absorbing layer is provided on the surface of a molded article made of polyvinyl chloride, the plasticizer is introduced into the ultraviolet absorbing layer. There has been a problem in that the molded product made of polyvinyl chloride becomes brittle. Even when the ultraviolet absorbing layer is not provided on the surface of the molded article made of polyvinyl chloride, the plasticizer migrates into the ultraviolet absorbing layer when the member having the ultraviolet absorbing layer comes into contact with the molded article made of polyvinyl chloride. As a result, there has been a problem that both of them are fused and cannot be easily peeled off.
また、一方で、紫外線吸収層ではないが、特定組成のアクリル系粘着剤に可塑剤を配合し、さらにイソシアネートで架橋することにより、ポリ塩化ビニル基材から粘着剤層への可塑剤の移行を抑制する技術が開発されている（特許文献３）。 On the other hand, although it is not an ultraviolet absorbing layer, the plasticizer can be transferred from the polyvinyl chloride base material to the adhesive layer by blending with a specific composition acrylic adhesive and further crosslinking with isocyanate. The technique to suppress is developed (patent document 3).
しかし、紫外線吸収層を形成するための塗工液に架橋剤を配合した後は、貯蔵安定性に乏しいため、直ぐに塗工しなければならず、何らかの原因で製造ラインが止まったりすると、塗工液を廃棄しなければならなくなる。また、架橋剤で架橋するには、製造設備として加熱炉が必要となる。さらに長時間の養生も必要となるため、生産コスト・生産効率的に望ましくない。
上記特許文献２には、農業用塩化ビニル系樹脂フィルムの片面に紫外線吸収層を設けることが記載されているが、可塑剤の移行の問題については何ら触れられていない。また、特許文献３の技術では、上記したように、生産コスト・生産効率的に好ましくない。 Patent Document 2 describes that an ultraviolet absorbing layer is provided on one side of an agricultural vinyl chloride resin film, but does not mention any problem of plasticizer migration. Further, the technique of Patent Document 3 is not preferable in terms of production cost and production efficiency as described above.
そこで本発明では、可塑剤を含む樹脂製のフィルムや板等の成形体に別体の紫外線吸収層を接触させる場合や、前記成形体表面に紫外線吸収層を設ける場合を考慮して、架橋剤で架橋することなく、耐候性はもとより、耐可塑剤移行性に優れ、塗膜としての諸特性（耐指紋性、耐ブロッキング性）も良好な紫外線吸収層を形成し得る紫外線吸収性ポリマー組成物の提供を課題とした。 Therefore, in the present invention, in consideration of a case where a separate ultraviolet absorbing layer is brought into contact with a molded body such as a resin film or plate containing a plasticizer, or a case where an ultraviolet absorbing layer is provided on the surface of the molded body, a crosslinking agent is considered. UV-absorbing polymer composition capable of forming an ultraviolet-absorbing layer that is excellent in weather resistance, plasticizer transfer resistance and various properties as a coating film (fingerprint resistance and blocking resistance) without crosslinking Was the issue.
本発明は、樹脂成形体表面に紫外線吸収層を形成するために用いられる紫外線吸収性ポリマー組成物であって、
（Ａ）紫外線吸収性モノマー２０〜５０質量％、
（Ｂ）アクリル酸、メタクリル酸、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレートおよび２−ヒドロキシプロピルメタクリレートよりなる群から選択される１種以上の親水性モノマー３０〜７０質量％、
（Ｃ）その他のモノマー０〜５０質量％、
からなるモノマー混合物から合成される紫外線吸収性ポリマーを含むところに特徴がある。
The present invention is an ultraviolet absorbing polymer composition used to form an ultraviolet absorbing layer on the surface of a resin molded body,
(A) 20-50% by mass of an ultraviolet absorbing monomer,
(B) One or more hydrophilic monomers selected from the group consisting of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate 30 to 70 mass %,
(C) 0-50 mass% of other monomers,
It is characterized in that it contains a UV-absorbing polymer synthesized from a monomer mixture consisting of
上記その他のモノマー（Ｃ）が炭素数２以下のアルキル基を有するアルキル（メタ）アクリレートを含む態様、紫外線吸収性ポリマーのＴｇが５０℃以上１００℃未満である態様、上記親水性モノマー（Ｂ）が、２−ヒドロキシエチルメタクリレートおよび／または２−ヒドロキシプロピルメタクリレートである態様、上記紫外線吸収性モノマー（Ａ）が、ベンゾトリアゾール系紫外線吸収性モノマーを含む態様は、いずれも本発明の好ましい実施態様である。 An embodiment in which the other monomer (C) includes an alkyl (meth) acrylate having an alkyl group having 2 or less carbon atoms, an embodiment in which the Tg of the UV-absorbing polymer is 50 ° C. or more and less than 100 ° C., the hydrophilic monomer (B) Is a preferred embodiment of the present invention, and the embodiment in which the UV-absorbing monomer (A) contains a benzotriazole-based UV-absorbing monomer is a 2-hydroxyethyl methacrylate and / or 2-hydroxypropyl methacrylate. is there.
本発明には、一液型紫外線吸収性ポリマー組成物を樹脂成形体表面に塗布することにより紫外線吸収層を積層した紫外線吸収性積層体も含まれる。 The present invention also includes an ultraviolet-absorbing laminate in which an ultraviolet-absorbing layer is laminated by applying a one-component ultraviolet-absorbing polymer composition to the surface of a resin molded body.
本発明の一液型紫外線吸収性ポリマー組成物は、架橋剤を用いずとも、耐可塑剤移行性に優れ、塗膜としての諸特性（耐指紋性、耐ブロッキング性）も良好な紫外線吸収層を形成することができた。従って、樹脂成形体表面、例えば、ポリ塩化ビニル樹脂製の農業用フィルムや電線被覆層等の表面に、良好な特性の紫外線吸収層を形成することが可能となった。 The one-pack type UV-absorbing polymer composition of the present invention has an excellent plasticizer transfer property without using a cross-linking agent, and has various properties (fingerprint resistance and blocking resistance) as a coating film. Could be formed. Accordingly, it has become possible to form an ultraviolet absorbing layer having good characteristics on the surface of a resin molded body, for example, the surface of an agricultural film made of polyvinyl chloride resin, a wire coating layer, or the like.
本発明は、一液型紫外線吸収性ポリマー組成物に関する。ここで、「一液型」とは、架橋剤を配合せずに、紫外線吸収層を形成するために用いられるという意味である。 The present invention relates to a one-component ultraviolet absorbing polymer composition. Here, “one-pack type” means that it is used to form an ultraviolet absorbing layer without blending a crosslinking agent.
本発明の一液型紫外線吸収性ポリマー組成物の主成分である紫外線吸収性ポリマーは、 （Ａ）紫外線吸収性モノマー２０〜５０質量％、
（Ｂ）アクリル酸、メタクリル酸、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレートおよび２−ヒドロキシプロピルメタクリレートよりなる群から選択される１種以上の親水性モノマー３０〜７０質量％、
（Ｃ）その他のモノマー０〜５０質量％、
からなるモノマー混合物から合成される。
The UV-absorbing polymer as the main component of the one-pack type UV-absorbing polymer composition of the present invention is: (A) 20-50% by mass of UV-absorbing monomer,
(B) One or more hydrophilic monomers selected from the group consisting of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate 30 to 70 mass %,
(C) 0-50 mass% of other monomers,
From a monomer mixture consisting of
紫外線吸収性モノマー（Ａ）は、紫外線吸収性基を有し、耐候性を確保するために必要なモノマーである。紫外線吸収性モノマー（Ａ）としては、下記式（１）で示されるベンゾトリアゾール系モノマーが好適例として挙げられる。 The ultraviolet absorbing monomer (A) is a monomer having an ultraviolet absorbing group and necessary for ensuring weather resistance. Preferred examples of the ultraviolet absorbing monomer (A) include benzotriazole monomers represented by the following formula (1).
上記ハロゲン原子とは、フッ素、塩素、臭素、ヨウ素のいずれかを表す。炭素数１〜８のアルキル基の具体例としては、例えば、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、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖式アルキル基；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、シクロオクチル基等の脂環式アルキル基；フェニル基、トリル基、キシリル基、ベンジル基、フェネチル基等の芳香族アルキル基；等を挙げることができる。炭素数１〜６のアルコキシ基とは、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基である。 The halogen atom represents any of fluorine, chlorine, bromine and iodine. Specific examples of the alkyl group having 1 to 8 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group. A chain alkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc .; aromatic group such as phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group, etc. An alkyl group; and the like. A C1-C6 alkoxy group is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Ｒ2で表される炭素数１〜６のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基等の直鎖状アルキレン基；イソプロピレン基、イソブチレン基、ｓｅｃ−ブチレン基、ｔ−ブチレン基、イソペンチレン基、ネオペンチレン基等の分枝鎖状アルキレン基；等を挙げることができる。 Examples of the alkylene group having 1 to 6 carbon atoms represented by R 2 include linear alkylene groups such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group; an isopropylene group and an isobutylene group. , Sec-butylene group, t-butylene group, isopentylene group, neopentylene group, and the like;
上記式（１）で表される化合物の具体例として、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−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等を挙げることができる。これらのモノマーは、単独で用いても２種以上を併用してもよい。 Specific examples of the compound represented by the above formula (1) include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5′- (Methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′- Hydroxy-5'-tert-butyl-3 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-chloro-2H- Benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl]- - it can be exemplified methoxy -2H- benzotriazole. These monomers may be used alone or in combination of two or more.
紫外線吸収性モノマーとして、下記式（２）で示されるベンゾフェノン系モノマーを用いてもよい。 As the ultraviolet absorbing monomer, a benzophenone monomer represented by the following formula (2) may be used.
上記式（２）において、炭素数１〜１０のアルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、デカメチレン基等を挙げることができる。炭素数１〜６のアルキレン基が好ましい。また、炭素数１〜１０のオキシアルキレン基としては、例えば、オキシメチレン基、オキシエチレン基、オキシプロピレン基等を挙げることができる。 In the above formula (2), examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group. Etc. An alkylene group having 1 to 6 carbon atoms is preferred. Examples of the oxyalkylene group having 1 to 10 carbon atoms include an oxymethylene group, an oxyethylene group, and an oxypropylene group.
ベンゾフェノン系モノマーの好ましい具体例としては、２−ヒドロキシ−４−(メタ)アクロイルオキシベンゾフェノン、２−ヒドロキシ−４−[２−(メタ)アクリロイルオキシ]エトキシベンゾフェノン、２−ヒドロキシ−４−[２−(メタ)アクリロイルオキシ]ブトキシベンゾフェノン、２，２'−ジヒドロキシ−４−[２−(メタ)アクリロイルオキシ]エトキシベンゾフェノン、２−ヒドロキシ−４−[２−(メタ)アクリロイルオキシ]エトキシ−４'−(２−ヒドロキシエトキシ)ベンゾフェノン、２−ヒドロキシ−３−ｔｅｒｔ−ブチル−４−[２−(メタ)アクリロイルオキシ]エトキシベンゾフェノン、２−ヒドロキシ−３−ｔｅｒｔ−ブチル−４−[２−(メタ)アクリロイルオキシ]ブトキシベンゾフェノン等を挙げることができる。これらのモノマーは、単独で用いても２種以上を併用してもよい。 Preferable specific examples of the benzophenone monomer include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2 -(Meth) acryloyloxy] butoxybenzophenone, 2,2'-dihydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxy-4 ' -(2-hydroxyethoxy) benzophenone, 2-hydroxy-3-tert-butyl-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-3-tert-butyl-4- [2- (meta ) Acryloyloxy] butoxybenzophenone and the like. These monomers may be used alone or in combination of two or more.
また、下記式（３）で表されるトリアジン系紫外線吸収性モノマーを用いてもよい。 Further, a triazine ultraviolet absorbing monomer represented by the following formula (3) may be used.
（式中、Ｒ10〜Ｒ17はそれぞれ独立して、水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、または炭素数１〜１０のアルコキシ基を表し、Ｒ18は水素原子またはメチル基を表し、Ｘ2は、−(ＣＨ2ＣＨ2Ｏ)n−、−ＣＨ2ＣＨ（ＯＨ）−ＣＨ2Ｏ−、−(ＣＨ2)p−Ｏ−、−ＣＨ2ＣＨ（ＣＨ2ＯＲ19)−Ｏ−、−ＣＨ2ＣＨ（Ｒ19)−Ｏ−、または、−ＣＨ2(ＣＨ2)qＣＯＯ−Ｘ3−Ｏ−を表し、Ｒ19は炭素数１〜１０のアルキル基を表し、Ｘ3は、メチレン基、エチレン基、または、−ＣＨ2ＣＨ（ＯＨ）−ＣＨ2−を表し、ｐは１〜２０の整数を表し、ｑは０または１を表す。） (Wherein R 10 to R 17 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R 18 Represents a hydrogen atom or a methyl group, and X 2 represents — (CH 2 CH 2 O) n —, —CH 2 CH (OH) —CH 2 O—, — (CH 2 ) p —O—, —CH 2. CH (CH 2 OR 19 ) —O—, —CH 2 CH (R 19 ) —O—, or —CH 2 (CH 2 ) q COO—X 3 —O—, wherein R 19 represents 1 to 1 carbon atoms 10 represents an alkyl group, X 3 represents a methylene group, an ethylene group, or —CH 2 CH (OH) —CH 2 —, p represents an integer of 1 to 20, and q represents 0 or 1 .)
トリアジン系モノマーの具体例としては、２，４−ジフェニル−６−［２−ヒドロキシ−４−（２−アクリロイルオキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２−メチルフェニル）−６−［２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２−メトキシフェニル）−６−［２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２−エチルフェニル）−６−［２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２−エトキシフェニル）−６−［２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ジフェニル−６−［２−ヒドロキシ−４−（２−メタクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２−メチルフェニル）−６−［２−ヒドロキシ−４−（２−メタクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２−メトキシフェニル）−６−［２−ヒドロキシ−４−（２−メタクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２−エチルフェニル）−６−［２−ヒドロキシ−４−（２−メタクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２−エトキシフェニル）−６−［２−ヒドロキシ−４−（２−メタクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２，４−ジメトキシフェニル）−６−［２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２，４−ジメチルフェニル）−６−［２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２，４−ジエトキシフェニル）−６−［２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２，４−ジエチルフェニル）−６−［２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル］−１，３，５−トリアジン、２−［２−ヒドロキシ−４−（１１−アクリロイルオキシ−ウンデシルオキシ）フェニル］−４，６−ジフェニル−１，３，５−トリアジン、２−［２−ヒドロキシ−４−（１１−メタクリロイルオキシ−ウンデシルオキシ）フェニル］−４，６−ジフェニル−１，３，５−トリアジン、２−［２−ヒドロキシ−４−（２−メタクリロイルオキシエトキシ）フェニル］−４，６−ジフェニル−１，３，５−トリアジン、２−［２−ヒドロキシ−４−（１１−アクリロイルオキシ−ウンデシルオキシ）フェニル］−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン、２，４−ビス（２，４−ジメチルフェニル）−６−［２−ヒドロキシ−４−（１１−メタクロイルオキシウンデシルオキシ）フェニル］−１，３，５−トリアジン、２，４−ビス（２，４−ジメチルフェニル）−６−［２−ヒドロキシ−４−（２−メタクロイルオキシエトキシ）フェニル］−１，３，５−トリアジン等を挙げることができる。これらのモノマーは、単独で用いても２種以上を併用してもよい。 Specific examples of the triazine monomer include 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxy) phenyl] -1,3,5-triazine, 2,4-bis (2-methyl). Phenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4 -(2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl]- 1,3,5-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5- Liazine, 2,4-diphenyl-6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-methylphenyl) -6- [ 2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-methacryloyloxy) Ethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1,3,5- Triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1,3,5-triazi 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2, 4-Dimethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2,4-diethoxyphenyl) -6 [2-Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- (2 -Acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2- [2-hydroxy-4- (11-acryloyloxy-undecyloxy) phenyl] -4,6-diphenyl-1, 3,5-triazine, 2- [2-hydroxy-4- (11-methacryloyloxy-undecyloxy) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4 -(2-Methacryloyloxyethoxy) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (11-acryloyloxy-undecyloxy) phenyl] -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (11-methacryloyloxyundecyl) Oxy) phenyl] -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy) Phenyl] -1,3,5-triazine and the like. These monomers may be used alone or in combination of two or more.
前記ベンゾトリアゾール系紫外線吸収性モノマーとは異なる構造の下記ベンゾトリアゾール系モノマー（４）も好適に用いることができる。 The following benzotriazole monomer (4) having a structure different from that of the benzotriazole UV-absorbing monomer can also be suitably used.
上記において、水素結合を形成し得る元素を有する基としては、例えば、−ＮＨ−、−ＣＨ2ＮＨ−、−ＯＣＨ2ＣＨ（ＯＨ）ＣＨ2Ｏ−、−ＣＨ2ＣＨ2ＣＯＯＣＨ2ＣＨ（ＯＨ）ＣＨ2Ｏ−等を挙げることができる。これらの基のうち、活性水素を有する窒素原子が含まれている点で、−ＮＨ−、−ＣＨ2ＮＨ−が好適であり、−ＣＨ2ＮＨ−が特に好適である。 In the above, examples of the group having an element that can form a hydrogen bond include —NH—, —CH 2 NH—, —OCH 2 CH (OH) CH 2 O—, —CH 2 CH 2 COOCH 2 CH (OH ) CH 2 O— and the like. Among these groups, in that they contain a nitrogen atom having an active hydrogen, -NH -, - CH 2 NH- are preferred, -CH 2 NH- is particularly preferred.
上記において、炭素数１〜１２のアルキル基としては、例えば、上記炭素数１〜８のアルキル基として列挙した上記の置換基に加えて、ノニル基、デシル基、ウンデシル基、ドデシル基等の直鎖状または分枝状アルキル基；フェニル基、トリル基、キシリル基、ベンジル基、フェネチル基等の芳香族アルキル基；等を挙げることができる。これらの置換基のうち、炭素数４〜１２の直鎖状または分岐状アルキル基が好適であり、１，１，３，３−テトラメチルブチル基等の嵩高い分岐状アルキル基（またはこれらを有している基）が特に好適である。 In the above, the alkyl group having 1 to 12 carbon atoms includes, for example, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and the like in addition to the above-described substituents listed as the alkyl group having 1 to 8 carbon atoms. A chain or branched alkyl group; an aromatic alkyl group such as phenyl group, tolyl group, xylyl group, benzyl group, and phenethyl group; Among these substituents, a linear or branched alkyl group having 4 to 12 carbon atoms is preferable, and a bulky branched alkyl group such as 1,1,3,3-tetramethylbutyl group (or the like). Particularly preferred are groups having
上記式（４）で表されるベンゾトリアゾール系モノマーの具体例としては、２−［２’−ヒドロキシ−３’−（メタ）アクリロイルアミノフェニル］−２Ｈ−ベンゾトリアゾール、２−［２’−ヒドロキシ−３’−（メタ）アクリロイルアミノメチルフェニル］−２Ｈ−ベンゾトリアゾール、２−［２’−ヒドロキシ−３’−（メタ）アクリロイルアミノ−５’−（１，１，３，３−テトラメチルブチル）フェニル］−２Ｈ−ベンゾトリアゾール、２−［２’−ヒドロキシ−３’−（メタ）アクリロイルアミノメチル−５’−（１，１，３，３−テトラメチルブチル）フェニル］−２Ｈ−ベンゾトリアゾール等を挙げることができる。これらのモノマーは、単独で用いても２種以上を併用してもよい。 Specific examples of the benzotriazole monomer represented by the above formula (4) include 2- [2′-hydroxy-3 ′-(meth) acryloylaminophenyl] -2H-benzotriazole, 2- [2′-hydroxy. -3 ′-(meth) acryloylaminomethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′-(meth) acryloylamino-5 ′-(1,1,3,3-tetramethylbutyl) ) Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′-(meth) acryloylaminomethyl-5 ′-(1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole Etc. These monomers may be used alone or in combination of two or more.
なお、これらのモノマーのうち、嵩高い置換基Ｒ22が５位に結合している、２−［２’−ヒドロキシ−３’−（メタ）アクリロイルアミノ−５’−（１，１，３，３−テトラメチルブチル）フェニル］−２Ｈ−ベンゾトリアゾール、および、２−［２’−ヒドロキシ−３’−（メタ）アクリロイルアミノメチル−５’−（１，１，３，３−テトラメチルブチル）フェニル］−２Ｈ−ベンゾトリアゾールが好適である。 Among these monomers, 2- [2′-hydroxy-3 ′-(meth) acryloylamino-5 ′-(1,1,3,3) having a bulky substituent R 22 bonded to the 5-position. 3-tetramethylbutyl) phenyl] -2H-benzotriazole and 2- [2′-hydroxy-3 ′-(meth) acryloylaminomethyl-5 ′-(1,1,3,3-tetramethylbutyl) Phenyl] -2H-benzotriazole is preferred.
上記式（１）または（４）で示されるベンゾトリアゾール系モノマーは、例えば、対応するベンゾトリアゾール（紫外線吸収剤として市販されている）に（メタ）アクリル酸クロライドやＮ−メチロールアクリルアミドまたはそのアルキルエーテルを反応させる等の方法で合成することができる。例えば、２−［２’−ヒドロキシ−３’−メタクリロイルアミノ−５’−（１，１，３，３−テトラメチルブチル）フェニル］−２Ｈ−ベンゾトリアゾールは、２−［２’−ヒドロキシ−３’−アミノ−５’−（１，１，３，３−テトラメチルブチル）フェニル］−ベンゾトリアゾールとメタクリル酸クロライドを反応させて得ることができる。また、２−［２’−ヒドロキシ−３’−メタクリロイルアミノメチル−５’−（１，１，３，３−テトラメチルブチル）フェニル］−２Ｈ−ベンゾトリアゾールは、２−［２’−ヒドロキシ−５’−（１，１，３，３−テトラメチルブチル）フェニル］−ベンゾトリアゾール（例えば、ＣＹＡＳＯＲＢ（登録商標）ＵＶ−５４１１、ＣＹＴＥＣ社製）にＮ−メチロールアクリルアミド（例えば、日東化学工業株式会社製等）を反応させて得ることができる。 The benzotriazole monomer represented by the above formula (1) or (4) is, for example, a corresponding benzotriazole (commercially available as an ultraviolet absorber), (meth) acrylic acid chloride, N-methylolacrylamide or an alkyl ether thereof. It can synthesize | combine by methods, such as making it react. For example, 2- [2′-hydroxy-3′-methacryloylamino-5 ′-(1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole is 2- [2′-hydroxy-3 It can be obtained by reacting '-amino-5'-(1,1,3,3-tetramethylbutyl) phenyl] -benzotriazole with methacrylic acid chloride. Further, 2- [2′-hydroxy-3′-methacryloylaminomethyl-5 ′-(1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole is 2- [2′-hydroxy- 5 ′-(1,1,3,3-tetramethylbutyl) phenyl] -benzotriazole (for example, CYASORB (registered trademark) UV-5411, manufactured by CYTEC) and N-methylolacrylamide (for example, Nitto Chemical Industries, Ltd.) Etc.) can be obtained by reaction.
上記の紫外線吸収性モノマーは、紫外線吸収性ポリマーの原料であるモノマー混合物１００質量％中、２０〜５０質量％の範囲で用いる。紫外線吸収性モノマーを多く用いるほど得られるポリマーの紫外線吸収能は高くなるが、紫外線吸収性モノマーは常温（２５℃）で固体状であり、そもそも溶媒に溶けにくいため、５０質量％を超えて用いようとすると、溶液重合の際の溶媒量を多くせざるを得ず、塗工に適した粘度にするのに煩雑な処理が必要となる。また、紫外線吸収性モノマーは疎水性が高いため、親水性モノマーの使用で紫外線吸収層を親水性にして耐可塑剤移行性を高める、という本発明の効果を阻害する。紫外線吸収性モノマー量が上記範囲であれば、好適な不揮発分濃度で溶液重合を行うことができ、しかも、薄膜でも充分な耐候性を確保することができる。より好ましい下限は２５質量％、より好ましい上限は４５質量％である。 Said ultraviolet-absorbing monomer is used in 20-50 mass% in 100 mass% of monomer mixtures which are the raw materials of an ultraviolet-absorbing polymer. The more the UV-absorbing monomer is used, the higher the UV-absorbing ability of the polymer obtained. However, the UV-absorbing monomer is solid at room temperature (25 ° C) and is hardly soluble in the solvent. If it tries to do so, the amount of the solvent at the time of solution polymerization must be increased, and complicated processing is required to obtain a viscosity suitable for coating. In addition, since the ultraviolet absorbing monomer has high hydrophobicity, the use of the hydrophilic monomer inhibits the effect of the present invention that the ultraviolet absorbing layer is made hydrophilic and the plasticizer migration resistance is improved. If the amount of the UV-absorbing monomer is within the above range, solution polymerization can be performed at a suitable nonvolatile concentration, and sufficient weather resistance can be ensured even with a thin film. A more preferable lower limit is 25% by mass, and a more preferable upper limit is 45% by mass.
本発明の紫外線吸収性ポリマーは、紫外線吸収性モノマー（Ａ）の他に、親水性モノマー（Ｂ）を必須構成モノマーとする。 The ultraviolet absorbing polymer of the present invention comprises a hydrophilic monomer (B) as an essential constituent monomer in addition to the ultraviolet absorbing monomer (A).
本発明で用い得る親水性モノマー（Ｂ）は、アクリル酸、メタクリル酸、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレートおよび２−ヒドロキシプロピルメタクリレートよりなる群から選択される１種以上のモノマーである。親水性モノマー（Ｂ）は紫外線吸収層の親水性を高めるため、可塑剤を含む樹脂製成形体から疎水性の可塑剤が紫外線吸収層へ移行してくるのを有効に抑制する。また、上記６種類のモノマーは、それぞれのホモポリマーのＴｇが比較的高いため、得られる紫外線吸収性ポリマーのＴｇを後述する好適範囲に調整するのに好適である。耐可塑剤移行性や耐指紋性の観点からは、２−ヒドロキシエチルメタクリレートと２−ヒドロキシプロピルメタクリレートが好ましい。なお、親水性モノマーとしては、側鎖にオキシアルキレン鎖を有する、例えば、アルコキシポリエチレングリコール（メタ）アクリレート等の側鎖の長い親水性モノマーも知られているが、耐可塑剤移行性を確保できる量を共重合すると得られる紫外線吸収性ポリマーのＴｇがかなり低くなるため、耐可塑剤移行性、耐指紋性、耐ブロッキング性等の各特性が劣化し、本発明には好適でない。 The hydrophilic monomer (B) that can be used in the present invention is 1 selected from the group consisting of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. More than a species of monomer. Since the hydrophilic monomer (B) increases the hydrophilicity of the ultraviolet absorbing layer, it effectively suppresses the transfer of the hydrophobic plasticizer from the resin molded body containing the plasticizer to the ultraviolet absorbing layer. In addition, the above six types of monomers are suitable for adjusting the Tg of the obtained UV-absorbing polymer to a suitable range described later, because each homopolymer has a relatively high Tg. From the viewpoint of plasticizer migration resistance and fingerprint resistance, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are preferred. In addition, as the hydrophilic monomer, a hydrophilic monomer having a side chain having an oxyalkylene chain and having a long side chain such as alkoxy polyethylene glycol (meth) acrylate is also known, but the plasticizer migration resistance can be secured. When the amount is copolymerized, the UV-absorbing polymer obtained has a considerably low Tg, so that the properties such as plasticizer transfer resistance, fingerprint resistance, and blocking resistance are deteriorated, which is not suitable for the present invention.
上記親水性モノマー（Ｂ）は、紫外線吸収性ポリマーの原料であるモノマー混合物１００質量％中、３０〜７０質量％の範囲で用いる。３０質量％より少ないと、耐可塑剤移行性や耐指紋性が発現しない。７０質量％を超えても、耐可塑剤移行性が低下する。また、紫外線吸収層が吸湿し易くなって耐ブロッキング性が低下するため好ましくない。より好ましい親水性モノマー（Ｂ）の量の下限は４０質量％であり、上限は６０質量％である。 The said hydrophilic monomer (B) is used in 30-70 mass% in 100 mass% of monomer mixtures which are the raw materials of an ultraviolet absorptive polymer. When it is less than 30% by mass, the plasticizer migration resistance and the fingerprint resistance are not exhibited. Even if it exceeds 70% by mass, the plasticizer migration resistance decreases. Moreover, since an ultraviolet absorption layer becomes easy to absorb moisture and blocking resistance falls, it is unpreferable. The minimum of the quantity of a more preferable hydrophilic monomer (B) is 40 mass%, and an upper limit is 60 mass%.
本発明の紫外線吸収性ポリマーの原料モノマー混合物には、紫外線吸収性モノマー（Ａ）と親水性モノマー（Ｂ）以外の、その他のモノマー（Ｃ）が含まれていてもよい。このその他のモノマー（Ｃ）としては、紫外線吸収性モノマー（Ａ）および親水性モノマー（Ｂ）との共重合が可能なモノマーであれば特に限定されないが、耐候性に優れたポリマーを合成することができ、紫外線吸収性モノマー（Ａ）との共重合性が良好な（メタ）アクリレート類が好ましい。より好ましいのは、炭素数２以下のアルキル基を有するアルキル（メタ）アクリレートである。具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート等である。紫外線吸収性ポリマーのＴｇや紫外線吸収層の物性を考慮すると、メチルメタクリレート、エチルメタクリレート等が好ましい。 In the raw material monomer mixture of the ultraviolet absorbing polymer of the present invention, other monomers (C) other than the ultraviolet absorbing monomer (A) and the hydrophilic monomer (B) may be contained. The other monomer (C) is not particularly limited as long as it is a monomer that can be copolymerized with the ultraviolet absorbing monomer (A) and the hydrophilic monomer (B), but a polymer excellent in weather resistance is synthesized. (Meth) acrylates having good copolymerizability with the ultraviolet absorbing monomer (A) are preferable. More preferred is an alkyl (meth) acrylate having an alkyl group having 2 or less carbon atoms. Specific examples include methyl (meth) acrylate and ethyl (meth) acrylate. In view of the Tg of the ultraviolet absorbing polymer and the physical properties of the ultraviolet absorbing layer, methyl methacrylate, ethyl methacrylate and the like are preferable.
また、その他のモノマー（Ｃ）としては、上記以外の（メタ）アクリレート類；酢酸ビニル等のビニルエステル類；トリフルオロエチル（メタ）アクリレート等のハロゲン含有モノマー類；アクリロニトリル、（メタ）アクリルアミド、Ｎ−ビニルピロリドン等の窒素含有モノマー類；ビニルメチルエーテル等のビニルエーテル類；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（例えば、ＡＤＥＫＡ社製「アデカスタブ（登録商標）ＬＡ８７」）、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（例えば、ＡＤＥＫＡ社製「アデカスタブ（登録商標）ＬＡ−８２」）、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等の紫外線安定性モノマー類；スチレン等のスチレン誘導体類；等も使用可能である。 Other monomers (C) include other (meth) acrylates; vinyl esters such as vinyl acetate; halogen-containing monomers such as trifluoroethyl (meth) acrylate; acrylonitrile, (meth) acrylamide, N -Nitrogen-containing monomers such as vinyl pyrrolidone; Vinyl ethers such as vinyl methyl ether; 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine (for example, “Adeka Stub (registered trademark) LA87 manufactured by ADEKA) )), 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine (for example, manufactured by ADEKA) “ADK STAB (registered trademark) LA-82”), 4- (meth) acryloyl Amino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2, UV-stable monomers such as 6,6-tetramethylpiperidine and 4-crotonoylamino-2,2,6,6-tetramethylpiperidine; styrene derivatives such as styrene; and the like can also be used.
上記その他のモノマー（Ｃ）は、紫外線吸収性ポリマーの原料であるモノマー混合物１００質量％中、０〜５０質量％の範囲で用いる。より好ましい上限は２０質量％である。その他のモノマー（Ｃ）が多すぎると、結果的に紫外線吸収性モノマー（Ａ）や親水性モノマー（Ｂ）の量が少なくなって、充分な耐候性や耐可塑剤移行性等を確保することができない。 The other monomer (C) is used in the range of 0 to 50% by mass in 100% by mass of the monomer mixture which is a raw material of the ultraviolet absorbing polymer. A more preferred upper limit is 20% by mass. If there are too many other monomers (C), the amount of the UV-absorbing monomer (A) and hydrophilic monomer (B) will be reduced as a result, and sufficient weather resistance, plasticizer migration, etc. will be ensured. I can't.
紫外線吸収性モノマー（Ａ）、親水性モノマー（Ｂ）およびその他のモノマー（Ｃ）からなるモノマー混合物を重合することで、本発明の紫外線吸収性ポリマーを合成することができる。紫外線吸収性ポリマーを合成する際の重合方法には、公知の重合法、例えば溶液重合法、塊状重合法、水溶液重合法、懸濁重合法、乳化重合法などを使用することができるが、特に、溶液重合法は、得られた反応生成物をそのままあるいは希釈するだけで本発明の紫外線吸収性ポリマー組成物として用いることができることから好ましい。 The ultraviolet absorbing polymer of the present invention can be synthesized by polymerizing a monomer mixture composed of the ultraviolet absorbing monomer (A), the hydrophilic monomer (B) and the other monomer (C). As a polymerization method for synthesizing the ultraviolet absorbing polymer, a known polymerization method such as a solution polymerization method, a bulk polymerization method, an aqueous solution polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be used. The solution polymerization method is preferable because the obtained reaction product can be used as it is or simply as a diluted UV-absorbing polymer composition of the present invention.
溶液重合の際に用いる有機溶媒としては、トルエン、キシレン、その他の芳香族系溶媒；ｎ−ブチルアルコール、プロピレングリコールメチルエーテル、ダイアセトンアルコール、エチルセロソルブなどのアルコール系溶媒；酢酸ブチル、酢酸エチル、セロソルブアセテートなどのエステル系溶媒；メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶媒；ジメチルホルムアミドなどを使用することができる。使用する有機溶媒の種類はこれらに限定されるものではない。これらの有機溶媒は１種のみを使用してもよいし、２種以上を混合溶媒として使用してもよい。有機溶媒の使用量は、モノマー濃度や、紫外線吸収性ポリマーの所望の分子量、あるいはポリマー溶液濃度などを考慮して適宜定めればよい。 Examples of the organic solvent used in the solution polymerization include toluene, xylene, and other aromatic solvents; alcohol solvents such as n-butyl alcohol, propylene glycol methyl ether, diacetone alcohol, and ethyl cellosolve; butyl acetate, ethyl acetate, Ester solvents such as cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; dimethylformamide and the like can be used. The kind of organic solvent to be used is not limited to these. These organic solvents may use only 1 type and may use 2 or more types as a mixed solvent. The amount of the organic solvent used may be appropriately determined in consideration of the monomer concentration, the desired molecular weight of the UV-absorbing polymer, the polymer solution concentration, and the like.
溶液重合に用いることのできる重合開始剤としては、例えば、２，２’−アゾビス−（２−ジメチルバレロニトリル）、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などの公知のラジカル重合開始剤を挙げることができる。重合開始剤の使用量は、特に限定はないが、モノマー混合物１００質量部に対し０．０１質量部以上が好ましく、０．０５質量部以上がより好ましく、３０質量部以下が好ましく、１０質量部以下がより好ましい。また必要に応じて、例えば、ｎ−ドデシルメルカプタンのような連鎖移動剤を１種以上添加し、紫外線吸収性ポリマーの分子量を調整してもよい。 Examples of the polymerization initiator that can be used for solution polymerization include 2,2′-azobis- (2-dimethylvaleronitrile), tert-butylperoxy-2-ethylhexanoate, and 2,2′-azobis. Known radical polymerization initiators such as isobutyronitrile, benzoyl peroxide, and di-tert-butyl peroxide can be exemplified. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 30 parts by mass or less with respect to 100 parts by mass of the monomer mixture. The following is more preferable. If necessary, for example, one or more chain transfer agents such as n-dodecyl mercaptan may be added to adjust the molecular weight of the ultraviolet absorbing polymer.
本発明では、溶媒に溶解しにくい紫外線吸収性モノマー（Ａ）を比較的多量に用いているので、溶液重合をするに際しては、モノマー滴下法ではなく、一括仕込み重合法を用いることが好ましい。すなわち、固体（通常、粉体）である紫外線吸収性モノマー（Ａ）、親水性モノマー（Ｂ）、その他のモノマー（Ｃ）、重合溶媒といった、重合開始剤以外の原料を先に一括して反応容器に仕込み、８０℃程度に加熱しながらよく撹拌して、紫外線吸収性モノマー（Ａ）を、溶媒とモノマー（Ｂ）および（Ｃ）の混合物に溶解させてから、重合開始剤を添加して重合を開始するとよい。モノマー滴下法では、滴下ロートに加熱手段を設けなければ、紫外線吸収性モノマーが析出してくるおそれがある。なお、重合開始剤は溶媒と共に滴下しても構わない。 In the present invention, a relatively large amount of the UV-absorbing monomer (A) that is difficult to dissolve in a solvent is used. Therefore, it is preferable to use a batch charging polymerization method instead of a monomer dropping method when performing solution polymerization. That is, the raw materials other than the polymerization initiator such as the UV-absorbing monomer (A), the hydrophilic monomer (B), the other monomer (C), and the polymerization solvent, which are solid (usually powder), are collectively reacted first. Charge into a container, stir well while heating to about 80 ° C., dissolve the UV-absorbing monomer (A) in the mixture of solvent and monomers (B) and (C), then add the polymerization initiator. Polymerization may be initiated. In the monomer dropping method, if a heating means is not provided in the dropping funnel, there is a possibility that the ultraviolet absorbing monomer is deposited. The polymerization initiator may be dropped together with the solvent.
重合反応の温度は、５０℃〜１２０℃程度が好ましい。５０℃よりも低温では、一旦溶媒に紫外線吸収性モノマーを溶解させても、固体として析出してくるおそれがあるからである。反応時間は、用いるモノマー混合物の組成や重合開始剤の種類などに応じて、重合反応が効率よく完結し得るように適宜設定すればよい。 The temperature of the polymerization reaction is preferably about 50 ° C to 120 ° C. This is because at a temperature lower than 50 ° C., even if the UV-absorbing monomer is once dissolved in the solvent, it may be precipitated as a solid. What is necessary is just to set reaction time suitably so that a polymerization reaction can be completed efficiently according to the composition of the monomer mixture to be used, the kind of polymerization initiator, etc.
紫外線吸収性ポリマーの質量平均分子量（Ｍｗ）は、３０００〜２０万が好ましい。Ｍｗが３０００より小さいと、耐可塑剤移行性が不充分となるおそれがある。Ｍｗが２０万を超えると、紫外線吸収性ポリマー組成物のレベリング性が低下して、紫外線吸収層の外観が悪くなる場合があるため好ましくない。 The mass average molecular weight (Mw) of the ultraviolet absorbing polymer is preferably 3000 to 200,000. If Mw is less than 3000, the plasticizer migration may be insufficient. When Mw exceeds 200,000, the leveling property of the UV-absorbing polymer composition is lowered, and the appearance of the UV-absorbing layer may be deteriorated.
また、紫外線吸収性ポリマーの好ましいＴｇは５０℃以上〜１００℃未満である。５０℃よりも低いと、耐指紋性、耐可塑剤移行性、耐ブロッキング性が不充分となるおそれがある。Ｔｇが１００℃以上になると、紫外線吸収層の加工性が低下することがあるため、好ましくない。より好ましいＴｇの範囲は７５℃以上９５℃以下である。ＴｇはＤＳＣ（示差走査熱量測定装置）やＴＭＡ（熱機械測定装置）によって求めることができる。また、下記式によって求められる計算値を目安とすると、簡便である。 Moreover, preferable Tg of an ultraviolet-absorbing polymer is 50 degreeC or more and less than 100 degreeC. When it is lower than 50 ° C., fingerprint resistance, plasticizer migration resistance, and blocking resistance may be insufficient. When Tg is 100 ° C. or higher, the processability of the ultraviolet absorbing layer may be lowered, which is not preferable. A more preferable range of Tg is 75 ° C. or higher and 95 ° C. or lower. Tg can be determined by DSC (Differential Scanning Calorimetry) or TMA (Thermomechanical Measurement Device). Moreover, it is convenient if the calculated value calculated | required by the following formula is made into a standard.
式中、Ｔｇはガラス転移温度（Ｋ）を示し、Ｗ１、Ｗ２、…Ｗｎは、各モノマーの質量分率を示し、Ｔｇ１、Ｔｇ２、…Ｔｇｎは、対応するモノマーのホモポリマーのガラス転移温度（Ｋ）を示す。なお、ホモポリマーのＴｇは、「ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ 第４版」（John Wiley & Sons, Inc.発行）等の刊行物に記載されている数値を採用すればよい。 Wherein, Tg represents the glass transition temperature (K), W 1, W 2, ... W n represents the mass fraction of each monomer, Tg 1, Tg 2, ... Tg n is the corresponding monomers homo- The glass transition temperature (K) of the polymer is shown. The Tg of the homopolymer may be a value described in a publication such as “POLYMER HANDBOOK 4th edition” (published by John Wiley & Sons, Inc.).
本発明の紫外線吸収性ポリマー組成物は、上記溶液重合による生成物であり、紫外線吸収性ポリマー溶液である。塗工に適した粘度にするために、さらに溶媒で希釈してもよい。また、ベンゾトリアゾール系、ベンゾフェノン系、トリアジン系、インドール系等の有機系紫外線吸収剤や酸化亜鉛等の無機系紫外線吸収剤；立体障害ピペリジン化合物（例えば、チバ・スペシャルティ・ケミカルズ社製の「チヌビン（登録商標）１２３」、「チヌビン１４４」、「チヌビン７６５」等）等の添加型の紫外線安定剤；塩化ビニル系樹脂、ポリエステル系樹脂、アクリル系樹脂、シリコーン系樹脂、ウレタン系樹脂、エポキシ系樹脂等の他の樹脂；レベリング剤、酸化防止剤、タルク等の充填剤、防錆剤、蛍光性増白剤、酸化防止剤、帯電防止剤、顔料、染料、増粘剤、コロイダルシリカ、アルミナゾル等の無機微粒子やポリメチルメタクリレート系のアクリル系微粒子、成膜助剤等の塗料分野で一般的な添加剤を添加してもよい。これらの他の添加成分は、紫外線吸収層における本発明の紫外線吸収性ポリマー量が５０質量％以上（より好ましくは８０質量％以上）になるように使用することが望ましい。 The ultraviolet absorbing polymer composition of the present invention is a product obtained by the above solution polymerization, and is an ultraviolet absorbing polymer solution. In order to obtain a viscosity suitable for coating, it may be further diluted with a solvent. In addition, organic ultraviolet absorbers such as benzotriazole, benzophenone, triazine, and indole, and inorganic ultraviolet absorbers such as zinc oxide; sterically hindered piperidine compounds (eg, (Registered trademark) 123 "," Tinuvin 144 "," Tinuvin 765 ", etc.), etc .; vinyl chloride resins, polyester resins, acrylic resins, silicone resins, urethane resins, epoxy resins Other resins such as leveling agents, antioxidants, fillers such as talc, rust inhibitors, fluorescent whitening agents, antioxidants, antistatic agents, pigments, dyes, thickeners, colloidal silica, alumina sols, etc. Additives commonly used in the paint field, such as inorganic fine particles, polymethylmethacrylate acrylic fine particles, and film-forming aids There. These other additive components are desirably used so that the amount of the UV-absorbing polymer of the present invention in the UV-absorbing layer is 50% by mass or more (more preferably 80% by mass or more).
本発明の一液型紫外線吸収性ポリマー組成物には、架橋剤は配合しない。前記したとおり、架橋剤を配合することによるデメリットを避けるためである。 The one-component ultraviolet absorbing polymer composition of the present invention does not contain a crosslinking agent. As described above, this is to avoid the disadvantages of blending a crosslinking agent.
本発明の一液型紫外線吸収性ポリマー組成物は、可塑剤を含む樹脂成形体の表面に塗工され、紫外線吸収層を形成する。これにより、耐可塑剤移行性に優れた紫外線吸収層を備えた積層体を得ることができる。また、可塑剤を含まない樹脂成形体の表面に塗工してもよい。可塑剤を含む樹脂と接触した場合でも、可塑剤が紫外線吸収層へ移行しにくいため、紫外線吸収層と、可塑剤を含む樹脂とが融着して、剥がれにくくなるのを防止することができる。 The one-component ultraviolet absorbing polymer composition of the present invention is applied to the surface of a resin molded body containing a plasticizer to form an ultraviolet absorbing layer. Thereby, the laminated body provided with the ultraviolet absorption layer excellent in plasticizer transfer resistance can be obtained. Moreover, you may apply to the surface of the resin molding which does not contain a plasticizer. Even when it comes into contact with a resin containing a plasticizer, the plasticizer hardly migrates to the ultraviolet absorbing layer, so that it is possible to prevent the ultraviolet absorbing layer and the resin containing the plasticizer from fusing and becoming difficult to peel off. .
可塑剤としては、ジオクチルフタレート（ＤＯＰ）、ジノニルフタレート（ＤＮＰ）、ジイソノニルフタレート（ＤＩＮＰ）等のフタレート類；ジオクチルアジペート（ＤＯＡ）等のアジペート類；トリクレジルフォスフェート（ＴＣＰ）等のリン酸エステル類；トリメリット酸エステル類；ポリエステル系可塑剤；エポキシ系可塑剤；エポキシ化大豆油等が挙げられる。 Examples of the plasticizer include phthalates such as dioctyl phthalate (DOP), dinonyl phthalate (DNP) and diisononyl phthalate (DINP); adipates such as dioctyl adipate (DOA); and phosphoric acids such as tricresyl phosphate (TCP) Examples include esters; trimellitic acid esters; polyester plasticizers; epoxy plasticizers; epoxidized soybean oil.
樹脂成形体の素材としては、ポリ塩化ビニル樹脂やそのコポリマー類の他、ポリカーボネート系樹脂、ポリアリレート系樹脂、アクリル系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ＡＢＳ系樹脂、ポリスチレン系樹脂等が挙げられる。また、トリアセチルセルロース、ポリエーテルスルホン、芳香族ポリアミド、ポリビニルアルコール、ポリアセタール、ポリフェニレンエーテル、ポリフェニレンサルファイド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリエーテルエーテルケトン、ポリテトラフルオロエチレン等のフッ素樹脂等に適用してもよい。さらには、「ＡＲＴＯＮ（登録商標）」（ＪＳＲ社製）、「ＺＥＯＮＥＸ（登録商標）」（日本ゼオン社製）、「ＯＰＴＲＥＺ（登録商標）」（日立化成社製）等の光学用樹脂等に適用してもよい。 Examples of the resin molding material include polyvinyl chloride resin and copolymers thereof, polycarbonate resin, polyarylate resin, acrylic resin, polyolefin resin, polyester resin, ABS resin, polystyrene resin, and the like. It is done. Also applicable to fluororesins such as triacetyl cellulose, polyethersulfone, aromatic polyamide, polyvinyl alcohol, polyacetal, polyphenylene ether, polyphenylene sulfide, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polytetrafluoroethylene, etc. May be. Furthermore, optical resins such as “ARTON (registered trademark)” (manufactured by JSR), “ZEONEX (registered trademark)” (manufactured by Nippon Zeon), “OPTREZ (registered trademark)” (manufactured by Hitachi Chemical Co., Ltd.), etc. You may apply.
また、下記一般式（５） In addition, the following general formula (5)
［式中、Ｒ24、Ｒ25、Ｒ26は、それぞれ独立に、水素原子または炭素数１〜２０の有機残基を表す。なお、有機残基は酸素原子を含んでいてもよい。］
で示されるラクトン構造を有するポリマーのフィルムであってもよい。上記有機残基としては、炭素数１〜２０のアルキル基、アルケニル基、シクロアルキレン基、芳香環等を挙げることができる。
[Wherein, R 24 , R 25 and R 26 each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom. ]
The polymer film which has a lactone structure shown by these may be sufficient. As said organic residue, a C1-C20 alkyl group, an alkenyl group, a cycloalkylene group, an aromatic ring etc. can be mentioned.
上記成形体の形状や製法はどのようなものでもよく、特に限定はないが、汎用性の高いものは、平板状や曲板状、波板状等の板状あるいはフィルム状のものである。上記樹脂から成形体を形成する際には、従来公知の添加剤が添加されていてもよい。また、木目印刷等の印刷を施した意匠性のある樹脂基材を使用することも可能である。 There are no particular limitations on the shape and manufacturing method of the molded body, but a highly versatile one is a plate shape such as a flat plate shape, a curved plate shape, a corrugated plate shape, or a film shape. When forming a molded object from the said resin, the conventionally well-known additive may be added. Moreover, it is also possible to use the resin base material with the design which gave printing, such as wood grain printing.
紫外線吸収性ポリマー組成物を成形体に塗布する方法としては、浸漬、吹き付け、刷毛塗り、カーテンフローコート、グラビアコート、ロールコート、スピンコート、バーコート等の公知の塗工方法がいずれも採用可能である。 As a method for applying the UV-absorbing polymer composition to the molded body, any known coating method such as dipping, spraying, brush coating, curtain flow coating, gravure coating, roll coating, spin coating, bar coating, etc. can be adopted. It is.
紫外線吸収層の紫外線吸収性能は、層の厚みと、Ｌａｍｂｅｒｔ−Ｂｅｅｒの法則により、ポリマーに導入されている紫外線吸収性基の量、すなわち重合の際の紫外線吸収性モノマーの使用量に依存する。従って、ポリマー中の紫外線吸収性基の量と、紫外線吸収層に要求される耐候性や紫外線吸収性能を勘案して、紫外線吸収層の厚さを決定すればよいが、本発明の紫外線吸収性ポリマーの原料モノマー混合物には、紫外線吸収性モノマーが比較的多く含まれているので、紫外線吸収層を薄膜化しても充分な耐光性が確保できるため、０．３〜１０μｍが好適である。０．３μｍよりも薄膜では、耐可塑剤移行性、耐指紋性、耐候性が低下し、１０μｍを超えると、塗膜の乾燥性が低下し、耐指紋性や耐ブロッキング性が不充分となることがあるため、好ましくない。 The ultraviolet absorbing performance of the ultraviolet absorbing layer depends on the thickness of the layer and the amount of the ultraviolet absorbing group introduced into the polymer, that is, the amount of the ultraviolet absorbing monomer used in the polymerization, according to Lambert-Beer's law. Therefore, the thickness of the ultraviolet absorbing layer may be determined in consideration of the amount of the ultraviolet absorbing group in the polymer and the weather resistance and ultraviolet absorbing performance required for the ultraviolet absorbing layer. Since the polymer raw material monomer mixture contains a relatively large amount of the UV-absorbing monomer, sufficient light resistance can be ensured even if the UV-absorbing layer is thinned, so 0.3 to 10 μm is preferable. When the film is thinner than 0.3 μm, the plasticizer resistance, fingerprint resistance, and weather resistance are deteriorated. When it exceeds 10 μm, the drying property of the coating film is deteriorated, and the fingerprint resistance and blocking resistance are insufficient. This is not preferable because it sometimes occurs.
本発明の組成物を成形体に薄膜状に塗布して紫外線吸収層を形成するときの乾燥温度は、通常、室温（あるいは外気温）〜２００℃で乾燥させるのが好ましい。 The drying temperature when forming the ultraviolet absorbing layer by applying the composition of the present invention to a molded body in a thin film is usually preferably from room temperature (or outside temperature) to 200 ° C.
本発明の紫外線吸収性積層体は、成形体と紫外線吸収層（成形体と紫外線吸収層との間に可塑剤移行性の他の層があっても構わない）の積層構造である場合、紫外線吸収層が耐水性・強度・耐候性等種々の特性に優れているものであるため、このまま種々の用途に活用することができるが、最表面に、ハードコート層を備える構造のものであってもよい。ハードコート層は、高硬度で耐擦傷性に優れた塗膜を形成することのできる樹脂を用いて形成することが好ましく、このような樹脂であれば特に限定されないが、例えば、特開２０００−１７７０７０号公報で開示されているようなシリコーン系硬化性樹脂や有機系硬化性樹脂等が好ましく使用できる。 When the ultraviolet-absorbing laminate of the present invention has a laminated structure of a molded body and an ultraviolet-absorbing layer (other plasticizer migration layers may be provided between the molded body and the ultraviolet-absorbing layer), Since the absorbent layer is excellent in various properties such as water resistance, strength, and weather resistance, it can be used for various purposes as it is, but it has a structure with a hard coat layer on the outermost surface. Also good. The hard coat layer is preferably formed using a resin that can form a coating film having high hardness and excellent scratch resistance, and is not particularly limited as long as it is such a resin. A silicone-based curable resin, an organic curable resin, or the like as disclosed in Japanese Patent No. 177070 can be preferably used.
以下、実施例および比較例によって本発明をより詳細に説明するが、本発明はこれらに限定されるわけではなく、前・後記の趣旨に適合し得る範囲で適当に変更して実施することも可能であり、それらはいずれも本発明の技術的範囲に包含される。なお下記実施例および比較例において、「部」および「％」とあるのは、それぞれ質量部および質量％を表す。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples, and may be implemented with appropriate modifications within a range that can meet the purpose described above and below. All of these are possible within the scope of the present invention. In the following examples and comparative examples, “parts” and “%” represent mass parts and mass%, respectively.
合成例１
撹拌機、滴下口、温度計、冷却管および窒素ガス導入口を備えたフラスコに、粉体の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を２０部、２−ヒドロキシプロピルメタクリレート３０部、メチルメタクリレート５０部、酢酸エチル３０部とメチルエチルケトン５０部を仕込んで、窒素ガスを流入しながら撹拌し、８０℃まで昇温した。滴下槽に酢酸エチル２０部と２，２−アゾビス（２，４−ジメチルバレロニトリル）１部の混合物を仕込み、２時間かけて滴下した。滴下が終了してから２時間経過後に還流反応を始め、滴下終了時から６時間経過したところで、反応系を冷却した。反応生成物を不揮発分が４０％となるようにメチルエチルケトンで希釈した。得られた紫外線吸収性ポリマーＮｏ．１の質量平均分子量（Ｍｗ）は７２０００であり、Ｔｇは７９℃であった。
Synthesis example 1
20- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole as a powder was added to a flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet. Part, 2-hydroxypropyl methacrylate 30 parts, methyl methacrylate 50 parts, ethyl acetate 30 parts and methyl ethyl ketone 50 parts were stirred while flowing nitrogen gas, and the temperature was raised to 80 ° C. A mixture of 20 parts of ethyl acetate and 1 part of 2,2-azobis (2,4-dimethylvaleronitrile) was charged into the dropping tank and dropped over 2 hours. A reflux reaction was started 2 hours after the completion of dropping, and the reaction system was cooled when 6 hours passed from the end of dropping. The reaction product was diluted with methyl ethyl ketone so that the nonvolatile content was 40%. The obtained UV-absorbing polymer No. The mass average molecular weight (Mw) of 1 was 72000, and Tg was 79 degreeC.
［Ｍｗの測定］
ＧＰＣ装置：「ＨＬＣ−８１２０ＧＰＣ」（東ソー社製）と、カラム：ＴＳＫ−ＧＥＬ ＧＭＨＸＬ−Ｌを用いて、ポリスチレン標準試料換算値をＭｗとした。
[Measurement of Mw]
The polystyrene standard sample conversion value was set to Mw using GPC apparatus: "HLC-8120GPC" (made by Tosoh Corporation) and column: TSK-GEL GMHXL-L.
［Ｔｇの測定］
ポリマー溶液を２００℃で１５分乾燥し、乾燥物を乳鉢で粉砕した。この粉砕試料１０ｍｇを簡易密封容器に詰め、ＤＳＣ装置：「ＤＳＣ６２００」（Seiko Instruments Inc.社製）を用いて、窒素気流下、２０℃から１７０℃まで、昇温速度１０℃／分で昇温後、３０℃／分で２０℃まで急冷した。５分後に再び２０℃から１７０℃まで昇温速度１０℃／分で昇温し、得られたＤＳＣ曲線のピークの中点をガラス転移温度（℃）とした。
[Measurement of Tg]
The polymer solution was dried at 200 ° C. for 15 minutes, and the dried product was pulverized in a mortar. 10 mg of this pulverized sample is packed in a simple sealed container, and heated using a DSC apparatus: “DSC6200” (Seiko Instruments Inc.) from 20 ° C. to 170 ° C. under a nitrogen stream at a heating rate of 10 ° C./min. Thereafter, it was rapidly cooled to 20 ° C. at 30 ° C./min. After 5 minutes, the temperature was raised again from 20 ° C. to 170 ° C. at a rate of temperature rise of 10 ° C./min, and the midpoint of the peak of the obtained DSC curve was taken as the glass transition temperature (° C.).
合成例２〜１１
表１に示した組成に変更した以外は、合成例１と同様にして紫外線吸収性ポリマーＮｏ．２〜１１を合成した。
Synthesis Examples 2 to 11
Except for the change to the composition shown in Table 1, UV-absorbing polymer no. 2 to 11 were synthesized.
実施例および比較例
表２に示したＮｏ．の紫外線ポリマーを用い、各特性を評価した。合成例で得た不揮発分４０．０％のポリマー溶液をメチルエチルケトンで不揮発分が３０％になるまで希釈して、紫外線吸収性ポリマー組成物（塗工液）を調製した。これを片面が易接着処理された厚み１８８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（「コスモシャイン（登録商標）Ａ４１００」；東洋紡績社製）にバーコーターで塗工して、８０℃で１分乾燥し、乾燥膜厚が３μｍの紫外線吸収層を形成した。得られた積層体（ＰＥＴフィルム＋紫外線吸収層）について、下記特性を評価し、結果を表２に示した。
Examples and Comparative Examples No. 2 shown in Table 2 were used. Each characteristic was evaluated using the UV polymer. The polymer solution having a non-volatile content of 40.0% obtained in Synthesis Example was diluted with methyl ethyl ketone until the non-volatile content became 30% to prepare an ultraviolet-absorbing polymer composition (coating solution). This was coated on a 188 μm-thick polyethylene terephthalate (PET) film (“Cosmo Shine (registered trademark) A4100”; manufactured by Toyobo Co., Ltd.) with one side subjected to easy adhesion treatment, and dried at 80 ° C. for 1 minute. An ultraviolet absorbing layer having a dry film thickness of 3 μm was formed. The obtained laminate (PET film + ultraviolet absorption layer) was evaluated for the following characteristics, and the results are shown in Table 2.
なお、比較例７は、ポリマーＮｏ．８の１００部に対し、イソシアネート系架橋剤「デスモジュール（登録商標）Ｎ３２００」（住化バイエルウレタン社製）１０部添加し、メチルエチルケトンで不揮発分３０％になるまで希釈して、紫外線吸収性ポリマー組成物（塗工液）を調製した例である。 In Comparative Example 7, polymer No. 10 parts of isocyanate crosslinking agent “Desmodur (registered trademark) N3200” (manufactured by Sumika Bayer Urethane Co., Ltd.) is added to 100 parts of No. 8, diluted with methyl ethyl ketone until the non-volatile content becomes 30%, and UV-absorbing polymer It is the example which prepared the composition (coating liquid).
［耐候性］
上記積層体を紫外線劣化促進試験機（「アイスーパーＵＶテスター ＵＶ−Ｗ１３１」：岩崎電気社製）にセットして、８０℃、６０％ＲＨの雰囲気下で、紫外線吸収層側から１００ｍＷ／ｃｍ2の紫外線を８時間連続照射した。照射後の積層体を白い紙の上に置いて、塗膜外観を目視で観察し、全く黄変がないか、ほとんど黄変のないものを○、黄変があるものを×とした。
[Weatherability]
The above laminate was set in an ultraviolet deterioration accelerating tester (“I-Super UV Tester UV-W131” manufactured by Iwasaki Electric Co., Ltd.), and 100 mW / cm 2 from the ultraviolet absorbing layer side in an atmosphere of 80 ° C. and 60% RH. Were continuously irradiated for 8 hours. The laminated body after irradiation was placed on a white paper, and the appearance of the coating film was visually observed. The case where there was no yellowing or almost no yellowing was indicated as ◯, and the case where yellowing was indicated as x.
［耐指紋性］
上記積層体の紫外線吸収層の表面に指紋を付着させた後、８０℃の雰囲気下に４時間および８時間放置した。放置後の塗膜外観を目視で観察し、外観に全く異常がないものを○、微小クラックがわずかにあるものを△、微小クラックが多数あるものを×とした。
[Fingerprint resistance]
After the fingerprint was attached to the surface of the ultraviolet absorbing layer of the laminate, it was left in an atmosphere at 80 ° C. for 4 hours and 8 hours. The appearance of the coated film after standing was visually observed. The case where there was no abnormality in the appearance was indicated by ◯, the case where there were a few microcracks, and the case where there were many microcracks.
［耐可塑剤移行性］
軟質ポリ塩化ビニルフィルム（「アルトロン（登録商標）＃３３００；厚み０．１ｍｍ；三菱化学ＭＫＶ社製」）の表面に、上記積層体の紫外線吸収層を密着させ、６０℃の雰囲気下で、４８時間、９６時間および１４４時間放置し、ポリ塩化ビニルフィルムを剥がした。紫外線吸収層表面に可塑剤が移行した場合は、ポリ塩化ビニルフィルムと紫外線吸収層が付着するので、両者を剥離した場合に紫外線吸収層表面に油を塗ったような剥がし跡が残る。このような跡残りの全くないものを○、わずかに跡残りがあるものを△、著しく跡残りがあるものを×とした。
[Plasticizer migration resistance]
The ultraviolet absorbent layer of the laminate was adhered to the surface of a soft polyvinyl chloride film (“Altron (registered trademark) # 3300; thickness 0.1 mm; manufactured by Mitsubishi Chemical MKV Co., Ltd.)” The polyvinyl chloride film was peeled off after standing for 96 hours and 144 hours. When the plasticizer is transferred to the surface of the ultraviolet absorbing layer, the polyvinyl chloride film and the ultraviolet absorbing layer adhere to each other. Therefore, when the both are peeled off, a peeling mark such as oil applied to the surface of the ultraviolet absorbing layer remains. Those having no trace were marked with ◯, those with slight trace were marked with Δ, and those with marked trace were marked with X.
［耐ブロッキング性］
上記積層体を形成した後、直ぐに、紫外線吸収層表面にガーゼ（日本薬局方のガーゼ：タイプ１：萬星衛生材料社から入手）を５枚重ねておき、１００ｇ（直径１ｃｍ）の分銅を載せた。塗膜面にガーゼ痕が付かなくなるまでの時間を測定し、３０分未満を○、３０分以上１時間未満を△、１時間以上を×として評価した。
[Blocking resistance]
Immediately after forming the above laminate, five sheets of gauze (Japanese pharmacopoeia gauze: obtained from Comet Sanitary Materials Co., Ltd.) are stacked on the surface of the ultraviolet absorption layer, and a weight of 100 g (diameter 1 cm) is placed thereon. It was. The time until no gauze marks were left on the coating surface was measured, and the evaluation was evaluated as o for less than 30 minutes, Δ for 30 minutes to less than 1 hour, and x for 1 hour or more.
［塗工液の貯蔵安定性］
上記で調製した紫外線吸収性ポリマー組成物（塗工液）を、容器に入れて密栓した後、３０℃で８時間放置した。放置前後の粘度（Ｂ型粘度計による２５℃での粘度）の上昇率から、貯蔵安定性を判断した。上昇率は、１００×（８時間放置後の粘度）／（放置する前の粘度）で求めた。粘度変化のないものを○、上昇率が５０％以上のものを×とした。
[Storage stability of coating liquid]
The UV-absorbing polymer composition (coating solution) prepared above was put in a container and sealed, and then allowed to stand at 30 ° C. for 8 hours. The storage stability was judged from the rate of increase in viscosity before and after standing (viscosity at 25 ° C. using a B-type viscometer). The rate of increase was determined by 100 × (viscosity after standing for 8 hours) / (viscosity before leaving). A sample having no change in viscosity was rated as ○, and a sample having an increase rate of 50% or more was rated as ×.
なお、表１中の略語は以下の意味である。
ＵＶＡ：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
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ＨＰＭＡ：２−ヒドロキシプロピルメタクリレート
ＭＡＡ：メタクリル酸
ＣＨＭＡ：シクロヘキシルメタクリレート
Ｍ−９０Ｇ：メトキシポリエチレングリコール＃４００メタクリレート：「ＮＫエステルＭ−９０Ｇ」（新中村化学工業社製）
ＭＭＡ：メチルメタクリレート
ＥＭＡ：エチルメタクリレート
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
Abbreviations in Table 1 have the following meanings.
UVA: 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate MAA: methacrylate CHMA: cyclohexyl methacrylate M-90G : Methoxypolyethylene glycol # 400 methacrylate: “NK ester M-90G” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
MMA: Methyl methacrylate EMA: Ethyl methacrylate PGME: Propylene glycol monomethyl ether
本発明の一液型紫外線吸収性ポリマー組成物は、架橋剤を用いずとも、耐可塑剤移行性に優れ、塗膜としての諸特性（耐指紋性、耐ブロッキング性）も良好な紫外線吸収層を形成することができた。従って、可塑剤を含む樹脂成形体表面、例えば、ポリ塩化ビニル樹脂製の農業用フィルム、パスケース、カードケース、ファイルシート、電線被覆層、屋外貯蔵タンク、波板等の表面に、良好な特性の紫外線吸収層を形成することができる。 The one-pack type UV-absorbing polymer composition of the present invention has an excellent plasticizer transfer property without using a cross-linking agent, and has various properties (fingerprint resistance and blocking resistance) as a coating film. Could be formed. Therefore, it has good characteristics on the surface of resin molded body containing plasticizer, for example, agricultural film made of polyvinyl chloride resin, pass case, card case, file sheet, electric wire covering layer, outdoor storage tank, corrugated plate, etc. An ultraviolet absorbing layer can be formed.
本発明の一液型紫外線吸収性ポリマー組成物は、可塑剤を含む樹脂成形体と接触する可能性のある、可塑剤を含まない樹脂成形体表面に耐可塑剤移行性に優れた紫外線吸収層を形成するためにも、利用することができる。 The one-pack type UV-absorbing polymer composition of the present invention is a UV-absorbing layer excellent in plasticizer migration resistance on the surface of a resin-molded body that does not contain a plasticizer, which may come into contact with a resin-molded body that contains a plasticizer. Can also be used to form.
また、内容物や基材を紫外線から保護するための劣化保護用途、例えば、薬品・食品等を包装する材料やガラス瓶等に紫外線吸収層を形成するためのコーティング剤として利用可能である。染料等の色素の退色防止用コーティング剤としてや、フッ素樹脂フィルム等のプラスチック基材同士を貼り合わせする際の粘着剤や接着剤、あるいはシリコーン系やアクリル系のハードコート層用のプライマーとしても使用できる。さらには、耐候性記録液、繊維処理剤、絶縁素子や表示素子の絶縁用コーティング剤としても用い得る。 In addition, it can be used as a deterioration protecting application for protecting the contents and the substrate from ultraviolet rays, for example, as a coating agent for forming an ultraviolet absorbing layer on a material for packaging chemicals, foods, etc., or a glass bottle. Used as a coating for preventing discoloration of pigments such as dyes, as a pressure-sensitive adhesive or adhesive when laminating plastic substrates such as fluororesin films, or as a primer for silicone or acrylic hard coat layers it can. Furthermore, it can also be used as a weather-resistant recording liquid, a fiber treatment agent, and an insulating coating agent for insulating elements and display elements.
本発明の紫外線吸収性積層体（「フィルム」と表現される積層体も含む）は、記録材料（可逆性感熱用、溶融転写用、昇華転写用、インクジェット用、感熱用、ＩＣカード、ＩＣタグ等）、薬品・食品等の包装材、太陽電池用バックシート、マーキングフィルム、感光性樹脂版、粘着シート、色素増感型太陽電池、高分子固体電解質、紫外線吸収絶縁膜、各種光学フィルム（偏光板保護フィルム、反射防止フィルム、反射フィルム、光拡散フィルム等）、建築材料用フィルム（ガラス飛散防止フィルム、化粧シート、窓用フィルム）、屋内外のオーバーレイ用フィルム（表示材料、電飾看板）等として利用可能である。 The ultraviolet-absorbing laminate of the present invention (including laminates expressed as “films”) is a recording material (for reversible thermosensitive, melt transfer, sublimation transfer, ink jet, thermosensitive, IC card, IC tag). Etc.), packaging materials for chemicals and foods, back sheets for solar cells, marking films, photosensitive resin plates, adhesive sheets, dye-sensitized solar cells, polymer solid electrolytes, ultraviolet absorbing insulating films, various optical films (polarized light) Plate protection film, antireflection film, reflection film, light diffusion film, etc.), building material film (glass scattering prevention film, decorative sheet, window film), indoor / outdoor overlay film (display material, electric signboard), etc. Is available as
Claims (6)
（Ａ）紫外線吸収性モノマー２０〜５０質量％、
（Ｂ）アクリル酸、メタクリル酸、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレートおよび２−ヒドロキシプロピルメタクリレートよりなる群から選択される１種以上の親水性モノマー３０〜７０質量％、
（Ｃ）その他のモノマー０〜５０質量％、
からなるモノマー混合物から合成される紫外線吸収性ポリマーを含むことを特徴とする一液型紫外線吸収性ポリマー組成物。 An ultraviolet-absorbing polymer composition used for forming an ultraviolet-absorbing layer on the surface of a resin molded body,
(A) 20-50% by mass of an ultraviolet absorbing monomer,
(B) One or more hydrophilic monomers selected from the group consisting of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate 30 to 70 mass %,
(C) 0-50 mass% of other monomers,
A one-component ultraviolet absorbing polymer composition comprising an ultraviolet absorbing polymer synthesized from a monomer mixture comprising:
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| JP2007250193A JP2009079156A (en) | 2007-09-26 | 2007-09-26 | Uv absorbing polymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20140074493A (en) * | 2012-12-10 | 2014-06-18 | 동우 화인켐 주식회사 | Thin type polarising plate |
| KR20140074581A (en) * | 2012-12-10 | 2014-06-18 | 동우 화인켐 주식회사 | Acrylic copolymer and adhesive composition comprising the same and polarising plate using the same |
| CN104327432A (en) * | 2014-10-24 | 2015-02-04 | 无锡中洁能源技术有限公司 | Acrylic coating for solar battery backboard and preparation method of acrylic coating |
| KR20180101301A (en) * | 2018-08-31 | 2018-09-12 | 동우 화인켐 주식회사 | Acrylate film and polarising plate using the same |
| KR20200012911A (en) * | 2017-05-30 | 2020-02-05 | 리껭테크노스 가부시키가이샤 | Active energy curable resin compositions, hard coat laminated films, and films for application to glass |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140074493A (en) * | 2012-12-10 | 2014-06-18 | 동우 화인켐 주식회사 | Thin type polarising plate |
| KR20140074581A (en) * | 2012-12-10 | 2014-06-18 | 동우 화인켐 주식회사 | Acrylic copolymer and adhesive composition comprising the same and polarising plate using the same |
| KR102009381B1 (en) * | 2012-12-10 | 2019-08-09 | 동우 화인켐 주식회사 | Thin type polarising plate |
| CN104327432A (en) * | 2014-10-24 | 2015-02-04 | 无锡中洁能源技术有限公司 | Acrylic coating for solar battery backboard and preparation method of acrylic coating |
| KR20200012911A (en) * | 2017-05-30 | 2020-02-05 | 리껭테크노스 가부시키가이샤 | Active energy curable resin compositions, hard coat laminated films, and films for application to glass |
| KR102459495B1 (en) * | 2017-05-30 | 2022-10-26 | 리껭테크노스 가부시키가이샤 | Active Energy Curable Resin Compositions, Hard Coat Laminated Films, and Films for Application to Glass |
| KR20180101301A (en) * | 2018-08-31 | 2018-09-12 | 동우 화인켐 주식회사 | Acrylate film and polarising plate using the same |
| KR101983744B1 (en) * | 2018-08-31 | 2019-05-29 | 동우 화인켐 주식회사 | Acrylate film and polarising plate using the same |
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