JP2005325343A5 - - Google Patents
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- JP2005325343A5 JP2005325343A5 JP2005115199A JP2005115199A JP2005325343A5 JP 2005325343 A5 JP2005325343 A5 JP 2005325343A5 JP 2005115199 A JP2005115199 A JP 2005115199A JP 2005115199 A JP2005115199 A JP 2005115199A JP 2005325343 A5 JP2005325343 A5 JP 2005325343A5
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- JP
- Japan
- Prior art keywords
- resin molded
- molded product
- weight
- carboxylic acid
- unsaturated carboxylic
- 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.)
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- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 229920001169 thermoplastic Polymers 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 239000011342 resin composition Substances 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- VANNPISTIUFMLH-UHFFFAOYSA-N oxane-2,6-dione Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000004432 carbon atoms Chemical group C* 0.000 claims 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 5
- 0 CCC*(C)N(*(C)C)I Chemical compound CCC*(C)N(*(C)C)I 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- 210000000088 Lip Anatomy 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Description
上記課題を解決するため、本発明は以下の構成からなる。すなわち、
〔１〕(i)下記一般式（１）で表されるグルタル酸無水物構造単位２５〜５０重量％、(ii)不飽和カルボン酸アルキルエステル単位５０〜７５重量％、(iii)不飽和カルボン酸単位５重量％以下、および／または、(iv)その他のビニル系単量体単位１０重量％以下を有する熱可塑性重合体（Ａ）１００重量部に対して、（Ｂ）ゴム質含有重合体１〜１００重量部を含有する熱可塑性樹脂組成物を成形してなる熱可塑性樹脂成形品からなる基体の少なくとも一面に、ハードコート性を有する被膜を形成してなる樹脂成形品であって、かつ熱可塑性重合体（Ａ）中の(i)上記一般式（１）で表されるグルタル酸無水物構造単位の組成割合をＸ（重量％）、(iii)不飽和カルボン酸単位の組成割合をＹ（重量％）とした場合に、０≦Ｙ／Ｘ≦０．２であることを特徴とする樹脂成形品。
In order to solve the above problems, the present invention has the following configuration. That is,
[1] (i) 25 to 50% by weight of a glutaric anhydride structural unit represented by the following general formula (1), (ii) 50 to 75% by weight of an unsaturated carboxylic acid alkyl ester unit, (iii) an unsaturated carboxylic acid (B) Rubber-containing polymer with respect to 100 parts by weight of thermoplastic polymer (A) having 5% by weight or less of acid units and / or (iv) 10% by weight or less of other vinyl monomer units A resin molded product formed by forming a hard coat film on at least one surface of a substrate comprising a thermoplastic resin molded product formed by molding a thermoplastic resin composition containing 1 to 100 parts by weight , and The composition ratio of the glutaric anhydride structural unit represented by the general formula (1) in the thermoplastic polymer (A) is X (wt%), and (iii) the composition ratio of the unsaturated carboxylic acid unit is When Y (% by weight) is 0 ≦ Y / X ≦ 0.2 Characteristic resin molded product.
〔２〕ゴム質重合体が、コア層がアクリル酸ブチル／スチレン重合体で、最外層がメタクリル酸メチル／前記一般式（１）で表されるグルタル酸無水物含有単位からなる共重合体である〔１〕記載の樹脂成形品。 [2] The rubber polymer is a copolymer having a core layer of butyl acrylate / styrene polymer and an outermost layer of methyl methacrylate / glutaric anhydride-containing unit represented by the general formula (1). A resin molded product according to [1].
〔３〕熱可塑性重合体（Ａ）が、(ii)不飽和カルボン酸アルキルエステル単位および(iii)不飽和カルボン酸単位を含有する原共重合体を、スクリュー長さ／直径比（Ｌ／Ｄ）が３０以上、１１０以下の押出機を用いて加熱処理し、（イ）脱水及び／又は（ロ）脱アルコール反応を行うことにより、得られたものであることを特徴とする〔１〕、〔２〕のいずれかに記載の樹脂成形品。 [ 3 ] A thermoplastic polymer (A) is obtained by converting a raw copolymer containing (ii) an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit into a screw length / diameter ratio (L / D ) Is obtained by heat treatment using an extruder of 30 or more and 110 or less, and (i) dehydration and / or (b) dealcoholization reaction [1], [ 2 ] The resin molded product according to any one of [ 2 ].
〔４〕ハードコート性を有する被膜の表面にさらに、無機化合物の蒸着による単層または多層の反射防止膜を形成してなる〔１〕〜〔３〕のいずれかに記載の樹脂成形品。 [ 4 ] The resin molded product according to any one of [1] to [ 3 ], wherein a single-layer or multilayer antireflection film is further formed on the surface of the film having hard coat properties by vapor deposition of an inorganic compound.
〔５〕樹脂成形品が射出成形品であることを特徴とする〔１〕〜〔４〕のいずれかに記載の樹脂成形品。 [ 5 ] The resin molded product according to any one of [1] to [ 4 ], wherein the resin molded product is an injection molded product.
〔６〕樹脂成形品がシートであることを特徴とする〔１〕〜〔５〕のいずれかに記載の樹脂成形品。 [ 6 ] The resin molded product according to any one of [1] to [ 5 ], wherein the resin molded product is a sheet.
〔実施例１、比較例１〜８〕
参考例（２）で得られた各ペレット状の熱可塑性重合体、または参考例（４）で得られた熱可塑性樹脂組成物を、１００℃で３時間乾燥した後、射出成形機（名機製作所社製Ｍ−５０ＡII−ＳＪ）に供して、８０ｍｍ×８０ｍｍ×３ｍｍ厚みの角板状試験片を成形した。成形条件は成形温度：熱可塑性重合体のガラス転移温度＋１５０℃、金型温度：８０℃、射出速度：９０ｃｍ３／秒、射出時間：１０秒、冷却時間：３０秒、成形圧力：金型に樹脂が全て充填される圧力（成形下限圧力）＋１ＭＰａで行った。得られたそれぞれの角板状試験片を、表２に示したハードコート法（参考例（３）に記載した方法）で処理を行い、各種特性を評価した。尚、比較例２、３には、それぞれＰＭＭＡ（住友化学社製”スミペックスＬＧ”）、ＰＣ（三菱エンジニアリングプラスチックス社製”ユーピロンＨ４０００”を用い、上記の熱可塑性重合体の成形条件での射出成形法、ハードコート法と同様に、ハードコート層を有する角板状試験片を作成して評価した。
[Example 1 and Comparative Examples 1 to 8 ]
Each pellet-shaped thermoplastic polymer obtained in Reference Example (2) or the thermoplastic resin composition obtained in Reference Example (4) was dried at 100 ° C. for 3 hours, and then an injection molding machine (a famous machine). A square plate-shaped test piece having a thickness of 80 mm × 80 mm × 3 mm was formed using M-50AII-SJ manufactured by Seisakusho. Molding conditions are: molding temperature: glass transition temperature of thermoplastic polymer + 150 ° C., mold temperature: 80 ° C., injection speed: 90 cm 3 / sec, injection time: 10 seconds, cooling time: 30 seconds, molding pressure: resin on mold Were filled at a pressure (molding lower limit pressure) +1 MPa. Each obtained square plate-shaped test piece was processed by the hard coat method shown in Table 2 (the method described in Reference Example (3)), and various properties were evaluated. In Comparative Examples 2 and 3, PMMA (“SUMIPEX LG” manufactured by Sumitomo Chemical Co., Ltd.) and PC (“Iupilon H4000” manufactured by Mitsubishi Engineering Plastics Co., Ltd.) were used, respectively, and the above thermoplastic polymer was injected under molding conditions. Similar to the molding method and the hard coat method, a square plate-like test piece having a hard coat layer was prepared and evaluated.
実施例１および比較例１〜８の結果より、共重合組成を本発明の範囲内に制御した熱可塑性重合体（Ａ）１００重量部に対して、（Ｂ）ゴム質含有重合体１〜１００重量部を含有する熱可塑性樹脂組成物を用いることにより、透明性、耐熱性、落球衝撃強度に優れ、かつ高度な表面硬度と、湿熱処理後も強固なハードコート層との接着性を有した樹脂成形品が得られることが分かる。また、ゴム質含有重合体を添加した熱可塑性樹脂組成物は、熱可塑性重合体（Ａ）本来の特性を大きく損なうことなく、衝撃強度を向上できることがわかる。 From the results of Example 1 and Comparative Examples 1 to 8 , the thermoplastic polymer (A) whose copolymer composition was controlled within the scope of the present invention (A) was 100 parts by weight, and (B) the rubber-containing polymer 1 to 100. By using a thermoplastic resin composition containing parts by weight, it had excellent transparency, heat resistance , falling ball impact strength , high surface hardness, and adhesion to a hard coat layer that was strong even after wet heat treatment. It turns out that a resin molded product is obtained. The thermoplastic resin composition added pressure to the rubber-containing polymer, a thermoplastic polymer (A) without significantly impairing the original properties, impact strength it can be seen that improved.
〔実施例２、比較例９〕
参考例（４）で得られた熱可塑性樹脂組成物（Ｃ−１）を、１００℃で３時間乾燥した後、６５ｍｍφの単軸押出機（日本製鋼所社製、ＮＳ６５）を用いてリップ間隙０．５ｍｍのＴダイ（設定温度２７０℃）を介して押出し、表面仕上げ１Ｓのステンレス製ポリシングロール（７０℃）に両面を完全に接着させるようにして冷却して、厚み２００μｍのシートを得た。得られたシートを、表３に示したハードコート法（参考例（５）に記載した方法）で処理を行った後、参考例（６）に記載した反射防止膜を形成させて、各種特性を評価した。
[Example 2 and Comparative Example 9 ]
After the thermoplastic resin composition obtained in Reference Example (4) (C-1), and dried 3 hours at 100 ° C., a single-screw extruder of 65 mm-diameter (Japan Steel Works, Ltd., NS65) lip gap with The sheet was extruded through a 0.5-mm T-die (set temperature: 270 ° C.) and cooled so that both surfaces were completely adhered to a stainless steel polishing roll (70 ° C.) having a surface finish of 1S to obtain a sheet having a thickness of 200 μm. . After the obtained sheet was processed by the hard coat method shown in Table 3 (the method described in Reference Example (5)), the antireflection film described in Reference Example (6) was formed, and various properties were obtained. Evaluated.
実施例２および比較例９の結果より、シートにした場合も、共重合組成を本発明の範囲内に制御した熱可塑性重合体（Ａ）に（Ｂ）ゴム質含有重合体を含有する熱可塑性樹脂組成物を用いることにより、高度な表面硬度と、湿熱処理後もハードコート層との強固な接着性を有し、かつ反射防止膜とも十分に強固な接着性を有した樹脂成形品が得られることが分かる。 From the results of Example 2 and Comparative Example 9 , even in the case of a sheet, the thermoplastic polymer (A) having a copolymer composition controlled within the scope of the present invention contains (B) a rubber-containing polymer. By using the resin composition, it is possible to obtain a resin molded product having high surface hardness, strong adhesion to the hard coat layer even after wet heat treatment, and sufficiently strong adhesion to the antireflection film. You can see that
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005115199A JP4984419B2 (en) | 2004-04-16 | 2005-04-13 | Plastic molded product |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004121669 | 2004-04-16 | ||
| JP2004121669 | 2004-04-16 | ||
| JP2005115199A JP4984419B2 (en) | 2004-04-16 | 2005-04-13 | Plastic molded product |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2005325343A JP2005325343A (en) | 2005-11-24 |
| JP2005325343A5 true JP2005325343A5 (en) | 2008-05-29 |
| JP4984419B2 JP4984419B2 (en) | 2012-07-25 |
Family
ID=35471930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005115199A Expired - Fee Related JP4984419B2 (en) | 2004-04-16 | 2005-04-13 | Plastic molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4984419B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5186125B2 (en) * | 2007-03-29 | 2013-04-17 | 富士フイルム株式会社 | Hard coat laminate |
| JP5291919B2 (en) | 2007-11-20 | 2013-09-18 | 富士フイルム株式会社 | Protective film for polarizing plate used for display surface or film for image display device front plate |
| JP5306635B2 (en) * | 2007-11-27 | 2013-10-02 | 富士フイルム株式会社 | Method for producing hard coat laminate |
| JP5538489B2 (en) * | 2012-07-19 | 2014-07-02 | 富士フイルム株式会社 | Hard coat laminate |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60120734A (en) * | 1983-12-02 | 1985-06-28 | Asahi Chem Ind Co Ltd | Transparent, heat- and impact-resistant resin composition |
| JPH03205407A (en) * | 1990-01-04 | 1991-09-06 | Asahi Chem Ind Co Ltd | Transparent heat-resistant copolymer |
| JPH07268036A (en) * | 1994-03-30 | 1995-10-17 | Sumitomo Chem Co Ltd | Light-transmitting plastic filter with heat resistance |
| JPH0868901A (en) * | 1994-08-30 | 1996-03-12 | Nippon Hikyumen Lens Kk | Resin optical parts |
| JPH0948819A (en) * | 1995-05-29 | 1997-02-18 | Kuraray Co Ltd | Production of imidated acrylic resin |
| JP4889840B2 (en) * | 1997-12-25 | 2012-03-07 | 住友化学株式会社 | Laminated film or laminated sheet, production method thereof, laminated structure and use thereof |
| JP2000178399A (en) * | 1998-12-15 | 2000-06-27 | Mitsubishi Rayon Co Ltd | Acrylic resin film |
| JP4273794B2 (en) * | 2002-03-26 | 2009-06-03 | 東レ株式会社 | Thermoplastic polymer, process for producing the same, and molded article |
| JP2003313237A (en) * | 2002-04-18 | 2003-11-06 | Toray Ind Inc | Transparent heat-resistant copolymer, transparent heat- resistant resin composition, and molded article |
-
2005
- 2005-04-13 JP JP2005115199A patent/JP4984419B2/en not_active Expired - Fee Related
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