JP2000234066A - Clear thermoplastic resin composition and heat-ray- intercepting glazing material prepared therefrom - Google Patents
Clear thermoplastic resin composition and heat-ray- intercepting glazing material prepared therefromInfo
- Publication number
- JP2000234066A JP2000234066A JP11356134A JP35613499A JP2000234066A JP 2000234066 A JP2000234066 A JP 2000234066A JP 11356134 A JP11356134 A JP 11356134A JP 35613499 A JP35613499 A JP 35613499A JP 2000234066 A JP2000234066 A JP 2000234066A
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- Prior art keywords
- thermoplastic resin
- resin composition
- transparent thermoplastic
- inorganic compound
- heat ray
- 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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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、可視光には透過性
で選択的に赤外線を遮蔽する機能を有し、透明性、機械
強度、耐久性に優れ、一般窓、自動車のガラス部品等の
熱線遮蔽性グレージング材、赤外線カットフィルター等
の光学材、農業用フィルム等多くの用途に好適な、透明
熱可塑性樹脂組成物及びこれを用いた熱線遮蔽性グレー
ジング材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a function of transmitting visible light and selectively blocking infrared rays, and is excellent in transparency, mechanical strength, and durability. The present invention relates to a transparent thermoplastic resin composition suitable for many uses such as a heat ray shielding glazing material, an optical material such as an infrared cut filter, an agricultural film, and a heat ray shielding glazing material using the same.
【０００２】[0002]
【従来の技術】可視光線に対して透過性があり、かつ赤
外線を遮蔽する材料としては、酸化錫、酸化インジウム
等の金属酸化物、フタロシアニン系等の有機色素及びジ
チオール系等の有機金属錯塩等が知られているが、有機
色素及び有機金属錯塩系は可視光線の透過率が低く、暗
褐色から暗青色の濃厚な着色を有している上、耐久性の
点でも満足できるものではなかった。一方、酸化錫、酸
化インジウム等の金属酸化物は可視光線透過率が高く、
耐久性にも優れているものの、溶剤、樹脂等に不溶な粒
子状であるため、一次粒子を細かくしても凝集等による
分散不良を起こしやすく、透明樹脂中に溶融混練して分
散させた場合、特開平２−１３６２３０号公報に示され
るように可視領域の透過光を散乱や拡散してヘーズが増
大し、さらに機械強度等の品質も低下するという問題を
有していた。このため、積層体中のフィルムやコーティ
ング層等の薄膜としての利用がほとんどであり、成形体
としての使用法に多くの制限があった。2. Description of the Related Art Materials which are transparent to visible light and shield infrared rays include metal oxides such as tin oxide and indium oxide, organic dyes such as phthalocyanine, and organic metal complex salts such as dithiol. However, organic dyes and organometallic complex salts have low visible light transmittance, have a dark brown to dark blue color, and are not satisfactory in terms of durability. . On the other hand, metal oxides such as tin oxide and indium oxide have high visible light transmittance,
Although it has excellent durability, it is in the form of particles that are insoluble in solvents, resins, etc., so it is easy to cause poor dispersion due to aggregation etc. even if the primary particles are made fine, and when melt-kneaded and dispersed in a transparent resin As described in Japanese Patent Application Laid-Open No. 2-136230, there has been a problem that the haze is increased by scattering or diffusing the transmitted light in the visible region, and the quality such as mechanical strength is also reduced. For this reason, it is mostly used as a thin film such as a film or a coating layer in a laminate, and there are many restrictions on the use as a molded article.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、可視領域の
透過光の拡散や散乱が少なく、機械強度に優れ、熱線遮
蔽性能を有する透明熱可塑性樹脂組成物を提供するもの
である。SUMMARY OF THE INVENTION The present invention is to provide a transparent thermoplastic resin composition which has little diffusion and scattering of transmitted light in the visible region, has excellent mechanical strength, and has heat ray shielding performance.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、かかる問
題を解決すべく鋭意検討した結果、透明な熱可塑性樹脂
の溶融状態に熱線遮蔽性無機化合物を混練し分散化する
に際し、熱線遮蔽性無機化合物微粒子と特定の分散剤の
組み合わせが、成形体のヘイズ及び機械強度の悪化防止
に有効であるのみならず、驚くべきことに熱線遮蔽特性
も改善できることを見いだし本発明に至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve such a problem, and as a result, when kneading and dispersing a heat ray-shielding inorganic compound in a molten state of a transparent thermoplastic resin, a heat ray-shielding inorganic compound is used. The present inventors have found that the combination of the inorganic fine particles and the specific dispersant is effective not only for preventing haze and deterioration of mechanical strength of the molded article but also for surprisingly improving the heat ray shielding property.
【０００５】すなわち、本発明は、透明熱可塑性樹脂１
００重量部に、熱線遮蔽性無機化合物０．００１〜１重
量部及び下記式（１）で表される分散剤を、該樹脂の溶
融条件下で混練し、かつ該分散剤の含有量が下記関係式
（２）を満たすことを特徴とする透明熱可塑性樹脂組成
物及びこれを用いた熱線遮蔽性グレージング材に存す
る。 （ＲＣＯＯ）ｍＸ （１） （式中、Ｒは、炭素数７〜３０の飽和脂肪族炭化水素基
又は炭素数６〜３０の芳香族炭化水素基であり、ｍは、
１〜４の整数であり、Ｘは、水素原子又はアルコール性
水酸基を有する炭素数２〜３０の多価アルコール残基で
あり、ｍ個のＲは、同一でも異なってもよい。） ０．２５≦Ａ／Ｂ≦１００ （２） （式中、Ａは、該分散剤の含有量（重量部）であり、Ｂ
は、熱線遮蔽性無機化合物の含有量（重量部）であ
る。）That is, the present invention relates to a transparent thermoplastic resin 1
0.001 part by weight of a heat ray-shielding inorganic compound and 0.001 part by weight of a dispersant represented by the following formula (1) are kneaded under melting conditions of the resin, and the content of the dispersant is as follows: A transparent thermoplastic resin composition characterized by satisfying the relational expression (2) and a heat ray shielding glazing material using the same. (RCOO) mX (1) (wherein, R is a saturated aliphatic hydrocarbon group having 7 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and m is
X is an integer of 1 to 4, X is a hydrogen atom or a polyhydric alcohol residue having 2 to 30 carbon atoms having an alcoholic hydroxyl group, and m Rs may be the same or different. 0.25 ≦ A / B ≦ 100 (2) (where A is the content (parts by weight) of the dispersant;
Is the content (parts by weight) of the heat ray shielding inorganic compound. )
【０００６】[0006]
【発明の実施の形態】透明熱可塑性樹脂 本発明で使用する透明熱可塑性樹脂としては、可視領域
の光線透過率が高い透明な熱可塑性樹脂であれば特に制
限はなく、例えば、３ｍｍ厚の板状成形体としたときの
ＪＩＳ Ｒ ３１０６記載の可視光透過率が５０％以上
で、ＪＩＳ Ｋ７１０５記載のヘイズが３０％以下のも
のが挙げられる。具体的には、ポリカーボネート、ポリ
エステル、ポリスチレン、ポリメチルメタクリレート、
塩化ビニル、アクリロニトリル−スチレン共重合体、ポ
リ−４−メチルペンテン−１等を挙げることができる。
これらの中でも、ポリカーボネートは機械強度に優れる
ため好ましく、芳香族ポリカーボネートがさらに好まし
い。芳香族ポリカーボネートとしては、２，２−ビス
（４−ヒドロキシフェニル）プロパン、２，２−ビス
（３，５−ジブロモ−４−ヒドロキシフェニル）プロパ
ンで例示される、二価のフェノール系化合物の一種以上
と、ホスゲン又はジフェニルカーボネート等で例示され
る、カーボネート前駆体とから、界面重合、溶融重合又
は固相重合等の公知の方法によって得られる重合体が例
示できる。特に、本発明においては、機械強度、透明性
から、２５℃におけるメチレンクロライド溶液の粘度よ
り換算した粘度平均分子量が１００００〜４００００の
芳香族ポリカーボネートが特に好ましい。また、該芳香
族ポリカーボネートの末端構造は任意に選択でき、未封
止末端に存在するフェノール性ＯＨ基の量が、全末端の
５０〜０．１ｍｏｌ％の範囲であることが好ましく、末
端はその他の構造に修飾が行われていてもよく、分岐構
造を有していてもよい。また、該芳香族ポリカーボネー
トに、透明性を損なわない範囲で、他樹脂を配合しても
かまわない。配合可能な樹脂としては、ポリエチレンテ
レフタレート樹脂、ポリアリレート樹脂、ポリカプロラ
クトン等のポリエステル系樹脂、ポリスチレン系樹脂等
をあげることができる。透明熱可塑性樹脂の形状は、ペ
レット、粒状、粉体等、任意であるが、熱線遮蔽性無機
化合物との混合性の点で、粉末状であることが好まし
い。BEST MODE FOR CARRYING OUT THE INVENTION Transparent thermoplastic resin The transparent thermoplastic resin used in the present invention is not particularly limited as long as it is a transparent thermoplastic resin having a high light transmittance in the visible region. When the shaped article is formed, the visible light transmittance described in JIS R 3106 is 50% or more and the haze described in JIS K7105 is 30% or less. Specifically, polycarbonate, polyester, polystyrene, polymethyl methacrylate,
Examples thereof include vinyl chloride, acrylonitrile-styrene copolymer, and poly-4-methylpentene-1.
Among them, polycarbonate is preferable because of its excellent mechanical strength, and aromatic polycarbonate is more preferable. As the aromatic polycarbonate, one of divalent phenolic compounds exemplified by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane From the above and a carbonate precursor exemplified by phosgene or diphenyl carbonate, a polymer obtained by a known method such as interfacial polymerization, melt polymerization or solid phase polymerization can be exemplified. Particularly, in the present invention, from the viewpoint of mechanical strength and transparency, an aromatic polycarbonate having a viscosity average molecular weight of 10,000 to 40,000 calculated from the viscosity of a methylene chloride solution at 25 ° C. is particularly preferable. Further, the terminal structure of the aromatic polycarbonate can be arbitrarily selected, and the amount of the phenolic OH group present at the unsealed terminal is preferably in the range of 50 to 0.1 mol% of the entire terminal, and the terminal is other than that. May be modified or have a branched structure. Further, other resins may be added to the aromatic polycarbonate as long as the transparency is not impaired. Examples of resins that can be added include polyester resins such as polyethylene terephthalate resin, polyarylate resin, and polycaprolactone, and polystyrene resins. The shape of the transparent thermoplastic resin is arbitrary, such as pellets, granules, powders, etc., but is preferably in the form of powder from the viewpoint of mixing with the heat ray shielding inorganic compound.
【０００７】熱線遮蔽性無機化合物 本発明で使用する熱線遮蔽性無機化合物は、透明性を損
なわない点で、金属酸化物半導体が選択される。なかで
も、下記（ａ）、（ｂ）、（ｃ）から選ばれた少なくと
も１種であることが好ましい。 （ａ）アンチモンドープ酸化錫微粒子（ＡＴＯ） （ｂ）Ｉｎ、Ｇａ、Ａｌ及びＳｂよりなる群から選ばれ
た少なくとも１種の元素を含有する酸化亜鉛微粒子 （ｃ）錫ドープ酸化インジウム微粒子（ＩＴＯ） ＡＴＯは、酸化錫と酸化アンチモンの固溶体であり、Ａ
ＴＯ中のアンチモン含有量は１〜２０重量％であること
が好ましい。上記酸化亜鉛微粒子の場合、Ｉｎ、Ｇａ、
Ａｌ及びＳｂよりなる群から選ばれた少なくとも１種の
元素の含有量は、該微粒子の重量に対し１〜４０重量％
であることが好ましく、これらの元素の中では、アンチ
モンが好ましい。また、ＩＴＯの場合、ＩＴＯに対して
錫原子が３０重量％以下であることが好ましく、１〜２
０重量％であることがより好ましい。この他、酸化錫
や、インジウム−亜鉛−酸素を構成成分とする非晶質酸
化物も挙げられる。 Heat-Shielding Inorganic Compound As the heat-shielding inorganic compound used in the present invention, a metal oxide semiconductor is selected from the viewpoint that transparency is not impaired. Among them, at least one selected from the following (a), (b), and (c) is preferable. (A) Antimony-doped tin oxide fine particles (ATO) (b) Zinc oxide fine particles containing at least one element selected from the group consisting of In, Ga, Al and Sb (c) Tin-doped indium oxide fine particles (ITO) ATO is a solid solution of tin oxide and antimony oxide.
The content of antimony in TO is preferably 1 to 20% by weight. In the case of the zinc oxide fine particles, In, Ga,
The content of at least one element selected from the group consisting of Al and Sb is 1 to 40% by weight based on the weight of the fine particles.
Is preferable, and among these elements, antimony is preferable. In the case of ITO, tin atoms are preferably 30% by weight or less based on ITO.
More preferably, it is 0% by weight. In addition, an amorphous oxide containing tin oxide or indium-zinc-oxygen as a constituent is also used.
【０００８】熱線遮蔽性無機化合物は、平均一次粒子径
が１μｍ以下、好ましくは０．２μｍ以下、さらに好ま
しくは０．１μｍ以下の微粉末であることが好ましい。
平均一次粒子径が１μｍより大きいと、成形体のヘイズ
が増大し好ましくない。また、該熱線遮蔽性無機化合物
には、シランカップリング剤処理、ケイ酸コーティング
等、公知の表面処理を行うことができる。また、該熱線
遮蔽性無機化合物は、透明性樹脂１００重量部に対し
て、０．００１〜１重量部、好ましくは０．００１〜
０．２重量部である。０．００１重量部未満では熱線遮
蔽効果が低く、また１重量部以上ではヘイズが悪化し、
分散剤を添加しても十分な透明性が得られない。The heat ray shielding inorganic compound is preferably a fine powder having an average primary particle diameter of 1 μm or less, preferably 0.2 μm or less, more preferably 0.1 μm or less.
If the average primary particle size is larger than 1 μm, the haze of the molded article increases, which is not preferable. The heat ray-shielding inorganic compound can be subjected to a known surface treatment such as a silane coupling agent treatment and a silicic acid coating. The heat ray shielding inorganic compound is used in an amount of 0.001 to 1 part by weight, preferably 0.001 to 1 part by weight, based on 100 parts by weight of the transparent resin.
0.2 parts by weight. If the amount is less than 0.001 part by weight, the heat ray shielding effect is low, and if the amount is more than 1 part by weight, the haze deteriorates,
Even if a dispersant is added, sufficient transparency cannot be obtained.
【０００９】分散剤 本発明で使用される分散剤は、下記式（１）で表され
る。 （ＲＣＯＯ）ｍＸ （１） 上記式（１）中、Ｒは、炭素数７〜３０好ましくは１２
〜３０の飽和脂肪族炭化水素基又は炭素数６〜３０好ま
しくは１２〜３０の芳香族炭化水素基であり、ｍは、１
〜４の整数であり、Ｘは、水素原子又はアルコール性水
酸基を有する炭素数２〜３０の多価アルコール残基であ
り、好ましくはアルコール性水酸基を有する炭素数２〜
３０の多価アルコール残基であり、さらに好ましくはア
ルコール性水酸基を有する炭素数３〜１０の多価アルコ
ール残基であり、ｍ個のＲは、同一でも異なってもよ
い。 Dispersant The dispersant used in the present invention is represented by the following formula (1). (RCOO) mX (1) In the above formula (1), R represents a group having 7 to 30 carbon atoms, preferably 12 carbon atoms.
A saturated aliphatic hydrocarbon group having from 30 to 30 or an aromatic hydrocarbon group having from 6 to 30 carbon atoms, preferably from 12 to 30 carbon atoms;
And X is a hydrogen atom or a polyhydric alcohol residue having 2 to 30 carbon atoms having an alcoholic hydroxyl group, preferably 2 to 3 carbon atoms having an alcoholic hydroxyl group.
It is a polyhydric alcohol residue having 30 and more preferably a polyhydric alcohol residue having an alcoholic hydroxyl group and having 3 to 10 carbon atoms, and m Rs may be the same or different.
【００１０】該分散剤の性状は、常温で固体状態である
のが良く、粉末状、粒状等の性状をもつことが可能であ
るが、透明性樹脂、熱線遮蔽性無機化合物との混練操作
性、ヘイズ低下効果を考慮すると、粉末状であることが
好ましい。液体状態の分散剤では、樹脂と熱線遮蔽性無
機化合物微粒子を混合する際、樹脂に均一に分散し難
く、熱線遮蔽性無機化合物の樹脂への分散を阻害するの
で好ましくない。これらの具体例としては、ステアリン
酸、ベヘニン酸等のカルボン酸類；グリセリンモノステ
アレート、グリセリンジステアレート等のグリセリン脂
肪酸エステル類；ペンタエリスリトールモノステアレー
ト、ペンタエリスリトールジステアレート、ペンタエリ
スリトールトリステアレート等のペンタエリスリトール
脂肪酸エステル類；ソルビタンモノステアレート等のソ
ルビタン脂肪酸エステル類が挙げられる。これらの中
で、グリセリンモノステアレートが好ましい。The properties of the dispersant are preferably in a solid state at normal temperature, and can have properties such as powder and granules. However, the dispersant can be kneaded with a transparent resin or a heat ray shielding inorganic compound. In view of the effect of lowering the haze, the powder is preferably used. A liquid dispersant is not preferable because it is difficult to uniformly disperse the resin and the heat ray-shielding inorganic compound particles in the resin when mixing the resin and the heat ray-shielding inorganic compound particles, and hinders the dispersion of the heat ray-shielding inorganic compound in the resin. Specific examples thereof include carboxylic acids such as stearic acid and behenic acid; glycerin fatty acid esters such as glycerin monostearate and glycerin distearate; pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. And sorbitan fatty acid esters such as sorbitan monostearate. Of these, glycerin monostearate is preferred.
【００１１】これら分散剤の含有量（Ａ）は、透明熱可
塑性樹脂組成物中の熱線遮蔽性無機化合物の含有量
（Ｂ）によって決定され、すなわち、下記式（２）によ
って示される範囲内から選択される。 ０．２５≦Ａ／Ｂ≦１００ （２） 上記式（２）中、Ａは、該分散剤の含有量（重量部）で
あり、Ｂは、熱線遮蔽性無機化合物の含有量（重量部）
である。また、重量部は、いずれも透明熱可塑性樹脂１
００重量部に対する値である。すなわち、Ａ／Ｂは、
０．２５以上、好ましくは０．５以上である。０．２５
未満では、分散剤の効果が十分でなく、成形体のヘイズ
が増加し、赤外線遮蔽性能の改良効果もわずかである。
また、Ａ／Ｂが１００を超えると、ヘーズ改良及び赤外
線遮蔽性能改善効果はあるものの、分散剤の含有量が樹
脂成分量に対して過剰となり、機械強度等の品質に悪影
響を与える。The content (A) of these dispersants is determined by the content (B) of the heat ray-shielding inorganic compound in the transparent thermoplastic resin composition, that is, from the range represented by the following formula (2). Selected. 0.25 ≦ A / B ≦ 100 (2) In the above formula (2), A is the content (parts by weight) of the dispersant, and B is the content (parts by weight) of the heat ray shielding inorganic compound.
It is. In addition, all parts by weight are transparent thermoplastic resin 1
The value is based on 00 parts by weight. That is, A / B is
It is 0.25 or more, preferably 0.5 or more. 0.25
If it is less than 3, the effect of the dispersant is not sufficient, the haze of the molded article increases, and the effect of improving the infrared shielding performance is slight.
If the A / B exceeds 100, the dispersant content becomes excessive with respect to the amount of the resin component, although the haze is improved and the infrared ray shielding performance is improved, which adversely affects the quality such as mechanical strength.
【００１２】透明熱可塑性樹脂組成物 透明熱可塑性樹脂の溶融条件下で、上記熱線遮蔽性無機
化合物及び上記分散剤を混練する方法は、粉末を溶融樹
脂に練り込む際に慣用の、任意の方法で行うことができ
る。例えば、全成分をスーパーミキサー、タンブラー等
で混合後、又は、熱線遮蔽性無機化合物と分散剤等とを
予め混合したものを透明熱可塑性樹脂と混合後、単軸押
出機、二軸押出機、ロール混練機等を用いて混練する方
法が挙げられる。また、透明熱可塑性樹脂と熱線吸収性
無機化合物等を、別々の場所から同一押出機に添加し
て、混練することもできる。 Transparent thermoplastic resin composition The method of kneading the above-mentioned heat ray-shielding inorganic compound and the above-mentioned dispersant under the melting condition of the transparent thermoplastic resin may be any of the conventional methods for kneading powder into molten resin. Can be done with For example, after mixing all components with a super mixer, a tumbler or the like, or after mixing a heat-shielding inorganic compound and a dispersant in advance with a transparent thermoplastic resin, a single-screw extruder, a twin-screw extruder, A method of kneading using a roll kneader or the like can be given. Further, a transparent thermoplastic resin and a heat ray absorbing inorganic compound or the like can be added to the same extruder from different places and kneaded.
【００１３】本発明において、透明熱可塑性樹脂組成物
は、フタロシアニン系、ナフタロシアニン系、硫化銅、
銅イオン等の他の有機、無機系赤外線吸収剤のほか、慣
用の添加剤を配合したものであることができる。例え
ば、任意の色調を与えるため、アゾ系染料、シアニン系
染料、キノリン系染料、ペリレン系染料、カーボンブラ
ック等、通常熱可塑性樹脂の着色に使用されている染
料、顔料のほか、ヒンダードフェノール系、リン系等の
安定剤、離型剤、ヒドロキシベンゾフェノン系、サリチ
ル酸系、ＨＡＬＳ系、トリアゾール系、トリアジン系等
の紫外線吸収剤、カップリング剤、帯電防止剤等を、こ
れらの有効発現量配合したものでもよい。さらに、透明
性を極端に損なわない範囲で、ガラス等のフィラーを配
合したものでもよい。In the present invention, the transparent thermoplastic resin composition comprises phthalocyanine, naphthalocyanine, copper sulfide,
In addition to other organic and inorganic infrared absorbers such as copper ions, conventional additives can be blended. For example, in order to give an arbitrary color tone, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, etc., other than the dyes and pigments usually used for coloring thermoplastic resins, hindered phenol dyes , A phosphorus-based stabilizer, a release agent, a hydroxybenzophenone-based, salicylic acid-based, HALS-based, triazole-based, triazine-based, etc. ultraviolet absorber, coupling agent, antistatic agent, etc. It may be something. Further, a filler such as glass may be blended as long as the transparency is not extremely impaired.
【００１４】熱線遮蔽性グレージング材 本発明の透明熱可塑性樹脂組成物は、透明性及び熱線遮
蔽性に優れ、その成形体は、一般窓、自動車等乗り物の
ガラス部品等の熱線遮蔽性グレージング材として有用で
ある。本発明の熱線遮蔽性グレージング材は、板状、フ
ィルム状、その他任意の形状をとることができる。その
成形方法も、特に制限はなく、押出成形、射出成形、ブ
ロー成形、プレス成形等によることができる。 Heat ray-shielding glazing material The transparent thermoplastic resin composition of the present invention has excellent transparency and heat ray-shielding property, and its molded product is used as a heat ray-shielding glazing material for general windows, glass parts of vehicles such as automobiles and the like. Useful. The heat ray shielding glazing material of the present invention can take a plate shape, a film shape, or any other shape. The molding method is not particularly limited, and may be extrusion molding, injection molding, blow molding, press molding, or the like.
【００１５】本発明の熱線遮蔽性グレージング材は、本
発明組成物の成形体と他の材料との複合体であることが
できる。その場合、本発明組成物の成形体は、表面層又
はラミネート層として、他の透明基板と積層して利用す
る以外に、構造材料として機械強度を担う基板としての
利用も可能である。具体的には、本発明の熱線遮蔽性グ
レージング材が、その表面の両側又は片側に、本発明組
成物以外の材料による、表面層又はラミネート層を形成
したものである場合、該表面層又はラミネート層は、ハ
ードコート、紫外線吸収、防曇、帯電防止、反射防止、
熱線遮蔽等の機能を有する機能性層であってもよい。こ
のような表面層又はラミネート層の形成には、本発明組
成物の成形体の両表面又は一表面に、直接又はプライマ
ー層を介して、本発明組成物以外の材料の塗装等を施し
てもよく、また、本発明組成物以外の材料のフィルム又
はシートを積層一体化してもよい。The heat ray shielding glazing material of the present invention can be a composite of a molded article of the composition of the present invention and another material. In this case, the molded article of the composition of the present invention can be used as a surface layer or a laminate layer, as well as being used by laminating it with another transparent substrate, or as a substrate bearing mechanical strength as a structural material. Specifically, when the heat ray-shielding glazing material of the present invention has a surface layer or a laminate layer formed on both sides or one side of the surface by a material other than the composition of the present invention, the surface layer or the laminate The layers are hard coat, UV absorption, anti-fog, anti-static, anti-reflective,
It may be a functional layer having a function such as heat ray shielding. For the formation of such a surface layer or a laminate layer, both surfaces or one surface of a molded article of the composition of the present invention may be coated with a material other than the composition of the present invention, directly or via a primer layer. Alternatively, a film or sheet of a material other than the composition of the present invention may be laminated and integrated.
【００１６】本発明においては、上記機能性層を有し又
は有しないフィルム又はシートを積層一体化する方法は
特に限定されないが、好ましい例としては、金型の内壁
面の片側又は両側に、予め該フィルム又はシートを装着
し、残余の金型空間に本発明の透明熱可塑性樹脂組成物
を溶融射出充填することにより、該フィルム又はシート
と積層一体化した、機能性層を有し又は有しない、熱線
遮蔽性グレージング材を得ることができる。In the present invention, the method of laminating and integrating the film or sheet having or not having the functional layer is not particularly limited. However, a preferable example is that one side or both sides of the inner wall surface of the mold is previously formed. The film or sheet is mounted, and the remaining mold space is melt-injected and filled with the transparent thermoplastic resin composition of the present invention, whereby the film or sheet is laminated and integrated with the film or sheet, with or without a functional layer. Thus, a heat ray shielding glazing material can be obtained.
【００１７】上記の方法に従い、金型の内壁面に装着す
るフィルム又はシートは、その厚みが、通常１００〜１
０００μｍ、好ましくは２００〜７００μｍのものであ
る。このフィルム又はシートの材料は、いかなる樹脂か
らなるものでもよいが、このフィルム又はシートが、溶
融射出充填によって本発明組成物の成形体と積層一体化
されることを考慮に入れると、通常、本発明該透明熱可
塑性樹脂組成物を構成する樹脂と同一のものを選ぶの
が、熱融着性や光学的均一性の面から好ましく、従っ
て、透明熱可塑性樹脂組成物と同様に、芳香族ポリカー
ボネート又はその組成物であることが好ましい。また、
このフィルム又はシートには、所望により、片面にハー
ドコート、防曇、帯電防止、反射防止及び熱線遮断から
なる群から選ばれた少なくとも一種の機能性層を設ける
こともできる。According to the above method, the film or sheet to be mounted on the inner wall surface of the mold usually has a thickness of 100 to 1
000 μm, preferably 200 to 700 μm. The material of the film or sheet may be made of any resin, but in consideration of the fact that the film or sheet is laminated and integrated with the molded article of the composition of the present invention by melt injection filling, usually, Invention It is preferable to select the same resin as the resin constituting the transparent thermoplastic resin composition from the viewpoint of heat-fusibility and optical uniformity, and therefore, like the transparent thermoplastic resin composition, aromatic polycarbonate Or a composition thereof. Also,
If necessary, at least one functional layer selected from the group consisting of hard coat, anti-fogging, anti-static, anti-reflection, and heat ray blocking may be provided on one side of the film or sheet.
【００１８】該樹脂フィルム又はシートに機能性層を形
成するには、従来公知の種々の方法が用いられる。例え
ば、ハードコート層の形成には、所望によりプライマー
層を設けた上に、エポキシ系、アクリル系、アミノ樹脂
系、ポリシロキサン系、コロイダルシリカ系等のハード
コート剤を塗布し、熱又は紫外線等の手段により硬化す
る方法を用いることができる。防曇層の形成には、通常
水溶性又は親水性樹脂と界面活性剤を必須成分として含
有する防曇塗料を塗布し、硬化する方法を用いることが
できる。そのほか、帯電防止層、反射防止層、熱線遮断
層等を設ける方法も、これらの機能を与える塗料を塗布
して硬化するか、又はこれらの機能を有する薄膜層を真
空蒸着法等の方法により、形成する方法が挙げられる。
また、これらの機能性層を複合層として、二種以上の機
能を同時に備えたものとしてもよい。In order to form a functional layer on the resin film or sheet, various conventionally known methods are used. For example, to form a hard coat layer, a primer layer is provided as desired, and a hard coat agent such as an epoxy-based, acrylic-based, amino resin-based, polysiloxane-based, or colloidal silica-based is applied, and heat or ultraviolet light is applied. Can be used. For forming the anti-fog layer, a method of applying an anti-fog paint containing a water-soluble or hydrophilic resin and a surfactant as essential components and curing the same can be used. In addition, the method of providing an antistatic layer, an antireflection layer, a heat ray blocking layer, and the like is also possible to apply and cure a paint that provides these functions, or to form a thin film layer having these functions by a method such as a vacuum evaporation method. Forming method.
In addition, these functional layers may be used as a composite layer to simultaneously provide two or more functions.
【００１９】さらにこれらの機能性層の他に、又は該機
能性層に、予め美装用塗装処理を施して意匠性を持たせ
る等の方法により、意匠性付与層を形成することも可能
である。シートへの意匠性層の形成は、シートの表面
側、裏面側に限定されることなく、その用途や目的に応
じて任意の箇所に形成することが可能である。In addition to these functional layers, it is also possible to form a design-imparting layer by a method in which the functional layer is preliminarily subjected to a cosmetic coating treatment to impart design properties. . The formation of the designable layer on the sheet is not limited to the front side and the back side of the sheet, but can be formed at any position according to the use or purpose.
【００２０】本発明においては、溶融射出充填時の樹脂
組成物との熱融着を促進し、積層一体化をより確実にす
る目的で、熱可塑性樹脂フィルム又はシートに、プライ
マーコートを施すこともできる。プライマーコートに使
用する樹脂としては、射出用樹脂より溶融粘度が高く、
該フィルム又はシートとよく接着するものが選ばれる。
例えば、射出成形用樹脂と同種で、より高分子量の樹
脂、又はこれを主体とするもの、熱や紫外線により硬化
する樹脂がある。In the present invention, a primer coat may be applied to a thermoplastic resin film or sheet for the purpose of promoting thermal fusion with the resin composition at the time of melt-injection filling and further ensuring lamination integration. it can. As the resin used for the primer coat, the melt viscosity is higher than the injection resin,
Those that adhere well to the film or sheet are selected.
For example, there is a resin of the same kind as the resin for injection molding and having a higher molecular weight, a resin mainly composed of the same, or a resin which is cured by heat or ultraviolet rays.
【００２１】[0021]
【実施例】以下に、実施例により具体的に説明するが、
本発明はその要旨を逸脱しない限り、これによって何等
限定されるものではない。なお、以下の実施例及び比較
例で得られた成形品の物性は、次のようにして測定し
た。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples.
The present invention is not limited in any way without departing from the gist thereof. The physical properties of the molded articles obtained in the following Examples and Comparative Examples were measured as follows.
【００２２】光線透過率：成形品（実施例１〜７又は比
較例１〜４では４ｍｍ厚円盤；実施例８から１３では３
ｍｍ厚プレート）を試料とし、日立製作所（株）製 日
立自記分光光度計Ｕ−３４００を使用して測定した。Light transmittance: molded product (4 mm thick disk in Examples 1 to 7 or Comparative Examples 1 to 4; 3 in Examples 8 to 13)
The thickness was measured using a Hitachi auto-recording spectrophotometer U-3400 manufactured by Hitachi, Ltd. as a sample.
【００２３】ヘイズ：成形品（実施例１〜７又は比較例
１〜４では４ｍｍ厚円盤；実施例８から１３では３ｍｍ
厚板状成形体）を試料とし、ヘイズメーター（スガ試験
機株式会社、商品名ＨＧＭ−２ＤＰ）を使用して測定し
た。Haze: molded product (4 mm thick disk in Examples 1 to 7 or Comparative Examples 1 to 4; 3 mm in Examples 8 to 13)
The thickness was measured using a haze meter (Suga Test Instruments Co., Ltd., trade name HGM-2DP) as a sample.
【００２４】アイゾッド衝撃強度：ＡＳＴＭ Ｄ２５６
に従って３．２ｍｍ厚試験片のノッチありアイゾッド衝
撃強度を測定した。Izod impact strength: ASTM D256
The notched Izod impact strength of a 3.2 mm thick test specimen was measured according to the above.
【００２５】実施例又は比較例で使用した原材料及びそ
の略号は、次のとおりである。 透明熱可塑性樹脂： （１）ＰＣ ポリカーボネート（三菱エンジニアリング
プラスチックス（株）商品、ユーピロンＳ−３０００
Ｆ、粘度平均分子量２１，０００。） （２）ＰＳ ポリスチレン（三菱化学（株）製、商品名
ダイヤレックスＨＨ−１０２。） （３）ポリカーボネート樹脂シート（三菱エンジニアリ
ングプラスチックス（株）商品、ユーピロンシートＣＦ
Ｉ−１。シート中の樹脂の粘度平均分子量：２８００
０。）The raw materials used in Examples and Comparative Examples and their abbreviations are as follows. Transparent thermoplastic resin: (1) PC polycarbonate (a product of Mitsubishi Engineering-Plastics Corporation, Iupilon S-3000)
F, viscosity average molecular weight 21,000. (2) PS polystyrene (manufactured by Mitsubishi Chemical Corporation, trade name: Dialex HH-102) (3) Polycarbonate resin sheet (Mitsubishi Engineering Plastics Co., Ltd., Iupilon sheet CF)
I-1. Viscosity average molecular weight of resin in sheet: 2800
0. )
【００２６】熱線遮蔽性無機化合物： （４）ＡＴＯ アンチモンドープ酸化錫微粒子（平均一
次粒子径０．０１μｍ以下、触媒化成工業（株）商品、
ＥＬＣＯＭ ＴＬ３０。） （５）ＳＺＯ アンチモン酸亜鉛微粒子（平均一次粒子
径０．０２μｍ。） （６）ＩＴＯ 錫ドープ酸化インジウム微粒子（平均一
次粒子径０．１μｍ以下。）Heat ray shielding inorganic compound: (4) ATO antimony-doped tin oxide fine particles (average primary particle diameter: 0.01 μm or less, product of Catalyst Chemical Industry Co., Ltd.
ELCOM TL30. (5) SZO zinc antimonate fine particles (average primary particle diameter 0.02 μm.) (6) ITO tin-doped indium oxide fine particles (average primary particle diameter 0.1 μm or less.)
【００２７】分散剤： （７）ＳＭＧ ステアリン酸モノグリセリド （８）ＰＤＳ ペンタエリスリトールジステアレート （９）ＳＡ ステアリン酸 （１０）ＰＤＥＨ フタル酸ジエチルへキシル （１１）ＺＳ ステアリン酸亜鉛Dispersant: (7) SMG monoglyceride stearate (8) PDS pentaerythritol distearate (9) SA stearic acid (10) PDEH diethylhexyl phthalate (11) ZS zinc stearate
【００２８】実施例１〜７及び比較例１〜４樹脂組成物 ポリカーボネート１００重量部に対して、ＡＴＯ又はア
ンチモン酸亜鉛微粒子及び表−１記載の分散剤を、表−
１記載の割合で配合し、タンブラーで１０分から６０分
混合を行い、単軸押出機（田辺プラスチック株式会社
製、商品名ＶＳ−４０）によりバレル温度２８０℃で混
練しペレット化した。Examples 1 to 7 and Comparative Examples 1 to 4 ATO or zinc antimonate fine particles and the dispersant described in Table 1 were mixed with 100 parts by weight of the resin composition polycarbonate.
The mixture was blended at a ratio of 1 and mixed with a tumbler for 10 to 60 minutes, and kneaded at a barrel temperature of 280 ° C. with a single screw extruder (trade name: VS-40, manufactured by Tanabe Plastics Co., Ltd.) to form pellets.
【００２９】成形品 ａ） アイゾッド衝撃試験片 上記樹脂組成物を射出成形し、３．２ｍｍ厚試験片を調
製した。 ｂ） 光線透過率及びヘイズ測定用試験片 片面にシリコン系熱硬化型ハードコート層を施した、厚
み０．５ｍｍのポリカーボネート樹脂シート（商品名：
ユーピロンシートＣＦＩ−１）２枚を、いずれもハード
コート層が成形品の外表面となるように、直径１００ｍ
ｍ、厚み４ｍｍの円盤状金型内に装着し、両シート間に
溶融した上記樹脂組成物をサイドゲートから射出充填
し、積層一体成形を実施し、４ｍｍ厚円盤を調製した。
これらの試験片を用いて、物性測定を行った結果を、表
−１に示す。 Molded article a) Izod impact test piece The above resin composition was injection molded to prepare a 3.2 mm thick test piece. b) Test piece for measuring light transmittance and haze A 0.5 mm thick polycarbonate resin sheet having a silicon-based thermosetting hard coat layer on one surface (trade name:
Two Iupilon sheets (CFI-1) each having a diameter of 100 m so that the hard coat layer becomes the outer surface of the molded article.
m, a disk-shaped mold having a thickness of 4 mm, and the above resin composition melted between both sheets was injected and filled from a side gate, followed by lamination integral molding to prepare a 4 mm-thick disk.
Table 1 shows the results of measuring the physical properties using these test pieces.
【００３０】〔実施例８〜１２〕ポリカーボネート１０
０重量部に対して、ＩＴＯ及び表−１記載の分散剤を、
表−１記載の割合で配合し、単軸押出機（田辺プラスチ
ック株式会社製、商品名ＶＳ−４０）によりバレル温度
２８０℃で混練しペレット化した。得られたペレットを
射出成形し、厚み３ｍｍの板状成形体及びアイゾッド衝
撃試験用の３．２ｍｍの試験片を得た。これらの試験片
を用いて、物性測定を行った結果を表−１に示す。Examples 8 to 12 Polycarbonate 10
With respect to 0 parts by weight, ITO and the dispersant described in Table 1 were used.
The components were blended at the ratios shown in Table 1, and kneaded at a barrel temperature of 280 ° C using a single screw extruder (trade name: VS-40, manufactured by Tanabe Plastics Corporation) to form pellets. The obtained pellets were injection-molded to obtain a plate-shaped molded product having a thickness of 3 mm and a 3.2-mm test piece for an Izod impact test. Table 1 shows the results of measurement of physical properties using these test pieces.
【００３１】〔比較例５〕実施例８において、分散剤を
用いない以外は、実施例８同様にしてペレット化を行
い、同様に射出成形し、厚み３ｍｍの板状成形体及びア
イゾッド衝撃試験用の３．２ｍｍの試験片を得た。物性
測定結果を表−１に示す。Comparative Example 5 Pellets were formed in the same manner as in Example 8 except that the dispersant was not used, and injection molding was performed in the same manner as in Example 8, to obtain a plate-shaped molded product having a thickness of 3 mm and an Izod impact test. 3.2 mm test piece was obtained. Table 1 shows the measurement results of physical properties.
【００３２】〔比較例６〕実施例９において、分散剤と
して、ステアリン酸モノグリセリドの代わりにステアリ
ン酸亜鉛を用いる以外は、実施例９同様にしてペレット
化を行い、同様に射出成形し、厚み３ｍｍの板状成形体
及びアイゾッド衝撃試験用の３．２ｍｍの試験片を得
た。物性測定結果を表−１に示す。Comparative Example 6 Pelletization was performed in the same manner as in Example 9 except that zinc stearate was used instead of monoglyceride stearate as the dispersant, and injection molding was performed in the same manner as in Example 9 to obtain a thickness of 3 mm. And a 3.2 mm test piece for an Izod impact test were obtained. Table 1 shows the measurement results of physical properties.
【００３３】〔実施例１３〕ポリスチレン１００重量部
に対して、ＩＴＯ及び分散剤ステアリン酸モノグリセリ
ドを表−１記載の割合で配合し、単軸押出機（田辺プラ
スチック株式会社製、商品名ＶＳ−４０）によりバレル
温度２８０℃で混練しペレット化した。得られたペレッ
トを射出成形し、厚み３ｍｍの板状成形体及びアイゾッ
ド衝撃試験用の３．２ｍｍの試験片を得た。物性測定結
果を表−１に示す。Example 13 A single screw extruder (trade name: VS-40, manufactured by Tanabe Plastic Co., Ltd.) was blended with ITO and a dispersant stearic acid monoglyceride in the proportions shown in Table 1 with respect to 100 parts by weight of polystyrene. ) And kneaded at a barrel temperature of 280 ° C to form pellets. The obtained pellets were injection-molded to obtain a plate-shaped molded product having a thickness of 3 mm and a 3.2-mm test piece for an Izod impact test. Table 1 shows the measurement results of physical properties.
【００３４】〔比較例７〕実施例１３において分散剤を
用いない以外は、実施例１３と同様にしてペレット化を
行い、同様に射出成形し、厚み３ｍｍの板状成形体及び
アイゾッド衝撃試験用の３．２ｍｍの試験片を得た。物
性測定結果を表−１に示す。Comparative Example 7 Pelletization was performed in the same manner as in Example 13 except that the dispersant was not used in Example 13, and injection molding was performed in the same manner to obtain a 3 mm-thick plate-shaped molded product and an Izod impact test. 3.2 mm test piece was obtained. Table 1 shows the measurement results of physical properties.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【発明の効果】本発明の透明熱可塑性樹脂組成物は、透
明熱可塑性樹脂に熱線遮蔽性無機化合物微粒子及び特定
の分散剤を特定割合で配合したので、可視光には透過性
で選択的に赤外線を遮蔽する機能を有し、ヘイズが小さ
く、透明性、機械強度に優れ、一般窓、自動車のガラス
部品等の熱線遮蔽性グレージング材、赤外線カットフィ
ルター等の光学材、農業用フィルム等、多くの用途に好
適な、透明樹脂組成物を提供する。According to the transparent thermoplastic resin composition of the present invention, since the heat-shielding inorganic compound fine particles and the specific dispersant are blended in a specific ratio with the transparent thermoplastic resin, the transparent thermoplastic resin is selectively transparent to visible light. Has the function of shielding infrared rays, small haze, excellent transparency, excellent mechanical strength, heat ray shielding glazing materials for general windows and glass parts of automobiles, optical materials such as infrared cut filters, agricultural films, etc. The present invention provides a transparent resin composition suitable for use in the above.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年１２月２０日（１９９９．１２．
２０）[Submission date] December 20, 1999 (1999.12.
20)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３５[Correction target item name] 0035
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３５】[0035]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｋ 5:09） (72)発明者 今泉 洋行 神奈川県平塚市東八幡５丁目６番２号 三 菱エンジニアリングプラスチックス株式会 社技術センター内 (72)発明者 吉井 亨 神奈川県平塚市東八幡５丁目６番２号 三 菱エンジニアリングプラスチックス株式会 社技術センター内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat (Reference) C08K 5:09) (72) Inventor Hiroyuki Imaizumi 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Engineering Plastics (72) Inventor Toru Yoshii 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Engineering-Plastics Co., Ltd. Technical Center
Claims (7)
蔽性無機化合物０．００１〜１重量部及び下記式（１）
で表される分散剤を、該樹脂の溶融条件下で混練し、か
つ該分散剤の含有量が下記関係式（２）を満たすことを
特徴とする透明熱可塑性樹脂組成物。 （ＲＣＯＯ）ｍＸ （１） （式中、Ｒは、炭素数７〜３０の飽和脂肪族炭化水素基
又は炭素数６〜３０の芳香族炭化水素基であり、ｍは、
１〜４の整数であり、Ｘは、水素原子又はアルコール性
水酸基を有する炭素数２〜３０の多価アルコール残基で
あり、ｍ個のＲは、同一でも異なってもよい。） ０．２５≦Ａ／Ｂ≦１００ （２） （式中、Ａは、該分散剤の含有量（重量部）であり、Ｂ
は、熱線遮蔽性無機化合物の含有量（重量部）であ
る。）1. A heat-shielding inorganic compound in an amount of 0.001 to 1 part by weight based on 100 parts by weight of a transparent thermoplastic resin and the following formula (1):
A transparent thermoplastic resin composition characterized by kneading a dispersant represented by the formula (1) under the melting conditions of the resin, and wherein the content of the dispersant satisfies the following relational expression (2). (RCOO) mX (1) (wherein, R is a saturated aliphatic hydrocarbon group having 7 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and m is
X is an integer of 1 to 4, X is a hydrogen atom or a polyhydric alcohol residue having 2 to 30 carbon atoms having an alcoholic hydroxyl group, and m Rs may be the same or different. 0.25 ≦ A / B ≦ 100 (2) (where A is the content (parts by weight) of the dispersant;
Is the content (parts by weight) of the heat ray shielding inorganic compound. )
プ酸化錫微粒子であることを特徴とする請求項１に記載
の透明熱可塑性樹脂組成物。2. The transparent thermoplastic resin composition according to claim 1, wherein the heat ray shielding inorganic compound is antimony-doped tin oxide fine particles.
ｌ及びＳｂよりなる群から選ばれた少なくとも１種の元
素を含有する酸化亜鉛微粒子であることを特徴とする請
求項１に記載の透明熱可塑性樹脂組成物。3. The heat ray shielding inorganic compound is In, Ga, A.
The transparent thermoplastic resin composition according to claim 1, wherein the composition is zinc oxide fine particles containing at least one element selected from the group consisting of l and Sb.
ンジウム微粒子であることを特徴とする請求項１に記載
の透明熱可塑性樹脂組成物。4. The transparent thermoplastic resin composition according to claim 1, wherein the heat ray shielding inorganic compound is tin-doped indium oxide fine particles.
ートである請求項１〜４のいずれか１項に記載の透明熱
可塑性樹脂組成物。5. The transparent thermoplastic resin composition according to claim 1, wherein the transparent thermoplastic resin is an aromatic polycarbonate.
熱可塑性樹脂組成物の成形体であることを特徴とする熱
線遮蔽性グレージング材。6. A heat ray shielding glazing material, which is a molded article of the transparent thermoplastic resin composition according to claim 1.
ルム又はシートを装着し、残余の金型空間に請求項１〜
５のいずれか１項に記載の透明熱可塑性樹脂組成物を溶
融射出充填することにより、該フィルム又はシートと積
層一体化したことを特徴とする熱線遮蔽性グレージング
材。7. A film or sheet is mounted on one or both sides of the inner wall surface of the mold in advance, and the remaining mold space is provided in the remaining mold space.
A heat ray shielding glazing material, characterized by being laminated and integrated with the film or sheet by melt-injecting and filling the transparent thermoplastic resin composition according to any one of items 5 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35613499A JP4191347B2 (en) | 1998-12-16 | 1999-12-15 | Transparent thermoplastic resin composition and heat ray shielding glazing material using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35719198 | 1998-12-16 | ||
| JP10-357191 | 1998-12-16 | ||
| JP35613499A JP4191347B2 (en) | 1998-12-16 | 1999-12-15 | Transparent thermoplastic resin composition and heat ray shielding glazing material using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000234066A true JP2000234066A (en) | 2000-08-29 |
| JP4191347B2 JP4191347B2 (en) | 2008-12-03 |
Family
ID=26580381
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35613499A Expired - Fee Related JP4191347B2 (en) | 1998-12-16 | 1999-12-15 | Transparent thermoplastic resin composition and heat ray shielding glazing material using the same |
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| Country | Link |
|---|---|
| JP (1) | JP4191347B2 (en) |
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