JP2006257314A5

JP2006257314A5 -

Info

Publication number: JP2006257314A5
Application number: JP2005078373A
Authority: JP
Filing date: 2005-03-18
Publication date: 2007-10-18
Anticipated expiration: 2025-03-18

Description

本発明は、ＬＥＤの製造工程を想定した高温加熱処理を行っても、変色せずに、高い白色度を維持し、可視光領域での反射率特性に優れたＬＥＤ用リフレクタを与えるポリアミド樹脂組成物を提供することを目的とする。 The present invention provides a polyamide resin composition that provides a reflector for an LED that maintains high whiteness and is excellent in reflectance characteristics in the visible light region without being discolored even when subjected to a high-temperature heat treatment assuming an LED manufacturing process. The purpose is to provide goods.

上記の課題を解決すべく鋭意研究を重ねた結果、特定のポリアミド樹脂と、このポリアミド樹脂に対して、酸化チタン、水酸化マグネシウムおよび特定の強化材とをそれぞれ特定量含有したポリアミド樹脂組成物が、前述の目的を達成することを見出し、本発明を完成させるに至った。 As a result of earnest research to solve the above problems, a polyamide resin composition containing a specific amount of a specific polyamide resin and a specific amount of titanium oxide, magnesium hydroxide and a specific reinforcing material with respect to the polyamide resin is obtained. The present inventors have found that the above-described object can be achieved and have completed the present invention.

即ち、本発明は、テレフタル酸単位を５０〜１００モル％含有するジカルボン酸単位（ａ）と１，９−ノナンジアミン単位および／または２−メチル−１，８−オクタンジアミン単位を６０〜１００モル％含有するジアミン単位（ｂ）とからなるポリアミド樹脂（Ａ）、該ポリアミド樹脂（Ａ）１００質量部に対して、酸化チタン（Ｂ）を５〜１００質量部、水酸化マグネシウム（Ｃ）を０．５〜３０質量部、および繊維状充填剤および針状充填剤からなる群より選ばれる少なくとも１種の強化材（Ｄ）を２０〜１００質量部を含有するＬＥＤリフレクタ成形用ポリアミド樹脂組成物、およびこのＬＥＤリフレクタ成形用ポリアミド樹脂組成物からなるＬＥＤリフレクタを提供する。 That is, the present invention relates to a dicarboxylic acid unit (a) containing 50 to 100 mol% of terephthalic acid units, 60 to 100 mol% of 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit. 5-100 parts by mass of titanium oxide (B) and 0.1% of magnesium hydroxide (C) with respect to 100 parts by mass of the polyamide resin (A) comprising the diamine unit (b) to be contained and 100 parts by mass of the polyamide resin (A). 5 to 30 parts by mass, and a polyamide resin composition for molding an LED reflector containing 20 to 100 parts by mass of at least one reinforcing material (D) selected from the group consisting of a fibrous filler and an acicular filler, and An LED reflector comprising the polyamide resin composition for molding an LED reflector is provided.

また、本発明のＬＥＤリフレクタ成形用ポリアミド樹脂組成物は、その構成要件に高温加熱処理後にも高い白色度を維持するための要件を付加した場合には、ＬＥＤリフレクタのみならず他の用途にも好ましく適用可能となる。このような観点から把握した本発明は、テレフタル酸単位を５０〜１００モル％含有するジカルボン酸単位（ａ）と１，９−ノナンジアミン単位および／または２−メチル−１，８−オクタンジアミン単位を６０〜１００モル％含有するジアミン単位（ｂ）とからなるポリアミド樹脂（Ａ）、該ポリアミド樹脂（Ａ）１００質量部に対して、酸化チタン（Ｂ）を５〜１００質量部、水酸化マグネシウム（Ｃ）を０．５〜３０質量部、および繊維状充填剤および針状充填剤からなる群より選ばれる少なくとも１種の強化材（Ｄ）を２０〜１００質量部含有し、かつ１７０℃で２時間加熱処理後の、スペクトロフォトメーターによる波長４７０ｎｍの反射率が９２％以上であるポリアミド樹脂材料、およびこのポリアミド樹脂材料からなる成形品を提供する。 In addition, the polyamide resin composition for molding an LED reflector of the present invention can be used not only for LED reflectors but also for other applications when the requirement for maintaining high whiteness after high-temperature heat treatment is added to its constituent requirements. Preferably applicable. This invention grasped | ascertained from such a viewpoint WHEREIN: The dicarboxylic acid unit (a) containing a terephthalic acid unit 50-100 mol%, a 1,9-nonanediamine unit, and / or a 2-methyl- 1,8-octanediamine unit are contained. The polyamide resin (A) composed of 60 to 100 mol% of the diamine unit (b) and 100 parts by mass of the polyamide resin (A), 5 to 100 parts by mass of titanium oxide (B), magnesium hydroxide ( 0.5 to 30 parts by mass of C) and 20 to 100 parts by mass of at least one reinforcing material (D) selected from the group consisting of a fibrous filler and an acicular filler, and 2 at 170 ° C. A polyamide resin material having a reflectivity at a wavelength of 470 nm by a spectrophotometer of 92% or more after a time heat treatment, and a molded article comprising this polyamide resin material To provide.

本発明のＬＥＤリフレクタ成形用ポリアミド樹脂組成物は、ジカルボン酸単位とジアミン単位とからなるポリアミド樹脂（Ａ）、酸化チタン（Ｂ）、水酸化マグネシウム（Ｃ）、および特定の強化材（Ｄ）を含有する。 The polyamide resin composition for molding an LED reflector of the present invention comprises a polyamide resin (A) comprising a dicarboxylic acid unit and a diamine unit, titanium oxide (B), magnesium hydroxide (C), and a specific reinforcing material (D). contains.

また、本発明のポリアミド樹脂材料は、本発明のＬＥＤリフレクタ成形用ポリアミド樹脂組成物と同様に、ジカルボン酸単位とジアミン単位とからなるポリアミド樹脂（Ａ）、酸化チタン（Ｂ）、水酸化マグネシウム（Ｃ）、および特定の強化材（Ｄ）を含有し、更に、高温加熱処理後にも高い白色度を維持するために、１７０℃で２時間加熱処理後の、スペクトロフォトメーターによる波長４７０ｎｍの反射率が９２％以上の樹脂材料である。 In addition, the polyamide resin material of the present invention is composed of a polyamide resin (A), titanium oxide (B), magnesium hydroxide (comprising a dicarboxylic acid unit and a diamine unit, like the polyamide resin composition for molding an LED reflector of the present invention. C), and a specific reinforcing material (D), and in order to maintain high whiteness even after high-temperature heat treatment, reflectivity at a wavelength of 470 nm by a spectrophotometer after heat treatment at 170 ° C. for 2 hours Is a resin material of 92% or more.

白度
この板を使用し、ＳＭカラーコンピューター（スガ試験機（株）製）を用いて、ＪＩＳＺ８７３０に規定されるハンターの色差式による明度（Ｌ値）、赤色度（ａ値）および黄色度（ｂ値）を求めた。また、以下の式（２）に従って、白色度（ハンター式）を算出した。以下式（２）中、ａは上記赤色度（ａ値）を表し、ｂは上記黄色度（ｂ値）を表し、Ｌは上記明度（Ｌ値）を表す。 Whiteness Using this plate, using a SM color computer (manufactured by Suga Test Instruments Co., Ltd.), brightness (L value), redness (a value) and yellowness according to Hunter's color difference formula defined in JIS Z8730 (B value) was determined. Moreover, the whiteness (Hunter formula) was calculated according to the following formula (2). In the following formula (2) , a represents the redness (a value), b represents the yellowness (b value), and L represents the lightness (L value).

〔ポリアミド〕
ＰＡ９Ｔ：
特開平７−２２８６８９号公報の実施例１に記載された方法に従って調製した、テレフタル酸単位と、１，９−ノナンジアミン単位および２−メチル−１，８−オクタンジアミン単位（１，９−ノナンジアミン単位：２−メチル−１，８−オクタンジアミン単位のモル比が８５：１５）からなる、極限粘度［η］（濃硫酸中、３０℃で測定）が０．９ｄｌ／ｇ、融点が３０６℃、末端封止率が７７％（末端封止剤：安息香酸）であるポリアミド。〔polyamide〕
PA9T:
A terephthalic acid unit, a 1,9-nonanediamine unit and a 2-methyl-1,8 - octanediamine unit (1,9-nonanediamine unit) prepared according to the method described in Example 1 of JP-A-7-228689 : Mole ratio of 2-methyl-1,8 - octanediamine unit is 85:15), intrinsic viscosity [η] (measured in concentrated sulfuric acid at 30 ° C.) is 0.9 dl / g, melting point is 306 ° C. Polyamide having an end capping rate of 77% (end capping agent: benzoic acid).

〔強化材（Ｄ）〕
ｃ：日東紡績（株）社製、「ＣＳ３Ｊ２２５」（ガラス繊維）
ｄ：ＮｙｃｏＭｉｎｅｒａｌｓ，Ｉｎｃ、「Ｎｙｇｌｏｓ４」（ワラストナイト）
ｅ：四国化成社製、「ＹＳ３Ａ」（ホウ酸アルミニウム） [Reinforcing material (D)]
c: “CS3J225” (glass fiber) manufactured by Nittobo Co., Ltd.
d: Nyco Minerals, Inc, “Nygros 4” (Wollastonite)
e: “YS3A” (aluminum borate), manufactured by Shikoku Kasei Co., Ltd.

実施例１〜３および比較例１〜５
表１に示すポリアミドを減圧下、１２０℃で２４時間乾燥した後、表１に示す量の水酸化マグネシウム、酸化チタン、光安定剤および離型剤とドライブレンドし、得られた混合物を２軸押出機（スクリュー径：３０ｍｍ、Ｌ／Ｄ＝２８、シリンダー温度３２０℃、回転数１５０ｒｐｍ）のホッパーからフィードして、同時に、サイドフィーダーより表１に示す量の強化材を添加して溶融混練し、ストランド状に押出した後、ペレタイザにより切断してペレット状のポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物を使用し、前記した方法に従って所定形状の試験片を作製し、各種物性を評価した。結果を表１に示す。 Examples 1-3 and Comparative Examples 1-5
The polyamide shown in Table 1 was dried under reduced pressure at 120 ° C. for 24 hours, and then dry-blended with the amounts of magnesium hydroxide, titanium oxide, light stabilizer and release agent shown in Table 1, and the resulting mixture was biaxially mixed. Feed from the hopper of an extruder (screw diameter: 30 mm, L / D = 28, cylinder temperature 320 ° C., rotation speed 150 rpm), and simultaneously add the reinforcing material in the amount shown in Table 1 from the side feeder and melt knead. After extruding into a strand, the pellet was cut by a pelletizer to obtain a pellet-shaped polyamide resin composition. Using the obtained polyamide resin composition, test pieces having a predetermined shape were prepared according to the above-described method, and various physical properties were evaluated. The results are shown in Table 1.

表１から明らかなように、実施例１〜３の試験片は、ＬＥＤの製造工程を想定した高温加熱処理を行っても、白色度が高く、波長４７０ｎｍの反射率が９２％以上を保持している。さらに、鉛フリーハンダに対応した耐熱性を保持している。それに対し、比較例１の試験片の場合、水酸化マグネシウムを含有していないので、加熱処理後の波長４７０ｎｍの反射率が９２％未満となる。比較例２の試験片の場合には、酸化防止剤を含有するが、水酸化マグネシウムを含有しないので、やはり加熱処理後の波長４７０ｎｍの反射率が９２％未満となる。また、水酸化マグネシウムを含有するが、ポリアミド樹脂１００質量部に対し０．５質量部未満の含有量である比較例３の試験片の場合にも、やはり加熱処理後の波長４７０ｎｍの反射率が９２％未満となる。ポリアミド樹脂のジアミン単位として、１，９−ノナンジアミン単位および２−メチル−１，８−オクタンジアミン以外のヘキサンジアミンを使用した比較例４の試験片の場合には、比較例１に比べて、更に、白度と反射率の結果が劣ることがわかる。比較例４に水酸化マグネシウムを加えても加熱処理後の波長４７０ｎｍの反射率が９２％未満となることがわかる（比較例５参照）。 As can be seen from Table 1, the test pieces of Examples 1 to 3 have high whiteness and a reflectance of 470 nm at a wavelength of 92% or higher even when subjected to high-temperature heat treatment assuming the LED manufacturing process. ing. Furthermore, heat resistance corresponding to lead-free solder is maintained. On the other hand, since the test piece of Comparative Example 1 does not contain magnesium hydroxide, the reflectance at a wavelength of 470 nm after the heat treatment is less than 92%. In the case of the test piece of Comparative Example 2, since it contains an antioxidant but does not contain magnesium hydroxide, the reflectance at a wavelength of 470 nm after the heat treatment is also less than 92%. Further, in the case of the test piece of Comparative Example 3 containing magnesium hydroxide but having a content of less than 0.5 parts by mass with respect to 100 parts by mass of the polyamide resin, the reflectance at a wavelength of 470 nm after the heat treatment is still present. Less than 92%. In the case of the test piece of Comparative Example 4 using hexanediamine other than 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine as the diamine unit of the polyamide resin, compared to Comparative Example 1, It can be seen that the results of whiteness and reflectance are inferior. It can be seen that even when magnesium hydroxide is added to Comparative Example 4, the reflectance at a wavelength of 470 nm after the heat treatment is less than 92% (see Comparative Example 5).

Claims

Dicarboxylic acid unit (a) containing 50 to 100 mol% of terephthalic acid unit and diamine unit containing 60 to 100 mol% of 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit (b ), 100-100 parts by mass of the polyamide resin (A), 5-100 parts by mass of titanium oxide (B), 0.5-30 parts by mass of magnesium hydroxide (C), And a polyamide resin composition for molding an LED reflector, containing 20 to 100 parts by mass of at least one reinforcing material (D) selected from the group consisting of a fibrous filler and an acicular filler.

The polyamide resin composition for molding an LED reflector according to claim 1 or 2, wherein the reinforcing material (D) is at least one selected from the group consisting of glass fiber, wollastonite, potassium titanate whisker, and aluminum borate whisker.

Dicarboxylic acid unit (a) containing 50 to 100 mol% of terephthalic acid unit and diamine unit containing 60 to 100 mol% of 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit (b ), 100-100 parts by mass of the polyamide resin (A), 5-100 parts by mass of titanium oxide (B), 0.5-30 parts by mass of magnesium hydroxide (C), And at least one reinforcing material (D) selected from the group consisting of a fibrous filler and an acicular filler, and a wavelength by a spectrophotometer after heat treatment at 170 ° C. for 2 hours A polyamide resin material having a reflectance at 470 nm of 92% or more.

The polyamide resin material according to claim 7 or 8, wherein the reinforcing material (D) is at least one selected from the group consisting of glass fiber, wollastonite, potassium titanate whisker, and aluminum borate whisker.