JP2008303320A - Polylactic acid based flame retardant thin-wall sheet for electronic equipment - Google Patents
Polylactic acid based flame retardant thin-wall sheet for electronic equipment Download PDFInfo
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本発明は、ポリ乳酸樹脂を主成分とし、燃焼時にダイオキシン発生の可能性があり環境への悪影響が懸念されるハロゲン系難燃剤を使用することなく、石油資源枯渇防止／炭酸ガス排出抑制効果を有しながら、難燃性、耐熱性、および折曲げや打抜き加工性に優れた電子機器向け難燃性樹脂フィルムを提供することを目的としている。 The present invention has a polylactic acid resin as a main component and has the effect of preventing the depletion of petroleum resources / suppressing carbon dioxide emissions without using a halogen-based flame retardant that may cause dioxins during combustion and has an adverse effect on the environment. It aims at providing the flame-retardant resin film for electronic devices excellent in the flame retardance, heat resistance, and bending and punching workability.
なお、この発明においてフィルムなる用語は、シート及びフィルムの両方を意味するものとし、また特に断りのない限り透明の他、半透明、及び不透明のものを含むものとする。 In addition, in this invention, the term film shall mean both a sheet | seat and a film, and unless otherwise indicated, shall include a translucent and opaque thing other than transparent.
ポリ乳酸樹脂はとうもろこしなどの植物から得られる植物由来系の樹脂であり、従来から用いられているポリスチレン樹脂、ポリプロピレン樹脂、ポリ塩化ビニル樹脂、ポリエチレン樹脂などの石油系樹脂と異なり、石油資源枯渇防止／炭酸ガス排出抑制などの効果があるとされ、石油系樹脂に替わる材料として期待されている。 Polylactic acid resin is a plant-derived resin obtained from plants such as corn, and unlike conventional petroleum resins such as polystyrene resin, polypropylene resin, polyvinyl chloride resin, polyethylene resin, etc., prevention of petroleum resource depletion / It is said that it has effects such as suppression of carbon dioxide emission, and is expected as a material to replace petroleum resin.
しかしながら、ポリ乳酸樹脂は、既存の石油系樹脂と比較して難燃性、耐熱性、および折曲げや打抜き加工性に劣るため、特に電子機器向けの絶縁材料や印刷用材料のような難燃性、耐熱性、および折曲げや打抜き加工性が必要とされる材料分野では、早くからその改良が望まれている。 However, polylactic acid resin is inferior in flame retardancy, heat resistance, and bending and punching processability compared to existing petroleum-based resins, so that it is particularly flame retardant such as insulating materials and printing materials for electronic devices. In the field of materials that require heat resistance, heat resistance, and bendability and punching workability, improvements are desired from an early stage.
一般に、石油系熱可塑性樹脂において難燃性、耐熱性、および折曲げや打抜き加工性を改良するために、主に以下の方法が取られている。 In general, the following methods are mainly taken in order to improve flame retardancy, heat resistance, and bending and punching processability in petroleum-based thermoplastic resins.
難燃性を改良するためには、難燃剤を添加する方法が検討されており、特許第３５７９１６１号（特許文献１）では熱可塑性ポリエステル樹脂にハロゲン系難燃剤と無機系難燃剤を添加した例が、また特開２００２−１６７５００号（特許文献２）ではポリカーボネート樹脂にシリコーン系難燃剤と有機金属化合物を添加した例が示唆されている。 In order to improve the flame retardancy, a method of adding a flame retardant has been studied. Patent No. 3579161 (Patent Document 1) is an example in which a halogen-based flame retardant and an inorganic flame retardant are added to a thermoplastic polyester resin. However, JP-A-2002-167500 (Patent Document 2) suggests an example in which a silicone flame retardant and an organometallic compound are added to a polycarbonate resin.
耐熱性を改良するためには、その石油系熱可塑性樹脂よりも耐熱性の高い他の石油系熱可塑性樹脂をブレンドする方法が検討されており、特開平０８−２８３５５４号（特許文献３）ではポリエステル樹脂に対してポリカーボネート樹脂をブレンドした例が、また特開平１１−３３５５１７号（特許文献４）ではアクリロニトリル−スチレン−ブタジエン共重合体（以下、ＡＢＳ樹脂とする。）に対してポリカーボネート樹脂をブレンドした例が示唆されている。また、結晶核剤を加え結晶化を促進することで耐熱性を向上させる方法が、一般的に行われている。 In order to improve heat resistance, a method of blending another petroleum-based thermoplastic resin having higher heat resistance than that of the petroleum-based thermoplastic resin has been studied, and Japanese Patent Laid-Open No. 08-283554 (Patent Document 3) discloses. An example of blending a polycarbonate resin with a polyester resin, and JP-A-11-335517 (Patent Document 4) blends a polycarbonate resin with an acrylonitrile-styrene-butadiene copolymer (hereinafter referred to as ABS resin). An example has been suggested. In addition, a method of improving heat resistance by adding a crystal nucleating agent to promote crystallization is generally performed.
折曲げや打抜き加工性を改良するためには、折曲げや打抜き加工時の割れ防止の理由から、その石油系熱可塑性樹脂よりも耐衝撃性の高い他の石油系熱可塑性樹脂をブレンドする方法が検討されており、特開平０６−８０８４２号（特許文献５）では塩化ビニル樹脂やスチレン樹脂に対してそれよりも耐衝撃性の高いＡＢＳ樹脂等のゴム質重合体をブレンドした例が、また特開２００２−９７３６１号（特許文献６）ではポリカーボネート樹脂をブレンドした例が示唆されている。また、耐衝撃性改良剤として市販されているゴム成分を含む添加剤をブレンドすることにより耐衝撃性を改良する方法が、一般的に行われている。 In order to improve folding and punching processability, blending with other petroleum-based thermoplastic resins with higher impact resistance than that of petroleum-based thermoplastics for the purpose of preventing cracking during bending and punching In JP-A-06-80842 (Patent Document 5), an example in which a rubber polymer such as ABS resin having higher impact resistance than vinyl chloride resin or styrene resin is blended is also described. JP-A-2002-97361 (Patent Document 6) suggests an example in which a polycarbonate resin is blended. Moreover, the method of improving impact resistance is generally performed by blending the additive containing the rubber component marketed as an impact resistance improver.
一方、ポリ乳酸に対しても同様の検討がなされており、難燃性を改良した例としては、例えば特開２００４−１９００２５号（特許文献７）では臭素系難燃剤または塩素系難燃剤を添加する方法が、また特開２００６−１８２９９４号（特許文献８）ではタルクを添加する方法が示唆されている。 On the other hand, polylactic acid has been studied in the same manner. As an example of improving flame retardancy, for example, in Japanese Patent Application Laid-Open No. 2004-190025 (Patent Document 7), a brominated flame retardant or a chlorinated flame retardant is added. JP 2006-182994 (Patent Document 8) suggests a method of adding talc.
耐熱性を改良した例としては、特開２００３−１７１５３６号（特許文献９）では芳香族ポリエステル樹脂をブレンドした例が、また特開２００５−１７１２０４号（特許文献１０）ではポリメチルメタクリレート樹脂をブレンドした例が、また特開２００３−１２７３１１号（特許文献１１）では結晶核剤を加えることによりポリ乳酸樹脂を効率良く結晶化させ、耐熱性を向上した例が報告されている。 Examples of improved heat resistance include blending aromatic polyester resins in JP-A No. 2003-171536 (Patent Document 9) and blending polymethyl methacrylate resins in JP-A No. 2005-171204 (Patent Document 10). In addition, JP-A 2003-127711 (Patent Document 11) reports an example in which a polylactic acid resin is efficiently crystallized by adding a crystal nucleating agent to improve heat resistance.
折曲げや打抜き加工性を改良した例としては、特開２００６−１３７９０８号（特許文献１２）ではＡＢＳ樹脂をブレンドすることにより耐衝撃性を向上した例が、また特開２００６−１９９７４３号（特許文献１３）ではポリカーボネート樹脂をブレンドすることにより耐衝撃性を向上した例が報告されている。 As an example of improving bending and punching workability, Japanese Patent Application Laid-Open No. 2006-137908 (Patent Document 12) is an example in which impact resistance is improved by blending ABS resin, and Japanese Patent Application Laid-Open No. 2006-199743 (Patent Document 12). Reference 13) reports an example in which impact resistance is improved by blending polycarbonate resin.
しかしながら、いずれの場合においても難燃性、耐熱性、および折曲げや打抜き加工性の向上がその全てにおいてバランス良く十分とはいえず、パーソナルコンピューター、モバイル機器、携帯電話、ゲーム機、エアコン、及びテレビ等の、特に電子機器向けの絶縁材料として要求される厚さ０．５ｍｍ以下において、燃焼時にダイオキシン発生の可能性があり環境への悪影響が懸念されるハロゲン系難燃剤を使用することなく、石油資源枯渇防止／炭酸ガス排出抑制効果を有しながら、難燃性、耐熱性、および折曲げや打抜き加工性を満足することは出来ていない。例えばポリ乳酸樹脂に対して難燃性を付与する手段として、特開２００４−１９００２５号（特許文献７）では燃焼時にダイオキシン発生の可能性があるハロゲン系難燃剤が使用されており、環境負荷低減の観点から好ましくない。また、特開２００６−１８２９９４２号（特許文献８）ではタルクが使用されているが、タルクを使用した場合、難燃性は向上するものの同時に耐衝撃性が低下する。 However, in any case, the improvement in flame retardancy, heat resistance, and bending and punching workability is not sufficient in all balances, such as personal computers, mobile devices, mobile phones, game machines, air conditioners, and Without using halogen-based flame retardants that may cause dioxins during combustion and have a negative impact on the environment at a thickness of 0.5 mm or less, which is required as an insulating material especially for electronic devices such as televisions, Although it has the effect of preventing the depletion of petroleum resources / suppressing carbon dioxide emissions, it has not been able to satisfy flame retardancy, heat resistance, and bending and punching workability. For example, as a means for imparting flame retardancy to a polylactic acid resin, JP-A-2004-190025 (Patent Document 7) uses a halogen-based flame retardant that may generate dioxin at the time of combustion, thereby reducing environmental impact. From the viewpoint of Moreover, although talc is used in Unexamined-Japanese-Patent No. 2006-1829942 (patent document 8), when using a talc, although a flame retardance will improve, impact resistance will fall simultaneously.
本発明は、ポリ乳酸樹脂を主成分とし、燃焼時にダイオキシン発生の可能性があるハロゲン系難燃剤を使用することなく、石油資源枯渇防止／炭酸ガス排出抑制効果を有しながら、難燃性、耐熱性、および折曲げや打抜き加工性に優れた、電子機器向け難燃性樹脂シートを提供することを目的としている。 The present invention has a polylactic acid resin as a main component, and without using a halogen-based flame retardant that may generate dioxins during combustion, while having an effect of preventing the depletion of petroleum resources / suppressing carbon dioxide emissions, An object of the present invention is to provide a flame-retardant resin sheet for electronic equipment, which is excellent in heat resistance and bending and punching workability.
本発明者は鋭意努力した結果、ポリ乳酸樹脂５０重量部以下とポリカーボネート樹脂５０重量部以上の混合樹脂組成物１００重量部に対し、リン系難燃剤５〜２０重量部、窒素化合物系難燃剤０．１〜１０重量部、耐衝撃性改良剤０．１〜３重量部を含有し、ポリ乳酸樹脂含有量が２５重量％以上であるポリ乳酸系樹脂組成物からなり、燃焼時にダイオキシン発生の可能性があり環境への悪影響が懸念されるハロゲン系難燃剤を使用することなく、石油資源枯渇防止／炭酸ガス排出抑制効果を有しながら、難燃性、耐熱性、および折曲げや打抜き加工性の向上がその全てにおいてバランス良く十分である厚さ０．５ｍｍ以下の電子機器向け難燃性樹脂シートが得られることを見出し、本発明の完成に至った。 As a result of diligent efforts, the present inventor made 5 to 20 parts by weight of a phosphorus-based flame retardant and 0 nitrogen compound-based flame retardant for 100 parts by weight of a mixed resin composition of 50 parts by weight or less of a polylactic acid resin and 50 parts by weight or more of a polycarbonate resin. 0.1 to 10 parts by weight, 0.1 to 3 parts by weight of impact modifier, and a polylactic acid resin composition with a polylactic acid resin content of 25% by weight or more, capable of generating dioxins during combustion The flame retardant, heat resistance, and bending and punching workability are achieved without the use of halogenated flame retardants that are harmful to the environment and have the effect of preventing the depletion of petroleum resources / suppressing carbon dioxide emissions. As a result, it was found that a flame-retardant resin sheet for electronic devices having a thickness of 0.5 mm or less, in which all of the above improvements are well balanced, was achieved.
すなわち、請求項１に係る発明は、ポリ乳酸樹脂とポリカーボネート樹脂が含有され、ポリカーボネート樹脂が５０重量部以上である混合樹脂組成物１００重量部に対し、リン系難燃剤５〜２０重量部、窒素化合物系難燃剤０．１〜１０重量部、および反応型の官能基を有する耐衝撃性改良剤０．１〜３重量部を含有し、ポリ乳酸樹脂含有量が２５重量％以上であるポリ乳酸系樹脂組成物からなり、且つ厚さが０．５ｍｍ以下であることを特徴とする電子機器向け難燃性樹脂シートを要旨とするものである。 That is, the invention according to claim 1 includes 5 to 20 parts by weight of a phosphorus-based flame retardant and 100 parts by weight of a phosphorus-based flame retardant with respect to 100 parts by weight of a mixed resin composition containing a polylactic acid resin and a polycarbonate resin. Polylactic acid containing 0.1 to 10 parts by weight of a compound-based flame retardant and 0.1 to 3 parts by weight of an impact modifier having a reactive functional group and having a polylactic acid resin content of 25% by weight or more The gist of the present invention is a flame-retardant resin sheet for electronic equipment, which is made of a resin-based resin composition and has a thickness of 0.5 mm or less.
また、請求項２に係る発明は、前記リン系難燃剤が芳香族縮合リン酸エステルであることを特徴とする、請求項１に記載の電子機器向け難燃性樹脂シートを要旨とするものである。 The invention according to claim 2 is characterized in that the phosphorus-based flame retardant is an aromatic condensed phosphate ester, and the flame-retardant resin sheet for electronic devices according to claim 1 is characterized. is there.
また、請求項３に係る発明は、前記窒素化合物系難燃剤がトリアジン骨格を有する含窒素複素環化合物であることを特徴とする、請求項１または２のいずれかに記載の電子機器向け難燃性樹脂シートを要旨とするものである。 The invention according to claim 3 is the flame retardant for electronic device according to claim 1, wherein the nitrogen compound-based flame retardant is a nitrogen-containing heterocyclic compound having a triazine skeleton. The main point is a conductive resin sheet.
また、請求項４に係る発明は、前記反応型の官能基を有する耐衝撃性改良剤が反応型の官能基を有するシリコーン含有コアシェルゴムであることを特徴とする、請求項１〜３のいずれかに記載の電子機器向け難燃性樹脂シートを要旨とするものである。 The invention according to claim 4 is characterized in that the impact modifier having the reactive functional group is a silicone-containing core-shell rubber having a reactive functional group. The gist of the flame-retardant resin sheet for electronic devices described in the above.
また、請求項５に係る発明は、前記電子機器向け難燃性樹脂シートの厚さが０．２〜０．５ｍｍであることを特徴とする、請求項１〜４のいずれかに記載の電子機器向け難燃性樹脂シートを要旨とするものである。 The invention according to claim 5 is characterized in that the thickness of the flame-retardant resin sheet for electronic devices is 0.2 to 0.5 mm, according to any one of claims 1 to 4. The gist is a flame retardant resin sheet for equipment.
本発明によれば、ポリ乳酸樹脂とポリカーボネート樹脂が含有され、ポリカーボネート樹脂が５０重量部以上である混合樹脂組成物１００重量部に対し、リン系難燃剤５〜２０重量部、窒素化合物系難燃剤０．１〜１０重量部、および反応型の官能基を有する耐衝撃性改良剤０．１〜３重量部を含有し、ポリ乳酸樹脂含有量が２５重量％以上であるポリ乳酸系樹脂組成物からなり、難燃性、耐熱性、および折曲げや打抜き加工性の向上がその全てにおいてバランス良く十分である、厚さ０．５ｍｍ以下の電子機器向け難燃性樹脂フィルムを得ることが出来る。 According to the present invention, 5 to 20 parts by weight of a phosphorus-based flame retardant and a nitrogen compound-based flame retardant with respect to 100 parts by weight of a mixed resin composition containing a polylactic acid resin and a polycarbonate resin, and the polycarbonate resin being 50 parts by weight or more. A polylactic acid resin composition containing 0.1 to 10 parts by weight and an impact modifier 0.1 to 3 parts by weight having a reactive functional group and having a polylactic acid resin content of 25% by weight or more It is possible to obtain a flame-retardant resin film for an electronic device having a thickness of 0.5 mm or less, which is sufficiently balanced in all of the improvement in flame retardancy, heat resistance, and bending and punching workability.
本発明に係るポリ乳酸樹脂は、Ｌ−乳酸、Ｄ−乳酸、ＬＤ−乳酸、またはこれらの混合物を脱水縮合して得られるか、もしくは乳酸のラクチドを開環重合して得られたものが採用され、そのＬ−ポリ乳酸、Ｄ−ポリ乳酸の含有比率について制限はない。 The polylactic acid resin according to the present invention is obtained by dehydration condensation of L-lactic acid, D-lactic acid, LD-lactic acid, or a mixture thereof, or obtained by ring-opening polymerization of lactide of lactic acid. The content ratio of L-polylactic acid and D-polylactic acid is not limited.
また、乳酸以外の他の共重合成分を共重合してもよい。乳酸との共重合成分として用いられる単量体として、ヒドロキシカルボン酸としては、グリコール酸、３−ヒドロキシ酪酸、４−ヒドロキシ酪酸、３−ヒドロキシ吉草酸、４−ヒドロキシ吉草酸、６−ヒドロキシカプロン酸等が挙げられる。 Moreover, you may copolymerize other copolymerization components other than lactic acid. As a monomer used as a copolymerization component with lactic acid, as hydroxycarboxylic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid Etc.
また、脂肪族環状エステルとしては、グリコリド、ラクチド、β−プロピオラクトン、γ−ブチロラクトン、δ−バレロラクトン、ε−カプロラクトンおよびこれらにメチル基などの種々の基が置換したラクトン類が挙げられる。 Examples of the aliphatic cyclic ester include glycolide, lactide, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and lactones substituted with various groups such as a methyl group.
また、ジカルボン酸としては、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、テレフタル酸、イソフタル酸等、多価アルコールとしては、ビスフェノール／エチレンオキサイド付加反応物などの芳香族多価アルコール、エチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオール、オクタンジオール、グリセリン、ソルビタン、トリメチロールプロパン、ネオペンチルグリコールなどの脂肪族多価アルコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコールなどのエーテルグリコール等が挙げられる。 Examples of the dicarboxylic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of the polyhydric alcohol include aromatic polyhydric alcohols such as bisphenol / ethylene oxide addition reaction products, Aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, glycerin, sorbitan, trimethylolpropane, neopentyl glycol, ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, etc. Is mentioned.
本発明に使用されるポリカーボネート樹脂としては、特に限定されるものではないが、例えば芳香族二価フェノール系化合物とホスゲン、または炭酸ジエステルとを反応させることにより得られる芳香族ホモまたはコポリカーボネートなどの芳香族ポリカーボネートが挙げられる。 The polycarbonate resin used in the present invention is not particularly limited. For example, an aromatic homo- or copolycarbonate obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester can be used. An aromatic polycarbonate is mentioned.
また、前記の芳香族二価フェノール系化合物としては、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシ−３，５−ジフェニル）ブタン、２，２−ビス（４−ヒドロキシ−３，５−ジエチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジエチルフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１−フェニル−１，１−ビス（４−ヒドロキシフェニル）エタン等が使用出来、これら単独あるいは混合物として使用することが出来る。 Examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4- Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane or the like can be used, and these can be used alone or as a mixture.
ポリカーボネート樹脂の数平均分子量(Ｍｎ)は２５，０００以下であることが好ましい。数平均分子量（Ｍｎ）が２５，０００を超える場合、溶融温度がポリ乳酸樹脂と比べ高過ぎる為、シート成形時にポリ乳酸樹脂の分解や成形したシート表面のべつたきが発生する。 The number average molecular weight (Mn) of the polycarbonate resin is preferably 25,000 or less. When the number average molecular weight (Mn) exceeds 25,000, the melting temperature is too high as compared with the polylactic acid resin, so that the polylactic acid resin is decomposed during the sheet molding and the molded sheet surface is sticky.
ポリ乳酸樹脂とポリカーボネート樹脂の混合樹脂組成物におけるポリ乳酸樹脂の含有比率は、５０重量部以下であり、ポリカーボネート樹脂の含有比率は、５０重量部以上である。ポリ乳酸樹脂の含有量が５０重量部以下の場合は、ポリ乳酸樹脂組成物中のポリ乳酸樹脂含有量が２５重量％未満となり、石油資源枯渇防止、炭酸ガス排出抑制など効果の点から相応しくなく、ポリカーボネート樹脂の含有比率が５０重量部以下の場合は電子機器向け難燃性樹脂シートとして十分な難燃性、耐熱性、および折曲げや打抜き加工性を得ることが出来ない。 The content ratio of the polylactic acid resin in the mixed resin composition of the polylactic acid resin and the polycarbonate resin is 50 parts by weight or less, and the content ratio of the polycarbonate resin is 50 parts by weight or more. When the content of the polylactic acid resin is 50 parts by weight or less, the polylactic acid resin content in the polylactic acid resin composition is less than 25% by weight, which is not suitable from the viewpoint of effects such as prevention of petroleum resource depletion and suppression of carbon dioxide emission. When the content ratio of the polycarbonate resin is 50 parts by weight or less, it is impossible to obtain sufficient flame retardancy, heat resistance, and bending and punching workability as a flame retardant resin sheet for electronic equipment.
難燃性樹脂シートの厚さは０．５ｍｍ以下である必要があり、好ましくは０．２〜０．５ｍｍである。厚さが０．５ｍｍを超えると燃焼時に有炎滴下が生じ易い為、また厚さが０．２ｍｍ未満では燃焼時に延焼の広がりが大きい為、ＵＬ規格の難燃性、Ｖ−０またはＶＴＭ−０のいずれかを取得出来ない。 The thickness of the flame retardant resin sheet needs to be 0.5 mm or less, preferably 0.2 to 0.5 mm. If the thickness exceeds 0.5 mm, flaming dripping is likely to occur during combustion. If the thickness is less than 0.2 mm, the spread of fire spread is large during combustion. Therefore, UL standard flame retardancy, V-0 or VTM- Cannot get any of 0.
本発明に使用されるリン系難燃剤としてはリン酸エステルが好ましく、なかでも芳香族縮合リン酸エステルが特に好ましい。リン酸エステルとしては、例えば、リン酸メラミン、リン酸アンモン、レゾルシノールポリフェニルホスフェート、レゾルシノールポリ（ジ−２，６−キシリル）ホスフェート、ビスフェノールＡポリクレジルホスフェート、ハイドロキノンポリ（２，６−キシリル）ホスフェート、１，３−フェニレンビスジキレニルホスフェート、およびこれらの縮合物等が挙げられ、これらは単独でまたは２種以上混合して使用出来る。 As the phosphorus-based flame retardant used in the present invention, phosphate esters are preferable, and aromatic condensed phosphate esters are particularly preferable. Examples of phosphate esters include melamine phosphate, ammonium phosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) Examples thereof include phosphate, 1,3-phenylenebisdienyl phosphate, and condensates thereof. These can be used alone or in combination of two or more.
リン系難燃剤の含有量はポリ乳酸樹脂とポリカーボネート樹脂の混合樹脂組成物１００重量部に対し、５〜２０重量部である。５重量部未満の場合は電子機器向け難燃性樹脂フィルムとして十分な難燃性を得ることが出来ず、また２０重量部を超える場合はそれ以上の難燃性の向上が見られない。 The content of the phosphorus-based flame retardant is 5 to 20 parts by weight with respect to 100 parts by weight of the mixed resin composition of the polylactic acid resin and the polycarbonate resin. When the amount is less than 5 parts by weight, sufficient flame retardancy as a flame-retardant resin film for electronic devices cannot be obtained, and when the amount exceeds 20 parts by weight, no further improvement in flame retardancy is observed.
本発明に使用される窒素化合物系難燃剤としてはトリアジン骨格を有する含窒素複素環化合物が好ましい。窒素化合物系難燃剤としては、例えば、トリアジン、メラミン、ベンゾグアナミン、メチルグアナミン、シアヌル酸、メラミンシアヌレート、メラミンイソシアヌレート、トリメチルトリアジン、トリフェニルトリアジン、アメリン、アメリド、チオシアヌル酸、ジアミノメルカプトトリアジン、ジアミノメチルトリアジン、ジアミノフェニルトリアジン、ジアミノイソプロポキシトリアジン等が挙げられ、これらは単独でまたは２種以上混合して使用出来る。 The nitrogen compound-based flame retardant used in the present invention is preferably a nitrogen-containing heterocyclic compound having a triazine skeleton. Examples of the nitrogen compound flame retardant include triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amelin, ammelide, thiocyanuric acid, diaminomercaptotriazine, diaminomethyl Triazine, diaminophenyltriazine, diaminoisopropoxytriazine and the like can be mentioned, and these can be used alone or in admixture of two or more.
窒素化合物系難燃剤の含有量はポリ乳酸樹脂とポリカーボネート樹脂の混合樹脂組成物１００重量部に対し、０．１〜１０重量部である。０．１重量部未満の場合は電子機器向け難燃性樹脂フィルムとして十分な難燃性を得ることが出来ず、また１０重量部を超える場合はそれ以上の難燃性の向上が見られない。 Content of a nitrogen compound type flame retardant is 0.1-10 weight part with respect to 100 weight part of mixed resin compositions of a polylactic acid resin and a polycarbonate resin. When the amount is less than 0.1 part by weight, sufficient flame retardancy cannot be obtained as a flame retardant resin film for electronic devices. When the amount exceeds 10 parts by weight, no further improvement in flame retardancy is observed. .
本発明に使用される反応型の官能基を有する耐衝撃性改良剤としては、反応型の官能基を有するアクリル系ゴム、反応型の官能基を有するアクリル−スチレン系ゴム、反応型の官能基を有するシリコーン−アクリル系ゴムが好ましく、なかでも反応型の官能基を有するシリコーン−アクリル複合コアシェルゴムが特に好ましい。ここでいう反応型の官能基とは、ポリ乳酸、またはポリカーボネートの有する官能基と反応し、分子間力による結合である物理的結合、または共有結合等の化学的な結合を形成する、エポキシ基、アルコキシル基、メタクリル基、無水カルボン酸基、カルボキシル基、エポキシ基、メトキシ基、またはアミノ基等のことを言う。 Examples of the impact modifier having a reactive functional group used in the present invention include an acrylic rubber having a reactive functional group, an acrylic-styrene rubber having a reactive functional group, and a reactive functional group. A silicone-acrylic rubber having a functional group is preferable, and a silicone-acrylic composite core-shell rubber having a reactive functional group is particularly preferable. The reactive functional group here is an epoxy group that reacts with a functional group of polylactic acid or polycarbonate to form a physical bond, which is a bond by intermolecular force, or a chemical bond such as a covalent bond. , An alkoxyl group, a methacryl group, a carboxylic anhydride group, a carboxyl group, an epoxy group, a methoxy group, or an amino group.
反応型の官能基を有する耐衝撃性改良剤の含有量はポリ乳酸樹脂とポリカーボネート樹脂の混合樹脂組成物１００重量部に対し、０．１〜３重量部である。０．１重量部未満の場合は電子機器向け難燃性樹脂フィルムとして十分な折曲げや打抜き加工性を得ることが出来ず、また３重量部を超える場合はそれ以上の折曲げや打抜き加工性の向上が見られないばかりか難燃性の低下に繋がる。 The content of the impact modifier having a reactive functional group is 0.1 to 3 parts by weight with respect to 100 parts by weight of the mixed resin composition of polylactic acid resin and polycarbonate resin. If the amount is less than 0.1 part by weight, sufficient bending and punching processability as a flame-retardant resin film for electronic devices cannot be obtained, and if it exceeds 3 parts by weight, further bending and punching processability are not possible. As a result, the flame retardancy is lowered.
本発明のポリ乳酸系樹脂組成物には、必要に応じて各種の添加剤を配合する事が可能である。具体的には、公知の酸化防止剤、紫外線吸収剤、滑剤、可塑剤、安定剤、離型剤、帯電防止剤、着色剤、ガラス繊維、カーボン繊維、ドリップ防止剤等が挙げられる。 Various additives can be blended in the polylactic acid resin composition of the present invention as necessary. Specific examples include known antioxidants, ultraviolet absorbers, lubricants, plasticizers, stabilizers, mold release agents, antistatic agents, colorants, glass fibers, carbon fibers, and anti-drip agents.
以下、実施例、比較例により、本発明における電子機器向け難燃性樹脂フィルムの詳細について説明する。 Hereinafter, the details of the flame-retardant resin film for electronic devices in the present invention will be described with reference to Examples and Comparative Examples.
使用した樹脂、難燃剤、および補強剤は以下の通りである。
＜ポリ乳酸樹脂＞
ポリ乳酸樹脂（三井化学株式会社製、レイシアＨ４００）
＜ポリカーボネート樹脂（１）＞
ポリカーボネート樹脂、Ｍｎ＝１７，０００（三菱エンジニアプラスチック製、ユーピロンＨ４０００）
＜ポリカーボネート樹脂（２）＞
ポリカーボネート樹脂、Ｍｎ＝２０，０００（三菱エンジニアプラスチック製、ユーピロンＨ３０００）
＜ポリカーボネート樹脂（３）＞
ポリカーボネート樹脂、Ｍｎ＝２４，０００（三菱エンジニアプラスチック製、ユーピロンＳ１０００）
＜ポリカーボネート樹脂（４）＞
ポリカーボネート樹脂、Ｍｎ＝２７，０００（三菱エンジニアプラスチック製、ユーピロンＥ２０００）
＜リン系難燃剤（１）＞
芳香族縮合リン酸エステル（大八化学製、ＰＸ−２００）
＜リン系難燃剤（２）＞
トリフェニルホスフェート（大八化学製、ＴＰＰ）
＜シリコーン系難燃剤＞
シリコーン樹脂（東レダウコーニングシリコーン製、Ｓｉパウダー）
＜ハロゲン系難燃剤＞
ブロム化エポキシ樹脂（阪本薬品製、ＳＲ−Ｔ１０００）
＜タルク＞
タルク（日本タルク製、Ｐ−６）
＜窒素化合物系難燃剤（１）＞
メラミンシアヌレート（日産化学製、ＭＣ−４０００）
＜窒素化合物系難燃剤（２）＞
ポリリン酸メラミン（日産化学製、ＰＭＰ−２００）
＜耐衝撃性改良剤（１）＞
反応型の官能基を有するシリコーン−アクリル系コアシェルゴム（三菱レイヨン製、Ｓ−２２００）
＜耐衝撃性改良剤（２）＞
反応型の官能基を有するアクリル系ゴム（東亞合成株式会社製、ＡＲＵＦＯＮ ＵＧ−４０００）
＜耐衝撃性改良剤（３）＞
シリコーン−アクリル複合コアシェルゴム（三菱レイヨン製、ＳＸ−００５）
The resin, flame retardant, and reinforcing agent used are as follows.
<Polylactic acid resin>
Polylactic acid resin (Mitsui Chemicals, Lacia H400)
<Polycarbonate resin (1)>
Polycarbonate resin, Mn = 17,000 (Mitsubishi Engineer Plastic, Iupilon H4000)
<Polycarbonate resin (2)>
Polycarbonate resin, Mn = 20,000 (Mitsubishi Engineer Plastic, Iupilon H3000)
<Polycarbonate resin (3)>
Polycarbonate resin, Mn = 24,000 (Mitsubishi Engineer Plastic, Iupilon S1000)
<Polycarbonate resin (4)>
Polycarbonate resin, Mn = 27,000 (Mitsubishi Engineer Plastic, Iupilon E2000)
<Phosphorus flame retardant (1)>
Aromatic condensed phosphate (Daihachi Chemical, PX-200)
<Phosphorus flame retardant (2)>
Triphenyl phosphate (Daihachi Chemical, TPP)
<Silicone flame retardant>
Silicone resin (Toray Dow Corning Silicone, Si powder)
<Halogen flame retardant>
Brominated epoxy resin (Sakamoto Yakuhin, SR-T1000)
<Talc>
Talc (Nihon Talc, P-6)
<Nitrogen compound flame retardant (1)>
Melamine cyanurate (Nissan Chemical, MC-4000)
<Nitrogen compound flame retardant (2)>
Melamine polyphosphate (Nissan Chemical PMP-200)
<Impact resistance improver (1)>
Silicone-acrylic core shell rubber having reactive functional groups (Made by Mitsubishi Rayon, S-2200)
<Impact resistance improver (2)>
Acrylic rubber having a reactive functional group (manufactured by Toagosei Co., Ltd., ARUFON UG-4000)
<Impact resistance improver (3)>
Silicone-acrylic composite core shell rubber (Mitsubishi Rayon SX-005)
＜実施例１＞
ポリ乳酸樹脂２７重量部、ポリカーボネート樹脂（２）７３重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）５重量部、窒素化合物系難燃剤（１）２重量部、耐衝撃性改良剤（１）０．５重量部を添加したポリ乳酸系樹脂組成物を、スクリュー径４０ｍｍ、Ｌ／Ｄ＝３２の単軸押出機を用いて押出成形を行い、厚さ０．４ｍｍのシートを作成した。
<Example 1>
Phosphorus flame retardant (1) 5 parts by weight, nitrogen compound flame retardant (1) 2 parts by weight with respect to 100 parts by weight of the mixed resin composition comprising 27 parts by weight of polylactic acid resin and 73 parts by weight of polycarbonate resin (2), The polylactic acid resin composition to which 0.5 parts by weight of the impact resistance improver (1) was added was extruded using a single screw extruder having a screw diameter of 40 mm and L / D = 32. A 4 mm sheet was prepared.
＜実施例２＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）０．１重量部、耐衝撃性改良剤（１）０．５重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 2>
10 parts by weight of a phosphorus flame retardant (1) and 0.1 parts by weight of a nitrogen compound flame retardant (1) with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (2) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition to which 0.5 part by weight of the impact modifier (1) was added was used.
＜実施例３＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）２重量部、耐衝撃性改良剤（１）０．５重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 3>
10 parts by weight of a phosphorus-based flame retardant (1), 2 parts by weight of a nitrogen-based flame retardant (1), with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (2) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 0.5 parts by weight of the impact resistance improver (1) was used.
＜実施例４＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 4>
For 100 parts by weight of the mixed resin composition comprising 30 parts by weight of polylactic acid resin and 70 parts by weight of polycarbonate resin (2), 10 parts by weight of phosphorus flame retardant (1), 5 parts by weight of nitrogen compound flame retardant (1), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜実施例５＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１５重量部、窒素化合物系難燃剤（１）４重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 5>
15 parts by weight of a phosphorus flame retardant (1), 4 parts by weight of a nitrogen compound flame retardant (1) with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (2), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜実施例６＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）２０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）０．１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 6>
Phosphoric flame retardant (1) 20 parts by weight, nitrogen compound flame retardant (1) 5 parts by weight with respect to 100 parts by weight of a mixed resin composition comprising 50 parts by weight of polylactic acid resin and 50 parts by weight of polycarbonate resin (2), Impact resistance improver (1) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 0.1 part by weight was used.
＜実施例７＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）２０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）３重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 7>
Phosphoric flame retardant (1) 20 parts by weight, nitrogen compound flame retardant (1) 5 parts by weight with respect to 100 parts by weight of a mixed resin composition comprising 50 parts by weight of polylactic acid resin and 50 parts by weight of polycarbonate resin (2), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 3 parts by weight of the impact resistance improver (1) was used.
＜実施例８＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）２０重量部、窒素化合物系難燃剤（１）１０重量部、耐衝撃性改良剤（１）０．１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 8>
Phosphorus flame retardant (1) 20 parts by weight, nitrogen compound flame retardant (1) 10 parts by weight with respect to 100 parts by weight of a mixed resin composition comprising 50 parts by weight of a polylactic acid resin and 50 parts by weight of a polycarbonate resin (2). Impact resistance improver (1) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 0.1 part by weight was used.
＜実施例９＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（１）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 9>
10 parts by weight of a phosphorus-based flame retardant (1), 5 parts by weight of a nitrogen-based flame retardant (1), with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (1) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜実施例１０＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（３）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 10>
To 100 parts by weight of the mixed resin composition comprising 30 parts by weight of polylactic acid resin and 70 parts by weight of polycarbonate resin (3), 10 parts by weight of phosphorus flame retardant (1), 5 parts by weight of nitrogen compound flame retardant (1), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜実施例１１＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（４）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 11>
10 parts by weight of a phosphorus-based flame retardant (1), 5 parts by weight of a nitrogen-based flame retardant (1), with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (4) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜実施例１２＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（２）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 12>
10 parts by weight of a phosphorus-based flame retardant (2), 5 parts by weight of a nitrogen compound-based flame retardant (1) with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (2) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜実施例１３＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）２０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（２）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 13>
Phosphoric flame retardant (1) 20 parts by weight, nitrogen compound flame retardant (1) 5 parts by weight with respect to 100 parts by weight of a mixed resin composition comprising 50 parts by weight of polylactic acid resin and 50 parts by weight of polycarbonate resin (2), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (2) was used.
＜実施例１４＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）２０重量部、窒素化合物系難燃剤（２）１０重量部、耐衝撃性改良剤（１）０．５重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Example 14>
Phosphorus flame retardant (1) 20 parts by weight, nitrogen compound flame retardant (2) 10 parts by weight with respect to 100 parts by weight of a mixed resin composition comprising 50 parts by weight of polylactic acid resin and 50 parts by weight of polycarbonate resin (2), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 0.5 parts by weight of the impact resistance improver (1) was used.
＜実施例１５＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．２ｍｍのシートを作成した。
<Example 15>
For 100 parts by weight of the mixed resin composition comprising 30 parts by weight of polylactic acid resin and 70 parts by weight of polycarbonate resin (2), 10 parts by weight of phosphorus flame retardant (1), 5 parts by weight of nitrogen compound flame retardant (1), A sheet having a thickness of 0.2 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜比較例１＞
ポリ乳酸樹脂６０重量部、ポリカーボネート樹脂（２）４０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 1>
Phosphoric flame retardant (1) 10 parts by weight, nitrogen compound flame retardant (1) 5 parts by weight with respect to 100 parts by weight of a mixed resin composition comprising 60 parts by weight of polylactic acid resin and 40 parts by weight of polycarbonate resin (2). A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜比較例２＞
ポリ乳酸樹脂２０重量部、ポリカーボネート樹脂（２）８０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）５重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative example 2>
5 parts by weight of a phosphorus flame retardant (1), 5 parts by weight of a nitrogen compound flame retardant (1), with respect to 100 parts by weight of a mixed resin composition comprising 20 parts by weight of a polylactic acid resin and 80 parts by weight of a polycarbonate resin (2), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜比較例３＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）３重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 3>
3 parts by weight of a phosphorus-based flame retardant (1), 5 parts by weight of a nitrogen compound-based flame retardant (1), with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (2) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜比較例４＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）０．０５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 4>
10 parts by weight of a phosphorus flame retardant (1) and 0.05 parts by weight of a nitrogen compound flame retardant (1) with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (2) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition to which 1 part by weight of the impact modifier (1) was added was used.
＜比較例５＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）１５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 5>
10 parts by weight of a phosphorus flame retardant (1), 15 parts by weight of a nitrogen compound flame retardant (1) with respect to 100 parts by weight of a mixed resin composition comprising 30 parts by weight of a polylactic acid resin and 70 parts by weight of a polycarbonate resin (2), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜比較例６＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）１５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 6>
For 100 parts by weight of the mixed resin composition consisting of 50 parts by weight of polylactic acid resin and 50 parts by weight of polycarbonate resin (2), 10 parts by weight of phosphorus flame retardant (1), 15 parts by weight of nitrogen compound flame retardant (1), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (1) was used.
＜比較例７＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）４重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 7>
For 100 parts by weight of the mixed resin composition comprising 30 parts by weight of polylactic acid resin and 70 parts by weight of polycarbonate resin (2), 10 parts by weight of phosphorus flame retardant (1), 5 parts by weight of nitrogen compound flame retardant (1), Impact resistance improver (1) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 4 parts by weight was used.
＜比較例８＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、シリコーン系難燃剤１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 8>
10 parts by weight of a silicone-based flame retardant, 5 parts by weight of a nitrogen-based flame retardant (1), and impact resistance with respect to 100 parts by weight of a mixed resin composition comprising 50 parts by weight of a polylactic acid resin and 50 parts by weight of a polycarbonate resin (2) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the improving agent (1) was used.
＜比較例９＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）０．０５重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 9>
10 parts by weight of a phosphorus flame retardant (1), 5 parts by weight of a nitrogen compound flame retardant (1) with respect to 100 parts by weight of a mixed resin composition comprising 50 parts by weight of a polylactic acid resin and 50 parts by weight of a polycarbonate resin (2), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 0.05 part by weight of the impact resistance improver (1) was used.
＜比較例１０＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、リン系難燃剤（１）１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（３）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 10>
For 100 parts by weight of the mixed resin composition comprising 30 parts by weight of polylactic acid resin and 70 parts by weight of polycarbonate resin (2), 10 parts by weight of phosphorus flame retardant (1), 5 parts by weight of nitrogen compound flame retardant (1), A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the impact resistance improver (3) was used.
＜比較例１１＞
ポリ乳酸樹脂３０重量部、ポリカーボネート樹脂（２）７０重量部からなる混合樹脂組成物１００重量部に対し、ハロゲン系難燃剤１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 11>
10 parts by weight of halogen-based flame retardant, 5 parts by weight of nitrogen-based flame retardant (1), impact resistance with respect to 100 parts by weight of the mixed resin composition comprising 30 parts by weight of polylactic acid resin and 70 parts by weight of polycarbonate resin (2) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight of the improving agent (1) was used.
＜比較例１２＞
ポリ乳酸樹脂５０重量部、ポリカーボネート樹脂（２）５０重量部からなる混合樹脂組成物１００重量部に対し、タルク１０重量部、窒素化合物系難燃剤（１）５重量部、耐衝撃性改良剤（１）１重量部を添加したポリ乳酸系樹脂組成物を用いた他は、実施例１と同様にして厚さ０．４ｍｍのシートを作成した。
<Comparative Example 12>
10 parts by weight of talc, 5 parts by weight of a nitrogen compound-based flame retardant (1), impact modifier (100 parts by weight of a mixed resin composition comprising 50 parts by weight of a polylactic acid resin and 50 parts by weight of a polycarbonate resin (2) 1) A sheet having a thickness of 0.4 mm was prepared in the same manner as in Example 1 except that the polylactic acid resin composition added with 1 part by weight was used.
得られたシートの難燃性、耐熱性、および加工性を、以下の方法により○、×で評価した。
＜難燃性＞
１２．７×１２７ｍｍの試験片を用い、アメリカＵＬ規格サブジェクト９４（ＵＬ９４）の垂直燃焼試験法に準拠し燃焼試験を行い、Ｖ−０またはＶＴＭ−０の評価が得られたものを○、それ以外を×とした。
＜耐熱性＞
ＡＳＴＭ Ｄ６４８に準拠し熱変形温度（荷重１．８２ＭＰａ）を測定し、８５℃以上のものを○、それ以下のものを×とした。なお、ＡＳＴＭ Ｄ６４８では試験片の最小厚さは３．０ｍｍと規定されているので、この耐熱性評価においてのみ、押出成形により作成した厚さ３．０ｍｍのシートを用いた。
＜折曲げおよび打抜き加工性＞
罫線曲げおよびトムソン打抜きを行い、割れおよび欠けの発生しなかったものを○、発生したものを×とした。
The flame retardancy, heat resistance, and workability of the obtained sheet were evaluated by ○ and × by the following methods.
<Flame retardance>
Using a test piece of 12.7 × 127 mm, a combustion test was performed in accordance with the vertical combustion test method of the US UL standard subject 94 (UL94), and V-0 or VTM-0 evaluation was obtained. Except for x.
<Heat resistance>
The heat distortion temperature (load 1.82 MPa) was measured in accordance with ASTM D648. In ASTM D648, since the minimum thickness of the test piece is defined as 3.0 mm, a sheet having a thickness of 3.0 mm produced by extrusion molding was used only in this heat resistance evaluation.
<Bending and punching workability>
Ruled line bending and Thomson punching were performed, and no crack or chipping occurred.
また、石油資源枯渇防止／炭酸ガス排出抑制効果につき、下記の基準により○、×で評価した。
＜石油資源枯渇防止／炭酸ガス排出抑制効果＞
バイオプラマークが取得可能な、ポリ乳酸系樹脂組成物中のポリ乳酸樹脂含有量が２５重量％以上のものを○、未満のものを×とした。
＜環境への影響＞
ハロゲン系の物質が含まれていないものを○、含まれているものを×とした。
<Prevention of oil resource depletion / CO2 emission control effect>
A sample having a polylactic acid resin content of 25% by weight or more in the polylactic acid-based resin composition from which a bioplastic mark can be obtained is rated as ○, and a value less than that is marked as ×.
<Environmental impact>
A sample that does not contain a halogen-based substance is indicated by ○, and a sample that contains a halogen-based material is indicated by ×.
表１および表２の結果より、本発明の範囲の通りのポリ乳酸樹脂、ポリカーボネート樹脂、リン系難燃剤、窒素化合物系難燃剤、反応型の官能基を有する耐衝撃性改良剤を含有するポリ乳酸系樹脂組成物から得られた電子機器向け難燃性樹脂シートである実施例１〜１５においては、難燃性、耐熱性、および折曲げや打抜き加工性に優れ、且つ石油資源枯渇防止／炭酸ガス排出抑制効果に良好な結果を示している。これに対し本発明の技術範囲を逸脱する比較例１〜１２においては、難燃性、耐熱性、折曲げや打抜き加工性、または石油資源枯渇防止／炭酸ガス排出抑制効果のいずれかに劣るものであった。 From the results of Tables 1 and 2, the polylactic acid resin, polycarbonate resin, phosphorus-based flame retardant, nitrogen compound-based flame retardant, and the impact resistance improver having a reactive functional group as in the scope of the present invention are included. In Examples 1 to 15 which are flame retardant resin sheets for electronic devices obtained from lactic acid-based resin compositions, they are excellent in flame retardancy, heat resistance, and bendability and punching workability, and prevent petroleum resource depletion / It shows good results for the carbon dioxide emission suppression effect. On the other hand, in Comparative Examples 1 to 12 that depart from the technical scope of the present invention, the flame retardancy, heat resistance, bending and punching workability, or oil resource depletion prevention / carbon dioxide emission suppression effect is inferior. Met.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007152687A JP2008303320A (en) | 2007-06-08 | 2007-06-08 | Polylactic acid based flame retardant thin-wall sheet for electronic equipment |
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| JP2007152687A JP2008303320A (en) | 2007-06-08 | 2007-06-08 | Polylactic acid based flame retardant thin-wall sheet for electronic equipment |
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