JP6262286B2 - High refractive index polymer and method for producing the same - Google Patents
High refractive index polymer and method for producing the same Download PDFInfo
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- JP6262286B2 JP6262286B2 JP2016105844A JP2016105844A JP6262286B2 JP 6262286 B2 JP6262286 B2 JP 6262286B2 JP 2016105844 A JP2016105844 A JP 2016105844A JP 2016105844 A JP2016105844 A JP 2016105844A JP 6262286 B2 JP6262286 B2 JP 6262286B2
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- refractive index
- group
- carbon atoms
- high refractive
- less carbon
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
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- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 12
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- 125000005843 halogen group Chemical group 0.000 claims description 10
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 239000005083 Zinc sulfide Substances 0.000 description 1
- FCRMARSNWJWNPW-UHFFFAOYSA-N [3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxypropyl] 2-methylprop-2-enoate Chemical compound OC1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 FCRMARSNWJWNPW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 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 1
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- 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 1
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- 238000007641 inkjet printing Methods 0.000 description 1
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- 150000002513 isocyanates Chemical class 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 229940090181 propyl acetate Drugs 0.000 description 1
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- 239000000565 sealant Substances 0.000 description 1
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- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、耐光性を有する高屈折率ポリマー及びその製造方法、高屈折率ポリマー組成物、並びにこの高屈折率ポリマーを用いて製造される物品に関する。 The present invention relates to a high refractive index polymer having light resistance, a method for producing the same, a high refractive index polymer composition, and an article produced using the high refractive index polymer.
高屈折率樹脂を構成するためのモノマーとして、例えば、スチレン、フルオレン等の芳香族基を含むモノマーや、トリブロモフェニルアクリレート等のハロゲンを含むモノマーを挙げることができる。しかしながら、これらのモノマーを用いて得られる樹脂（ポリマー）は耐光性に乏しく、紫外線により容易に変色することが知られている。 Examples of the monomer for constituting the high refractive index resin include a monomer containing an aromatic group such as styrene and fluorene, and a monomer containing a halogen such as tribromophenyl acrylate. However, it is known that resins (polymers) obtained using these monomers have poor light resistance and are easily discolored by ultraviolet rays.
そこで、ホスファイト系酸化防止剤やフェノール系酸化防止剤等の低分子酸化防止剤、或いは酸化ジルコニア等の耐光性が良好な無機粒子を高屈折率樹脂に添加して、耐光性を向上させることが知られている（特許文献１及び２参照）。 Therefore, low light antioxidants such as phosphite antioxidants and phenolic antioxidants, or inorganic particles with good light resistance such as zirconia oxide should be added to the high refractive index resin to improve the light resistance. Is known (see Patent Documents 1 and 2).
樹脂物品の耐光性を向上させるには、通常、光安定剤や、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系、及びシアン系の紫外線吸収剤等の多様な化学構造を有する化合物が樹脂に添加される。しかしながら、これらの紫外線吸収剤等は、通常、低分子量であるため、樹脂との相溶性の程度によっては樹脂物品の表面にブリードすることがあり、外観不良が生ずる場合がある。また、これらの紫外線吸収剤等は高温に曝されると揮散しやすいため、樹脂物品中の有効濃度が徐々に低下することがある。このため、時間経過とともに耐光性等が低下してしまい、劣化してしまう場合があった。 In order to improve the light resistance of resin articles, compounds having various chemical structures such as light stabilizers and benzophenone-based, benzotriazole-based, triazine-based, and cyan-based ultraviolet absorbers are usually added to the resin. . However, these ultraviolet absorbers or the like usually have a low molecular weight, and depending on the degree of compatibility with the resin, they may bleed on the surface of the resin article, resulting in poor appearance. Moreover, since these ultraviolet absorbers etc. are easily volatilized when exposed to high temperature, the effective concentration in the resin article may gradually decrease. For this reason, light resistance etc. may fall with time and may deteriorate.
紫外線吸収剤は、一般的に嵩高い分子構造を有する。また、スチレン等の芳香族基を含む高屈折率樹脂を構成するためのモノマーは、一般的に反応性が乏しい。このため、紫外線吸収剤と高屈折率樹脂を構成するためのモノマーとを反応させて、高分子量の共重合体（樹脂）を製造することは困難である。 The ultraviolet absorber generally has a bulky molecular structure. Moreover, the monomer for constituting high refractive index resin containing aromatic groups, such as styrene, generally has little reactivity. For this reason, it is difficult to produce a high molecular weight copolymer (resin) by reacting an ultraviolet absorber with a monomer for constituting a high refractive index resin.
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、耐光性に優れているとともに、ブリードアウトが発生せず、塗料、コーティング剤、インキ、フィルム、及びシート等の各種の高屈折率な物品を製造することが可能な高屈折率ポリマーを提供することにある。また、本発明の課題とするところは、この高屈折率ポリマーの製造方法、この高屈折率ポリマーを含有する高屈折率ポリマー組成物、及びこの高屈折率ポリマーを用いて製造される物品を提供することにある。 The present invention has been made in view of such problems of the prior art, and the object is to have excellent light resistance, no bleed out, paint, coating agent, ink Another object of the present invention is to provide a high refractive index polymer capable of producing various high refractive index articles such as films and sheets. The present invention also provides a method for producing the high refractive index polymer, a high refractive index polymer composition containing the high refractive index polymer, and an article produced using the high refractive index polymer. There is to do.
すなわち、本発明によれば、以下に示す高屈折率ポリマーが提供される。
［１］二重結合及び紫外線吸収基を有する化合物（Ａ）に由来する構成単位（ａ）と、二重結合及び芳香族基を有する化合物（Ｂ）（但し、前記化合物（Ａ）を除く）に由来する構成単位（ｂ）と、を含み、前記化合物（Ａ）が、下記一般式（１）〜（４）のいずれかで表されるモノマーであり、前記化合物（Ｂ）が、アクリル酸系モノマー及びメタクリル酸系モノマーの少なくともいずれかであり、形成される塗膜の表面のグロス値が７３．１以上であり、屈折率が１．５８以上であり、重量平均分子量（Ｍｗ）が７３，０００以上である高屈折率ポリマー。
That is, according to the present invention, the following high refractive index polymers are provided.
[1] The structural unit (a) derived from the compound (A) having a double bond and an ultraviolet absorbing group, and the compound (B) having a double bond and an aromatic group (excluding the compound (A)) The compound (A) is a monomer represented by any one of the following general formulas (1) to (4), and the compound (B) is an acrylic acid Ri der least one of systems monomers and methacrylate monomers, gloss value of the surface of the coating film formed is at 73.1 or more, a refractive index of 1.58 or more, a weight average molecular weight (Mw) der Ru high refractive index polymer or 73,000.
［２］前記化合物（Ｂ）が、メタクリル酸ベンジル、アクリル酸ベンジル、メタクリル酸フェニル、アクリル酸フェニル、及びｏ−フェニルフェノールＥＯ変性アクリレートからなる群より選択される少なくとも一種である前記［１］に記載の高屈折率ポリマー。
［３］前記構成単位（ａ）の含有割合が１〜８０質量％である前記［１］又は［２］に記載の高屈折率ポリマー。
［４］ガラス転移点（Ｔｇ）が−２０〜１６０℃であり、重量平均分子量（Ｍｗ）が１，５００，０００以下である前記［１］〜［３］のいずれかに記載の高屈折率ポリマー。
[2] In the above [1], the compound (B) is at least one selected from the group consisting of benzyl methacrylate, benzyl acrylate, phenyl methacrylate, phenyl acrylate, and o-phenylphenol EO-modified acrylate. The high refractive index polymer described .
[3 ] The high refractive index polymer according to [1] or [2] , wherein the content of the structural unit (a) is 1 to 80% by mass .
[4] a glass transition point (Tg) is the -20～160 ° C., a high refractive index according to any one of the weight-average molecular weight (Mw) of 1, 500,000 or less [1] to [3] polymer.
また、本発明によれば、以下に示す高屈折率ポリマー組成物が提供される。
［５］前記［１］〜［４］のいずれかに記載の高屈折率ポリマーと、屈折率が２．０以上の無機粒子と、を含有する高屈折率ポリマー組成物（以下、「第１の高屈折率ポリマー組成物」とも記す）。
［６］前記［１］〜［４］のいずれかに記載の高屈折率ポリマーと、屈折率が１．５８以上のポリマー（但し、前記高屈折率ポリマーを除く）と、を含有する高屈折率ポリマー組成物（以下、「第２の高屈折率ポリマー組成物」とも記す）。
Moreover, according to this invention, the high refractive index polymer composition shown below is provided.
[ 5 ] A high refractive index polymer composition (hereinafter referred to as “first”) containing the high refractive index polymer according to any one of [1] to [ 4 ] and inorganic particles having a refractive index of 2.0 or more. Of high refractive index polymer composition).
[ 6 ] A high refractive index containing the high refractive index polymer according to any one of [1] to [ 4 ] and a polymer having a refractive index of 1.58 or more (excluding the high refractive index polymer). Index polymer composition (hereinafter also referred to as “second high refractive index polymer composition”).
さらに、本発明によれば、以下に示す高屈折率ポリマーの製造方法が提供される。
［７］前記［１］〜［４］のいずれかに記載の高屈折率ポリマーの製造方法であって、前記化合物（Ａ）及び前記化合物（Ｂ）を含有する重合成分を反応させる工程を有する高屈折率ポリマーの製造方法。
Furthermore, according to this invention, the manufacturing method of the high refractive index polymer shown below is provided.
[ 7 ] The method for producing a high refractive index polymer according to any one of [1] to [ 4 ], wherein the polymer (A) and a polymerization component containing the compound (B) are reacted. A method for producing a high refractive index polymer.
また、本発明によれば、以下に示す物品が提供される。
［８］前記［１］〜［４］のいずれかに記載の高屈折率ポリマーを用いて製造される物品。
Moreover, according to this invention, the article | item shown below is provided.
[ 8 ] An article produced using the high refractive index polymer according to any one of [1] to [ 4 ].
本発明の高屈折率ポリマーは、耐光性に優れているとともに、紫外線吸収基を有する化合物に由来する構成単位をそのポリマー鎖中に含むものであるため、ブリードアウトが実質的に発生することがない。このため、本発明の高屈折率ポリマーを用いれば、耐光性に優れているとともにブリードアウトが実質的に生じない、塗料、コーティング剤、インキ、フィルム、及びシート等の各種の高屈折率な物品を製造することができる。 Since the high refractive index polymer of the present invention is excellent in light resistance and contains a constitutional unit derived from a compound having an ultraviolet absorbing group in the polymer chain, bleed-out does not substantially occur. For this reason, if the high refractive index polymer of the present invention is used, various high refractive index articles such as paints, coating agents, inks, films, and sheets, which are excellent in light resistance and substantially free from bleeding out. Can be manufactured.
以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。本発明の高屈折率ポリマーは、二重結合及び紫外線吸収基を有する化合物（Ａ）に由来する構成単位（ａ）と、二重結合及び芳香族基を有する化合物（Ｂ）（但し、化合物（Ａ）を除く）に由来する構成単位（ｂ）とを含む。以下、本発明の高屈折率ポリマーの詳細について説明する。 Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. The high refractive index polymer of the present invention comprises a structural unit (a) derived from the compound (A) having a double bond and an ultraviolet absorbing group, and a compound (B) having a double bond and an aromatic group (provided that the compound ( And a structural unit (b) derived from (except A). Hereinafter, the details of the high refractive index polymer of the present invention will be described.
（化合物（Ａ））
化合物（Ａ）は、重合反応性を有する二重結合及び紫外線吸収基をその分子構造中に有する化合物（重合性モノマー）である。本発明の高屈折率ポリマーは、この化合物（Ａ）に由来する構成単位（ａ）を含むために、耐光性に優れているとともに、ブリードアウトが実質的に発生することがない。紫外線吸収基の構造としては、例えば、一般的に用いられているベンゾトリアゾール系、ベンゾフェノン系、サリシレート系、及びトリアジン系の各種紫外線吸収剤を構成する分子構造を挙げることができる。なお、化合物（Ａ）には、これらの紫外線吸収剤を構成する分子構造以外の紫外線吸収基が含まれていてもよい。
(Compound (A))
The compound (A) is a compound (polymerizable monomer) having a double bond having polymerization reactivity and an ultraviolet absorbing group in its molecular structure. Since the high refractive index polymer of the present invention contains the structural unit (a) derived from this compound (A), it is excellent in light resistance and bleed-out does not substantially occur. Examples of the structure of the ultraviolet absorbing group include molecular structures constituting various commonly used benzotriazole-based, benzophenone-based, salicylate-based, and triazine-based ultraviolet absorbers. The compound (A) may contain an ultraviolet absorbing group other than the molecular structure constituting these ultraviolet absorbers.
化合物（Ａ）は、下記一般式（１）〜（４）のいずれかで表されるモノマーである。 The compound (A) is a monomer represented by any one of the following general formulas (1) to (4).
一般式（１）で表される化合物（Ａ）は、ベンゾトリアゾール系紫外線吸収剤の分子構造を有する化合物である。一般式（１）で表される化合物（Ａ）の具体例としては、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、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−３’−ｔ−ブチル−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’−メチルフェニル）−５−（２’−メタクリロイルオキシエチル）−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−クロロ］−２Ｈ−ベンゾトリアゾール等を挙げることができる。これらの化合物（Ａ）は、一種単独で又は二種以上を組み合わせて用いることができる。 The compound (A) represented by the general formula (1) is a compound having the molecular structure of a benzotriazole ultraviolet absorber. Specific examples of the compound (A) represented by the general formula (1) include 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy. -3'-tert-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxypropyl) phenyl]- 2H-benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) -5- (2′-methacryloyloxyethyl) -2H-benzotriazole, 2-[(2′-hydroxy-5 ′-(methacryloyl) And oxyethyl) phenyl) -5-chloro] -2H-benzotriazole. These compounds (A) can be used individually by 1 type or in combination of 2 or more types.
一般式（２）で表される化合物（Ａ）は、ベンゾフェノン系紫外線吸収剤の分子構造を有する化合物である。一般式（２）で表される化合物（Ａ）の具体例としては、２−ベンゾイル−５−（２’−ヒドロキシ−３’−メタクリロイルオキシプロポキシ）−フェノール、２−ベンゾイル−５−（２’−メタクリロイルオキシエトキシ）−フェノール、２−ベンゾイル−５−（２’−アクリロイルオキシエトキシ）−フェノール、２−ベンゾイル−５−（２’−アクリロイルオキシエトキシ）−６−ｔｅｒｔ−ブチル−フェノール等を挙げることができる。これらの化合物（Ａ）は、一種単独で又は二種以上を組み合わせて用いることができる。 The compound (A) represented by the general formula (2) is a compound having a molecular structure of a benzophenone-based ultraviolet absorber. Specific examples of the compound (A) represented by the general formula (2) include 2-benzoyl-5- (2′-hydroxy-3′-methacryloyloxypropoxy) -phenol, 2-benzoyl-5- (2 ′ -Methacryloyloxyethoxy) -phenol, 2-benzoyl-5- (2'-acryloyloxyethoxy) -phenol, 2-benzoyl-5- (2'-acryloyloxyethoxy) -6-tert-butyl-phenol, etc. be able to. These compounds (A) can be used individually by 1 type or in combination of 2 or more types.
一般式（３）で表される化合物（Ａ）は、サリシレート系紫外線吸収剤の分子構造を有する化合物である。また、一般式（４）で表される化合物（Ａ）は、トリアジン系紫外線吸収剤の分子構造を有する化合物である。一般式（４）で表される化合物（Ａ）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エトキシ）］−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−（３−アクリロイルオキシ−２−ヒドロキシプロピオキシ）］−１，３，５−トリアジン、２，４−ジフェニル−６−［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］−１，３，５−トリアジン等を挙げることができる。これらの化合物（Ａ）は、一種単独で又は二種以上を組み合わせて用いることができる。 The compound (A) represented by the general formula (3) is a compound having a molecular structure of a salicylate ultraviolet absorber. Moreover, the compound (A) represented by General formula (4) is a compound which has the molecular structure of a triazine type ultraviolet absorber. Specific examples of the compound (A) represented by the general formula (4) include 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-1,3,5-triazine. 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy)]-1,3,5-triazine, 2,4-diphenyl- Examples include 6- [2-hydroxy-4- (11-acryloyloxy-undecyloxy) phenyl] -1,3,5-triazine. These compounds (A) can be used individually by 1 type or in combination of 2 or more types.
本発明の高屈折率ポリマーに含まれる構成単位（ａ）の割合は、高屈折率ポリマー全体に対して、１〜８０質量％であることが好ましく、２〜６０質量％であることがさらに好ましく、３〜４０質量％であることが特に好ましい。構成単位（ａ）の含有割合が１質量％未満であると、耐光性が不十分となる傾向にある。一方、構成単位（ａ）の含有割合が８０質量％超であると、構成単位（ｂ）の含有割合が相対的に減少するため、屈折率が低下する傾向にある。 The proportion of the structural unit (a) contained in the high refractive index polymer of the present invention is preferably 1 to 80% by mass and more preferably 2 to 60% by mass with respect to the entire high refractive index polymer. 3 to 40% by mass is particularly preferable. When the content ratio of the structural unit (a) is less than 1% by mass, the light resistance tends to be insufficient. On the other hand, when the content ratio of the structural unit (a) is more than 80% by mass, the content ratio of the structural unit (b) is relatively decreased, so that the refractive index tends to decrease.
（化合物（Ｂ））
化合物（Ｂ）は、重合反応性を有する二重結合及び芳香族基をその分子構造中に有する化合物（重合性モノマー）である。本発明の高屈折率ポリマーは、この化合物（Ｂ）に由来する構成単位（ｂ）を含むために屈折率が高い。化合物（Ｂ）は、スチレン系モノマー、アクリル酸系モノマー、メタクリル酸系モノマー、及びアクリロニトリル系モノマーからなる群より選択される少なくとも一種であることが好ましい。なお、化合物（Ｂ）中の二重結合は、反応性及び入手又は合成の容易さなどの観点から、アクリル系又はメタクリル系の二重結合が好ましい。以下、「アクリル」と「メタクリル」を、併せて「（メタ）アクリル」とも記す。
(Compound (B))
The compound (B) is a compound (polymerizable monomer) having a polymerization-reactive double bond and an aromatic group in its molecular structure. Since the high refractive index polymer of this invention contains the structural unit (b) derived from this compound (B), a refractive index is high. The compound (B) is preferably at least one selected from the group consisting of styrene monomers, acrylic monomers, methacrylic monomers, and acrylonitrile monomers. In addition, the double bond in the compound (B) is preferably an acrylic or methacrylic double bond from the viewpoints of reactivity and availability or synthesis ease. Hereinafter, “acryl” and “methacryl” are also referred to as “(meth) acryl”.
化合物（Ｂ）の具体例としては、スチレン、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェニル、フェノールＥＯ変性（メタ）アクリレート、ｏ−フェニルフェノールＥＯ変性（メタ）アクリレート、パラクミルフェノールＥＯ変性（メタ）アクリレート、ノニルフェノールＥＯ変性（メタ）アクリレート、ノニルフェノールＰＯ変性（メタ）アクリレート、２−エチルヘキシルＥＯ変性（メタ）アクリレート、Ｎ−アクリロイルオキシエチルヘキサヒドロフタルイミド、トリブロモフェニル（メタ）アクリレート、ＥＯ変性トロブロモフェニル（メタ）アクリレート、ペンタブロモフェニル（メタ）アクリレート、ペンタブロモベンジル（メタ）アクリレート、エトキシ化ｏ−フェニルフェノール（メタ）アクリレート、ｐ-スチリルトリメトキシシラン等を挙げることができる。これらの化合物（Ｂ）は、一種単独で又は二種以上を組み合わせて用いることができる。 Specific examples of the compound (B) include styrene, benzyl (meth) acrylate, phenyl (meth) acrylate, phenol EO-modified (meth) acrylate, o-phenylphenol EO-modified (meth) acrylate, paracumylphenol EO modification. (Meth) acrylate, nonylphenol EO modified (meth) acrylate, nonylphenol PO modified (meth) acrylate, 2-ethylhexyl EO modified (meth) acrylate, N-acryloyloxyethylhexahydrophthalimide, tribromophenyl (meth) acrylate, EO modified Trobromophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, pentabromobenzyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, p-styryl Examples include rutrimethoxysilane. These compounds (B) can be used individually by 1 type or in combination of 2 or more types.
（その他の化合物）
本発明の高屈折率ポリマーは、屈折率やガラス転移点（Ｔｇ）を調整するために、その分子構造中に重合反応性を有する二重結合を有するが芳香族基を有しないその他の化合物に由来する構成単位を含んでいてもよい。その他の化合物の具体例としては、（メタ）アクリル酸、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−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、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘプチル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ｎ−ラウリル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、２−イソシアナトエチル（メタ）アクリレート等のアクリレート系モノマー；アクリロニトリル系モノマー等を挙げることができる。これらの化合物（Ｃ）は、一種単独で又は二種以上を組み合わせて用いることができる。
(Other compounds)
In order to adjust the refractive index and the glass transition point (Tg), the high refractive index polymer of the present invention can be used for other compounds having a double bond having polymerization reactivity in the molecular structure but not having an aromatic group. The derived structural unit may be included. Specific examples of other compounds include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate , Tridecyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, 2-isocyanatoethyl Examples thereof include acrylate monomers such as (meth) acrylate; acrylonitrile monomers. These compounds (C) can be used individually by 1 type or in combination of 2 or more types.
なお、本発明の高屈折率ポリマーは、２−ヒドロキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、及び（メタ）アクリル酸等の水酸基、エポキシ基、又はカルボキシル基等の官能基を有するモノマーに由来する構成単位をさらに含むことが好ましい。これらのモノマーに由来する構成単位を含むと、イソシアネート、メルカプタン、エポキシ樹脂、又はメラミン樹脂等と架橋させることが可能となり、高屈折率ポリマーの屈折率、耐光性、及び耐久性等をさらに向上させることができる。 The high refractive index polymer of the present invention is a monomer having a functional group such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylic acid, such as a hydroxyl group, an epoxy group, or a carboxyl group. It is preferable that the derived structural unit is further included. Including structural units derived from these monomers enables crosslinking with isocyanates, mercaptans, epoxy resins, melamine resins, etc., and further improves the refractive index, light resistance, durability, etc. of high refractive index polymers. be able to.
さらに、本発明の高屈折率ポリマーは、屈折率、ガラス転移点（Ｔｇ）、及び耐久性等を調整するために、ハロゲン基を含むモノマーとポリシロキサン構造を含むオリゴマーの少なくともいずれかに由来する構成単位（ｃ）をさらに含むことが好ましい。これらのモノマーやオリゴマーの具体例としては、２−（パーフルオロブチル）エチルアクリレート、パーフルオロヘキシルエチルアクリレート、２−（パーフルオロブチル）エチルメタクリレート、パーフルオロヘキシルエチルメタクリレート、ヘキサフルオロプロピレン、パーフルオロ（プロピルビニルエーテル）、塩化ビニルモノマー、塩化ビニリデンモノマー、トリブロモフェニル（メタ）アクリレート、ＥＯ変性トリブロモフェニル（メタ）アクリレート、ペンタブロモフェニル（メタ）アクリレート、ペンタブロモベンジル（メタ）アクリレート、片末端メタクリル変性ポリジメチルシロキサン、及び片末端メタクリル変性ポリジブチルシロキサン等を挙げることができる。これらの二重結合含有成分は、一種単独で又は二種以上を組み合わせて用いることができる。 Furthermore, the high refractive index polymer of the present invention is derived from at least one of a monomer containing a halogen group and an oligomer containing a polysiloxane structure in order to adjust the refractive index, glass transition point (Tg), durability and the like. It is preferable that the structural unit (c) is further included. Specific examples of these monomers and oligomers include 2- (perfluorobutyl) ethyl acrylate, perfluorohexylethyl acrylate, 2- (perfluorobutyl) ethyl methacrylate, perfluorohexylethyl methacrylate, hexafluoropropylene, perfluoro ( Propyl vinyl ether), vinyl chloride monomer, vinylidene chloride monomer, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, pentabromobenzyl (meth) acrylate, methacrylic modification at one end Examples thereof include polydimethylsiloxane and one-terminal methacryl-modified polydibutylsiloxane. These double bond-containing components can be used singly or in combination of two or more.
（高屈折率ポリマーの物性等）
本発明の高屈折率ポリマーの屈折率は、通常、１．５８以上、好ましくは１．６０以上である。なお、本明細書における「屈折率」は、例えば、多波長アッベ屈折率計（商品名「ＤＲ−Ｍ２」、ＡＴＡＧＯ社製）を使用し、干渉フィルターとしてλ＝５８９ｎｍ、及び中間液としてブロモナフタレンを用いて測定される値である。
(Physical properties of high refractive index polymer, etc.)
The refractive index of the high refractive index polymer of the present invention is usually 1.58 or more, preferably 1.60 or more. As used herein, “refractive index” refers to, for example, a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by ATAGO), λ = 589 nm as an interference filter, and bromonaphthalene as an intermediate solution. Is a value measured using.
本発明の高屈折率ポリマーのガラス転移点（Ｔｇ）は、通常、−２０〜１６０℃、好ましくは０〜１２０℃である。また、本発明の高屈折率ポリマーの重量平均分子量（Ｍｗ）は、非ブリードアウト性、耐光性、高屈折率、及び塗膜性能などの諸性能をより満足するために、１，０００〜１，５００，０００であることが好ましく、５，０００〜７５０，０００であることがさらに好ましい。なお、本明細書における「重量平均分子量（Ｍｗ）」及び「数平均分子量（Ｍｎ）」とは、特に断らない限り、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって測定されるポリスチレン換算の値を意味する。 The glass transition point (Tg) of the high refractive index polymer of the present invention is usually −20 to 160 ° C., preferably 0 to 120 ° C. Further, the weight average molecular weight (Mw) of the high refractive index polymer of the present invention is 1,000 to 1 in order to more satisfy various performances such as non-bleed out property, light resistance, high refractive index, and coating film performance. , 500,000, more preferably 5,000 to 750,000. In the present specification, “weight average molecular weight (Mw)” and “number average molecular weight (Mn)” mean values in terms of polystyrene measured by gel permeation chromatography (GPC) unless otherwise specified. .
（高屈折率ポリマーの製造方法）
本発明の高屈折率ポリマーは、例えば、化合物（Ａ）及び化合物（Ｂ）、並びに必要に応じて使用される化合物（Ｃ）を含む重合成分を、乳化重合、懸濁重合、溶液重合、又は塊状重合等の従来公知の重合方法により重合することで製造することができる。例えば、溶液重合においては、重合開始剤の存在下、適当な溶剤中で重合成分を重合させればよい。
(Method for producing high refractive index polymer)
The high refractive index polymer of the present invention comprises, for example, a polymerization component containing the compound (A) and the compound (B), and the compound (C) used as necessary, by emulsion polymerization, suspension polymerization, solution polymerization, or It can manufacture by superposing | polymerizing by conventionally well-known polymerization methods, such as block polymerization. For example, in solution polymerization, a polymerization component may be polymerized in an appropriate solvent in the presence of a polymerization initiator.
溶液重合の際に用いる溶剤の種類は、重合反応に悪影響を及ぼさないものであれば特に限定されない。溶剤の具体例としては、水；メタノール、エタノール、イソプロピルアルコール、ｎ−プロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ｔｅｒｔ−ブチルアルコール、ｎ−ペンチルアルコール、エチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、エチレングリコール、プロピレングリコール、ジエチレンングリコールなどのアルコール系溶剤；石油エーテル、ヘキサン、ヘプタンなどの脂肪族炭化水素系溶剤；ベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶剤；ジエチルエーテル、ジブチルエーテル、テトラヒドロフラン（ＴＨＦ）、ジオキサンなどのエーテル系溶剤；メチルエチルケトン、２−ペンタノン、３−ペンタノン、２−ヘプタノン、３−ヘプタノン、２−オクタノン、シクロヘキサノン、シクロペンタノン、メチルイソブチルケトンなどのケトン系溶剤；酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル系溶剤；Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン（ＮＭＰ）などのアミド系溶剤を挙げることができる。溶剤の使用量は、重合反応の条件によって適宜決定される。通常、重合成分に対して質量比で０．０１〜１００倍程度、好ましくは０．１〜２０倍程度である。なお、これらの溶剤は、一種単独で又は二種以上を組み合わせて用いることができる。 The kind of solvent used in the solution polymerization is not particularly limited as long as it does not adversely affect the polymerization reaction. Specific examples of the solvent include water; methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethylene Alcohol solvents such as glycol, propylene glycol and diethylene glycol; aliphatic hydrocarbon solvents such as petroleum ether, hexane and heptane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; diethyl ether, dibutyl ether and tetrahydrofuran (THF), ether solvents such as dioxane; methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, 2-octa Ketone solvents such as ethyl, cyclohexanone, cyclopentanone and methyl isobutyl ketone; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N- Examples include amide solvents such as methylpyrrolidone (NMP). The amount of solvent used is appropriately determined depending on the conditions of the polymerization reaction. Usually, it is about 0.01 to 100 times, preferably about 0.1 to 20 times by mass ratio to the polymerization component. In addition, these solvents can be used individually by 1 type or in combination of 2 or more types.
重合開始剤としては、従来既知のものを用いることができる。重合開始剤の具体例としては、過酸化ベンゾイル、過酸化ラウロイル、ジブチルパーオキサイド、クメンヒドロパーオキサイドなどの過酸化物類；２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２メチルプロピオネート）、２，２’−アゾビス（プロパン−２−カルボアミジン）・二塩酸、２，２’−アゾビス［Ｎ−（２−カルボキシエチル）−２−メチルプロピオンアミジン］水和物、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］、２，２’−アゾビス［Ｎ−（２−ヒドロキシエチル）−２−メチルプロパンアミド］などのアゾ系重合開始剤を挙げることができる。これらの重合開始剤は、一種単独で又は二種以上を組み合わせて用いることができる。重合開始剤の使用量は特に限定されないが、通常、重合成分に対して０．１〜１０質量％程度である。 Conventional polymerization initiators can be used. Specific examples of the polymerization initiator include peroxides such as benzoyl peroxide, lauroyl peroxide, dibutyl peroxide and cumene hydroperoxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionate), 2,2'-azobis (Propane-2-carboamidine) .dihydrochloric acid, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis [2- (2- Imidazolin-2-yl) propane], 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropanamide] and the like. That. These polymerization initiators can be used singly or in combination of two or more. Although the usage-amount of a polymerization initiator is not specifically limited, Usually, it is about 0.1-10 mass% with respect to a polymerization component.
重合反応の温度は、反応条件によって適宜設定される。通常は、室温（２５℃）〜使用する溶剤の沸点以下の温度であればよい。また、得られる高屈折率ポリマーの重合度を調整するために、メルカプタン類などの連鎖移動剤やハイドロキノンなどの重合禁止剤を重合反応系に添加してもよい。 The temperature of the polymerization reaction is appropriately set depending on the reaction conditions. Usually, the temperature may be any temperature from room temperature (25 ° C.) to the boiling point of the solvent used. In order to adjust the degree of polymerization of the resulting high refractive index polymer, a chain transfer agent such as mercaptans or a polymerization inhibitor such as hydroquinone may be added to the polymerization reaction system.
（高屈折率ポリマー組成物）
次に、本発明の高屈折率ポリマー組成物について説明する。本発明の第１のポリマー組成物は、前述の高屈折率ポリマーと、屈折率が２．０以上の無機粒子とを含有する。また、本発明の第２のポリマー組成物は、前述の高屈折率ポリマーと、屈折率が１．５８以上のポリマー（但し、前述の高屈折率ポリマーを除く）とを含有する。
(High refractive index polymer composition)
Next, the high refractive index polymer composition of the present invention will be described. The first polymer composition of the present invention contains the aforementioned high refractive index polymer and inorganic particles having a refractive index of 2.0 or more. The second polymer composition of the present invention contains the aforementioned high refractive index polymer and a polymer having a refractive index of 1.58 or more (excluding the aforementioned high refractive index polymer).
高屈折率ポリマーに高屈折率の無機粒子を添加することで、屈折率、耐光性、耐摩耗性、耐薬品性、及び耐熱性をさらに高めた高屈折率ポリマー組成物とすることができる。このような屈折率が２．０以上の無機粒子の具体例としては、酸化チタン、酸化ジルコニア、酸化亜鉛、硫化亜鉛、酸化クロム、シリコン等を挙げることができる。なお、これらの無機粒子を分散媒中に分散させた分散液を高屈折率ポリマーに添加することが、無機粒子の分散性が向上するために好ましい。 By adding high refractive index inorganic particles to the high refractive index polymer, a high refractive index polymer composition can be obtained in which the refractive index, light resistance, abrasion resistance, chemical resistance, and heat resistance are further improved. Specific examples of such inorganic particles having a refractive index of 2.0 or more include titanium oxide, zirconia oxide, zinc oxide, zinc sulfide, chromium oxide, and silicon. In addition, it is preferable to add a dispersion liquid in which these inorganic particles are dispersed in a dispersion medium to the high refractive index polymer in order to improve the dispersibility of the inorganic particles.
また、本発明の高屈折率ポリマーと、それ以外の屈折率が１．５８以上の高屈折率ポリマー（以下、第２のポリマーとも記す）とを混合することで、低コストであるとともに、屈折率、耐光性、耐摩耗性、耐薬品性、及び耐熱性がさらに向上した高屈折率ポリマー組成物とすることができる。第２のポリマーの具体例としては、ポリエステル系樹脂、ポリエステルメタクリレート系樹脂、メラミン系樹脂、ポリ塩化ビニリデン系樹脂、ポリスチレン系樹脂、ポリカーボネート系樹脂、エピスルフィド系樹脂、チオウレタン系樹脂等を挙げることができる。なお、ブリードアウトの抑制や物性向上のために、これらの樹脂を架橋させることがさらに好ましい。 Further, by mixing the high refractive index polymer of the present invention with other high refractive index polymer having a refractive index of 1.58 or more (hereinafter also referred to as a second polymer), the cost is low and the refractive index is reduced. The refractive index, light resistance, abrasion resistance, chemical resistance, and heat resistance can be further improved. Specific examples of the second polymer include polyester resins, polyester methacrylate resins, melamine resins, polyvinylidene chloride resins, polystyrene resins, polycarbonate resins, episulfide resins, thiourethane resins, and the like. it can. It is more preferable to crosslink these resins in order to suppress bleed out and improve physical properties.
（高屈折率ポリマーを用いた物品）
本発明の高屈折率ポリマーを用いれば、耐光性に優れているとともに、ブリードアウトが実質的に発生しない各種の高屈折率な物品を製造することができる。このような高屈折率な物品としては、例えば、光学用レンズ、有機ＥＬ光取り出し層、光封止剤、光学用接着剤、高屈折率粘着剤、光学用フィルター、メガネレンズ等を挙げることができる。また、屈折率が上昇すると表面反射率が高くなり、光沢性が向上することが知られている。このことから、高光沢で耐光性に優れるとともに、紫外線吸収剤が実質的にブリードアウトしない塗料、コーティング剤、インキ、フィルム、及びシート等の物品を得ることができる。なお、高屈折率ポリマーを第２のポリマー等と混合することで、耐候性及び耐久性に優れた塗料、コーティング剤、インキ、フィルム、及びシート等への応用が可能である。
(Article using high refractive index polymer)
By using the high refractive index polymer of the present invention, it is possible to produce various high refractive index articles that are excellent in light resistance and substantially free from bleeding out. Examples of such a high refractive index article include an optical lens, an organic EL light extraction layer, a light sealant, an optical adhesive, a high refractive index adhesive, an optical filter, and a spectacle lens. it can. Further, it is known that when the refractive index increases, the surface reflectance increases and the glossiness improves. From this, it is possible to obtain articles such as paints, coating agents, inks, films, and sheets that are highly glossy and excellent in light resistance and in which the ultraviolet absorber is not substantially bleed out. In addition, by mixing the high refractive index polymer with the second polymer or the like, it can be applied to paints, coating agents, inks, films, sheets and the like having excellent weather resistance and durability.
さらに、本発明の高屈折率ポリマーは、光沢仕上げが可能であるとともに、耐光性を有する。このため、印刷分野においては、昇華転写用又は感熱転写用の保護層、フォト用インクジェットプリントの保護インキ、高光沢紙、インクジェット記録媒体、ウォーターシールドメディア印刷、ラインジェット印刷、レーザー印刷方式の光沢仕上げ等への応用が可能である。また、フィルム分野においては、サインディスプレイ、ラッピング広告、加飾フィルム用の屋外用超耐光性光沢フィルム等への応用が可能である。そして、生地印刷分野においては、アパレルの光沢仕上げ等への応用が可能である。 Furthermore, the high refractive index polymer of the present invention can have a gloss finish and has light resistance. Therefore, in the printing field, a protective layer for sublimation transfer or thermal transfer, protective ink for inkjet printing for photo, high gloss paper, inkjet recording media, water shield media printing, line jet printing, laser printing gloss finish Etc. are possible. In the film field, it can be applied to sign displays, wrapping advertisements, outdoor ultra-light-resistant glossy films for decorative films, and the like. In the field of fabric printing, it can be applied to glossy finishing of apparel.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「％」は、特に断らない限り質量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.
＜ポリマーの製造＞
［参考例１］
撹拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、メチルエチルケトン（ＭＥＫ）６２．５ｇ、スチレン９５ｇ、及び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（商品名「ＲＵＶＡ−９３」、大塚化学社製）（以下、「（Ａ）−１」とも記す）５ｇを仕込んだ。窒素雰囲気下で８０℃に加熱した後、重合開始剤として２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２５ｇを添加した。８時間反応させて、重量平均分子量（Ｍｗ）が７３，０００、数平均分子量（Ｍｎ）が３５，０００であるポリマーの溶液（固形分濃度８０％）を得た。
<Manufacture of polymer>
[Reference Example 1]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After the inside of the reaction vessel was replaced with nitrogen gas, 62.5 g of methyl ethyl ketone (MEK), 95 g of styrene, and 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (trade name) 5 g of “RUVA-93” (manufactured by Otsuka Chemical Co., Ltd.) (hereinafter also referred to as “(A) -1”) was charged. After heating to 80 ° C. in a nitrogen atmosphere, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. The mixture was reacted for 8 hours to obtain a polymer solution (solid content concentration 80%) having a weight average molecular weight (Mw) of 73,000 and a number average molecular weight (Mn) of 35,000.
［参考例２〜７］
表１に示す配合としたこと以外は、前述の参考例１と同様にしてポリマーの溶液を得た。得られたポリマーの溶液の固形分濃度、並びにポリマーのガラス転移点、重量平均分子量（Ｍｗ）、及び数平均分子量（Ｍｎ）を表１に示す。なお、表１中の略号の意味を以下に示す。
[Reference Examples 2 to 7]
A polymer solution was obtained in the same manner as in Reference Example 1 except that the formulation shown in Table 1 was used. Table 1 shows the solid content concentration of the obtained polymer solution, and the glass transition point, weight average molecular weight (Mw), and number average molecular weight (Mn) of the polymer. In addition, the meaning of the symbol in Table 1 is shown below.
（Ａ）−１：２−［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
（Ａ）−２：２−［２’−ヒドロキシ−５’−（２’−ヒドロキシ−３’−メタクリロイルオキシプロポキシ）フェニル］−２Ｈ−ベンゾトリアゾール
（Ａ）−３：２−ベンゾイル−５−（２’−メタクリロイルオキシエチル）−フェノール
（Ａ）−４：フェニル−３−（２−ヒドロキシ−３−メタクリロイルオキシプロピル）サリシレート
（Ａ）−５：２，４−ビス（２，４−ジメチルフェニル）−６−［２−ヒドロキシ−４−（２−メタクリロイルオキシエトキシ，２−ドデシロキシメチル）］−１，３，５−トリアジン
(A) -1: 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (A) -2: 2- [2′-hydroxy-5 ′-(2′- Hydroxy-3'-methacryloyloxypropoxy) phenyl] -2H-benzotriazole (A) -3: 2-benzoyl-5- (2'-methacryloyloxyethyl) -phenol (A) -4: phenyl-3- (2 -Hydroxy-3-methacryloyloxypropyl) salicylate (A) -5: 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy, 2-dode) Siloxymethyl)]-1,3,5-triazine
［実施例８］
撹拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、メチルエチルケトン（ＭＥＫ）６２．５ｇ、メタクリル酸ベンジル（以下、「（Ｂ）−１」とも記す）９０ｇ、及び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（（Ａ）−１）１０ｇを仕込んだ。窒素雰囲気下で８０℃に加熱した後、重合開始剤として２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２５ｇを添加した。８時間反応させて、重量平均分子量（Ｍｗ）が７３，０００、数平均分子量（Ｍｎ）が３５，０００であるポリマーの溶液（固形分濃度８０％）を得た。
[Example 8]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 62.5 g of methyl ethyl ketone (MEK), 90 g of benzyl methacrylate (hereinafter also referred to as “(B) -1”), and 2- [2′-hydroxy-5′- 10 g of (methacryloyloxyethyl) phenyl] -2H-benzotriazole ((A) -1) was charged. After heating to 80 ° C. in a nitrogen atmosphere, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. The mixture was reacted for 8 hours to obtain a polymer solution (solid content concentration 80%) having a weight average molecular weight (Mw) of 73,000 and a number average molecular weight (Mn) of 35,000.
［実施例９〜１４］
表２に示す配合としたこと以外は、前述の実施例８と同様にしてポリマーの溶液を得た。得られたポリマーの溶液の固形分濃度、並びにポリマーのガラス転移点、重量平均分子量（Ｍｗ）、及び数平均分子量（Ｍｎ）を表２に示す。なお、表２中の略号の意味を以下に示す。
[Examples 9 to 14]
A polymer solution was obtained in the same manner as in Example 8 except that the formulation shown in Table 2 was used. Table 2 shows the solid content concentration of the obtained polymer solution, and the glass transition point, weight average molecular weight (Mw), and number average molecular weight (Mn) of the polymer. In addition, the meaning of the symbol in Table 2 is shown below.
（Ｂ）−１：メタクリル酸ベンジル
（Ｂ）−２：アクリル酸ベンジル
（Ｂ）−３：メタクリル酸フェニル
（Ｂ）−４：アクリル酸フェニル
（Ｂ）−５：ｏ−フェニルフェノールＥＯ変性アクリレート
(B) -1: benzyl methacrylate (B) -2: benzyl acrylate (B) -3: phenyl methacrylate (B) -4: phenyl acrylate (B) -5: o-phenylphenol EO-modified acrylate
［参考例１５］
撹拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、トルエン２７．８ｇ、スチレン９４ｇ、及び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（（Ａ）−１）５ｇ、２−（パーフルオロブチル）エチルアクリレート（商品名「ＣＨＥＭＩＮＯＸ ＦＡＡＣ−６」、ユニマテック社製）（以下、「（Ｃ）−１」とも記す）１ｇを仕込んだ。窒素雰囲気下で８０℃に加熱した後、重合開始剤として２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２５ｇを添加した。８時間反応させて、重量平均分子量（Ｍｗ）が１２２，０００、数平均分子量（Ｍｎ）が６０，０００であるポリマーの溶液（固形分濃度８０％）を得た。
[Reference Example 15]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 27.8 g of toluene, 94 g of styrene, and 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole ((A) -1 ) 5 g, 1 g of 2- (perfluorobutyl) ethyl acrylate (trade name “CHEMINOX FAAC-6”, manufactured by Unimatec) (hereinafter also referred to as “(C) -1”) was charged. After heating to 80 ° C. in a nitrogen atmosphere, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. The mixture was reacted for 8 hours to obtain a polymer solution (solid content concentration 80%) having a weight average molecular weight (Mw) of 122,000 and a number average molecular weight (Mn) of 60,000.
［参考例１６〜１８］
表３に示す配合としたこと以外は、前述の参考例１５と同様にしてポリマーの溶液を得た。得られたポリマーの溶液の固形分濃度、並びにポリマーのガラス転移点、重量平均分子量（Ｍｗ）、及び数平均分子量（Ｍｎ）を表３に示す。なお、表３中の略号の意味を以下に示す。
[Reference Examples 16 to 18]
A polymer solution was obtained in the same manner as in Reference Example 15 except that the formulation shown in Table 3 was used. Table 3 shows the solid content concentration of the obtained polymer solution, and the glass transition point, weight average molecular weight (Mw), and number average molecular weight (Mn) of the polymer. In addition, the meaning of the symbol in Table 3 is shown below.
（Ｃ）−１：２−（パーフルオロブチル）エチルアクリレート
（Ｃ）−２：片末端メタクリル変性ポリジメチルシロキサン
(C) -1: 2- (perfluorobutyl) ethyl acrylate (C) -2: Meth-modified methacryl-modified polydimethylsiloxane
［参考例１９〜２１］
参考例３で得たポリマーの溶液に、１ｐｈｒ（参考例１９）、５ｐｈｒ（参考例２０）、及び１０ｐｈｒ（参考例２１）となるようにＺｒＯ2分散液（商品名「ＳＺＲ−Ｋ」、堺化学工業製）を添加して、ポリマー組成物を得た。
[Reference Examples 19 to 21]
To the polymer solution obtained in Reference Example 3, a ZrO 2 dispersion (trade name “SZR-K”), 1 phr (Reference Example 19), 5 phr (Reference Example 20), and 10 phr (Reference Example 21) The chemical composition was added to obtain a polymer composition.
［参考例２２〜２４］
参考例３で得たポリマーの溶液に、０．１ｐｈｒ（参考例２２）、０．５ｐｈｒ（参考例２３）、及び１ｐｈｒ（参考例２４）となるようにメチル化メラミン樹脂（商品名「サイメル３０３」、日本サイテック社製）を添加して、ポリマー組成物を得た。
[Reference Examples 22 to 24]
In the polymer solution obtained in Reference Example 3, 0.1 phr (Reference Example 22), 0.5 phr (Reference Example 23), and 1 phr (Reference Example 24) were added to a methylated melamine resin (trade name “Cymel 303”). “Nippon Cytec Co., Ltd.) was added to obtain a polymer composition.
［比較例１］
撹拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、メチルエチルケトン（ＭＥＫ）６２．５ｇ、及びメタクリル酸メチル１００ｇを仕込んだ。窒素雰囲気下で８０℃に加熱した後、重合開始剤として２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２５ｇを添加した。８時間反応させてポリマーの溶液（固形分濃度８０％）を得た。
[Comparative Example 1]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 62.5 g of methyl ethyl ketone (MEK) and 100 g of methyl methacrylate were charged. After heating to 80 ° C. in a nitrogen atmosphere, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. Reaction was performed for 8 hours to obtain a polymer solution (solid content concentration 80%).
［比較例２］
撹拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、メチルエチルケトン（ＭＥＫ）６２．５ｇ、及びスチレン１００ｇを仕込んだ。窒素雰囲気下で８０℃に加熱した後、重合開始剤として２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２５ｇを添加した。８時間反応させてポリマーの溶液（固形分濃度８０％）を得た。
[Comparative Example 2]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 62.5 g of methyl ethyl ketone (MEK) and 100 g of styrene were charged. After heating to 80 ° C. in a nitrogen atmosphere, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. Reaction was performed for 8 hours to obtain a polymer solution (solid content concentration 80%).
［比較例３］
撹拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、メチルエチルケトン（ＭＥＫ）６２．５ｇ、及びスチレン１００ｇを仕込んだ。窒素雰囲気下で８０℃に加熱した後、重合開始剤として２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２５ｇを添加した。８時間反応させた後、２−（２Ｈ−べンゾトリアゾール−２−イル）−４’，６−ジ−ｔｅｒｔ−ペンチルフェノール（商品名「チヌビン３２８」、ＢＡＳＦ社製）５．３ｇを添加して、ポリマーの溶液（固形分濃度８０％）を得た。
[Comparative Example 3]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 62.5 g of methyl ethyl ketone (MEK) and 100 g of styrene were charged. After heating to 80 ° C. in a nitrogen atmosphere, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. After reacting for 8 hours, 5.3 g of 2- (2H-benzotriazol-2-yl) -4 ′, 6-di-tert-pentylphenol (trade name “Tinuvin 328”, manufactured by BASF) was added. Thus, a polymer solution (solid content concentration 80%) was obtained.
＜評価＞
［試験１：屈折率］
参考例１〜７、１５〜１８、実施例８〜１４、及び比較例１〜３で得たポリマーの溶液、並びに参考例１９〜２４で得たポリマー組成物を、それぞれ離型紙上にコーティングした後、加熱乾燥して、膜厚２０μｍの塗膜が形成された塗工フィルムを得た。得られた塗工フィルムについて、多波長アッベ屈折率計（商品名「ＤＲ−Ｍ２」、ＡＴＡＧＯ社製）を用いて屈折率を測定した。なお、干渉フィルターはλ＝５８９ｎｍのものを使用し、中間液にはブロモナフタレンを使用した。屈折率の測定結果を表４に示す。なお、「『レンズ特性とその選択について』、川村隆之著、視覚の科学、第２５巻、第２号、２００４年６月、日本眼光学学会発行、５５頁」の記載を参考とすれば、屈折率が１．５５以下である場合を「低屈折率」、屈折率が１．５８以上である場合を「高屈折率」と評価することもできる。
<Evaluation>
[Test 1: Refractive index]
The polymer solutions obtained in Reference Examples 1-7, 15-18, Examples 8-14, and Comparative Examples 1-3, and the polymer compositions obtained in Reference Examples 19-24 were coated on release paper, respectively. Then, it heat-dried and obtained the coating film in which the coating film with a film thickness of 20 micrometers was formed. About the obtained coating film, the refractive index was measured using the multiwavelength Abbe refractometer (Brand name "DR-M2", the product made by ATAGO). The interference filter used was λ = 589 nm, and bromonaphthalene was used as the intermediate solution. Table 4 shows the measurement results of the refractive index. In addition, referring to the description of “Lens Characteristics and Selection thereof” by Takayuki Kawamura, Visual Science, Vol. 25, No. 2, June 2004, published by the Japanese Ophthalmological Society, page 55, A case where the refractive index is 1.55 or less can be evaluated as “low refractive index”, and a case where the refractive index is 1.58 or more can be evaluated as “high refractive index”.
［試験２：耐光変色性］
前述の「試験１」で得た塗工フィルムに対して、キセノンウェザオメーター（アトラス社製）を使用して２０ＭＪ照射を行った。試験条件の具体的な内容を以下に示す。照射後の塗工フィルムの表面（塗膜表面）を目視観察し、耐光変色性を評価した。評価結果を表４に示す。
[Test 2: Light discoloration resistance]
The coated film obtained in the above “Test 1” was irradiated with 20 MJ using a xenon weatherometer (manufactured by Atlas). Specific contents of the test conditions are shown below. The surface (coating film surface) of the coated film after irradiation was visually observed to evaluate light discoloration resistance. The evaluation results are shown in Table 4.
（耐光変色性試験条件）
試験サイクル：連続照射（光照射のみ）
放射照度（制御波長）：１１０Ｗ／ｍ2 Ａｔ ３００〜４００ｎｍ
フィルター組み合わせ：ボロシリケイト（内側）、ソーダライム（外側）
ブラックパネル温度（制御センサ）：８９±３℃
槽内湿度：５０±５％
(Light discoloration resistance test conditions)
Test cycle: Continuous irradiation (light irradiation only)
Irradiance (control wavelength): 110 W / m 2 At 300 to 400 nm
Filter combination: borosilicate (inside), soda lime (outside)
Black panel temperature (control sensor): 89 ± 3 ℃
Humidity in the tank: 50 ± 5%
［試験３：ブリードアウト］
前述の「試験１」で得た塗工フィルムを室温条件下で放置し、放置後の塗工フィルムの表面（塗膜表面）を目視観察してブリードアウトの有無を評価した。評価結果を表４に示す。
[Test 3: Bleed out]
The coated film obtained in “Test 1” was allowed to stand at room temperature, and the surface of the coated film (coating surface) after the standing was visually observed to evaluate the presence or absence of bleed-out. The evaluation results are shown in Table 4.
［試験４：耐傷付き性］
前述の「試験１」で得た塗工フィルムに対して、スチールウール（＃００００）で軽く擦り、フィルムの表面（塗膜表面）を目視観察し、傷付き性を評価した。評価結果を表４に示す。
[Test 4: Scratch resistance]
The coated film obtained in the above “Test 1” was rubbed lightly with steel wool (# 0000), and the surface of the film (coating surface) was visually observed to evaluate scratch resistance. The evaluation results are shown in Table 4.
［試験５：グロス値］
参考例１〜７、１５〜１８、実施例８〜１４、及び比較例１〜３で得たポリマーの溶液、並びに参考例１９〜２４で得たポリマー組成物を、それぞれＬＥＮＥＴＡ Ｃｈａｒｔ（品番：ＫＬ−Ｎ２Ｃ、ＬＥＮＥＴＡ社製）上にコーティングした後、加熱乾燥して、膜厚１μｍの塗膜が形成された塗工フィルムを得た。フィルムの表面（塗膜表面）をデジタル光沢計（商品名「ＢＹＫガードナー・マイクロ−グロス６０°、東洋精機製作所社製）を用いてグロス値を測定した。評価結果を表４に示す。
[Test 5: gross value]
The polymer solutions obtained in Reference Examples 1 to 7, 15 to 18, Examples 8 to 14 and Comparative Examples 1 to 3, and the polymer compositions obtained in Reference Examples 19 to 24 were respectively used as LENETA Chart (product number: KL). -N2C (manufactured by LENETA) and then dried by heating to obtain a coated film having a coating film having a thickness of 1 μm. The gloss value of the surface of the film (coating surface) was measured using a digital gloss meter (trade name “BYK Gardner Micro-Gloss 60 °, manufactured by Toyo Seiki Seisakusho Co., Ltd.”).
本発明の高屈折率ポリマーは、高屈折率であるとともに、紫外線吸収剤がブリードアウトしないため、例えば、塗料、コーティング剤、インキ、フィルム、シート、染料への耐光性向上のためのサインディスプレイや昇華転写インクリボン等用のオーバコート層、耐光性が必須となる車輛内外装用加飾フィルム、カメラレンズ等の光学用レンズ、及びインクジェットプリンター用のインキワニス等を構成するための材料として好適である。 Since the high refractive index polymer of the present invention has a high refractive index and the ultraviolet absorber does not bleed out, for example, a sign display for improving light resistance to paints, coating agents, inks, films, sheets and dyes, It is suitable as a material for constituting an overcoat layer for a sublimation transfer ink ribbon, a decorative film for vehicle interior / exterior that requires light resistance, an optical lens such as a camera lens, and an ink varnish for an ink jet printer.
Claims (8)
前記化合物（Ａ）が、下記一般式（１）〜（４）のいずれかで表されるモノマーであり、
前記化合物（Ｂ）が、アクリル酸系モノマー及びメタクリル酸系モノマーの少なくともいずれかであり、
形成される塗膜の表面のグロス値が７３．１以上であり、
屈折率が１．５８以上であり、
重量平均分子量（Ｍｗ）が７３，０００以上である高屈折率ポリマー。
The compound (A) is a monomer represented by any one of the following general formulas (1) to (4),
The compound (B) state, and are at least one of acrylic monomer and methacrylic acid monomer,
The gloss value of the surface of the coating film to be formed is 73.1 or more,
Refractive index is 1.58 or more,
The weight average molecular weight (Mw) of high refractive index polymer Ru der least 73,000.
重量平均分子量（Ｍｗ）が１，５００，０００以下である請求項１〜３のいずれか一項に記載の高屈折率ポリマー。 The glass transition point (Tg) is -20 to 160 ° C,
The high refractive index polymer according to any one of claims 1 to 3 , wherein the weight average molecular weight (Mw) is 1,500,000 or less .
前記化合物（Ａ）及び前記化合物（Ｂ）を含有する重合成分を反応させる工程を有する高屈折率ポリマーの製造方法。 It is a manufacturing method of the high refractive index polymer as described in any one of Claims 1-4 ,
The manufacturing method of the high refractive index polymer which has the process of making the polymerization component containing the said compound (A) and the said compound (B) react.
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