JP6837148B2 - 粒状紫外線吸収剤および樹脂組成物 - Google Patents
粒状紫外線吸収剤および樹脂組成物 Download PDFInfo
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- JP6837148B2 JP6837148B2 JP2019538270A JP2019538270A JP6837148B2 JP 6837148 B2 JP6837148 B2 JP 6837148B2 JP 2019538270 A JP2019538270 A JP 2019538270A JP 2019538270 A JP2019538270 A JP 2019538270A JP 6837148 B2 JP6837148 B2 JP 6837148B2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
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Description
トリアジン系化合物を含む粒状紫外線吸収剤であって、
前記トリアジン系化合物が、下記化合物No.1および化合物No.2のいずれかで表される一または二の化合物を含み、
湿式のレーザー回折式粒度分布測定法による当該粒状紫外線吸収剤の、体積基準の粒子径分布における累積10%粒子径をD10(μm)、累積90%粒子径をD90(μm)としたとき、
D10/D90が0.040以上0.104以下の範囲にある、
湿式のレーザー回折式粒度分布測定法による当該粒状紫外線吸収剤の、体積基準の粒子径分布における体積平均粒子径をMV(μm)とし、個数平均粒子径をMN(μm)としたとき、
MV/MNが11.1以上21.6以下の範囲にある、
粒状紫外線吸収剤が提供される。
当該トリアジン系化合物は、下記一般式(I)で表される化合物を含有することが好ましい。これらを単独で用いても2種以上を組み合わせて用いてもよい。
なお、粒状紫外線吸収剤は下記トリアジン系化合物のみで構成されていてもよい。
R1は、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、炭素原子数3〜20のシクロアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアルキルアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜8のアルケニル基、又は下記一般式(II)で表される置換基を表し、
R2及びR3は、それぞれ独立に、水素原子、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、または−O−Rを表し、このRは、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、炭素原子数3〜20のシクロアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアルキルアリール基、又は炭素原子数7〜20のアリールアルキル基を表し、
R4、R5、R6、R7、R8、R9、R10、R11及びR12は、それぞれ独立に、水素原子、ハロゲン原子、置換又は無置換の、直鎖又は分岐の炭素原子数1〜8のアルキル基又は直鎖又は分岐の炭素原子数2〜8のアルケニル基を表し、
R13及びR14は、それぞれ独立に、水素原子またはヒドロキシ基を表す。
R21及びR22は、それぞれ独立に、水素原子、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、または−O−Rを表し、このRは、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、炭素原子数3〜20のシクロアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアルキルアリール基、又は炭素原子数7〜20のアリールアルキル基を表し、
R23、R24、R25、R26、R27、R28、R29、R30及びR31は、それぞれ独立に、水素原子、ハロゲン原子、置換又は無置換の、直鎖又は分岐の炭素原子数1〜8のアルキル基、又は直鎖または分岐の炭素原子数2〜8のアルケニル基を表し、
R32及びR33は、それぞれ独立に、水素原子またはヒドロキシ基を表し、
X1は、置換又は無置換の、直鎖又は分岐の炭素原子数8以上30以下のアルキレン基を表し、
Y1及びY2は、それぞれ独立に、−CO−O−、−O−CO−、−L1−、−O−L1O−、−O−L1−、−L1−O−CO−、−L1−CO−O−、−CO−CH=CH−、−CH=CH−CO−、−CH=CH−CO−O−、−CH=CH−O−CO−、−CO−O−CH=CH−を表し、
L1は、直鎖又は分岐の炭素原子数1〜8のアルキレン基であり、
m及びnは、それぞれ独立に、0〜8の整数を表し、
*は、式(I)中のR1と連結する酸素原子との結合手を表す。
また、上記一般式(I)で表されるトリアジン系化合物の一例として、下記一般式(A)で表される化合物、または下記一般式(B)で表される化合物が挙げられる。
RA1は、直鎖又は分岐の炭素原子数1〜12のアルキル基、炭素原子数3〜8のシクロアルキル基、直鎖又は分岐の炭素原子数3〜8のアルケニル基、炭素原子数6〜18のアリール基、炭素原子数7〜18のアルキルアリール基または炭素原子数7〜18のアリールアルキル基を表し、
RA2及びRA3は、互いに同一でも異なっていてもよく、水素原子、直鎖又は分岐の炭素原子数1〜12のアルキル基、若しくは、直鎖又は分岐の炭素原子数1〜12のアルコキシ基を表し、
RA4、RA7、RA10は、互いに同一でも異なっていてもよく、水素原子、直鎖又は分岐の炭素原子数1〜8のアルキル基または直鎖又は分岐の炭素原子数3〜8のアルケニル基を表し、
RA13及びRA17は、互いに同一で異なっていてもよく、水素原子またはヒドロキシ基を表す。
ただし、RA1、RA2及びRA3で表される直鎖又は分岐の炭素原子数1〜12のアルキル基、RA2及びRA3で表される直鎖又は分岐の炭素原子数1〜12のアルコキシ基中のメチレン基は、酸素原子、硫黄原子、炭素−炭素二重結合、−CO−、−CO−O−、−OC−O−、−CO−NH−、−NH−CO−、−CR05=N−および−N=CR06−から選択される少なくとも一以上の構造で置換されていてもよく、前記構造中のR05及びR06は、それぞれ独立に、直鎖又は分岐の炭素原子数1〜8のアルキル基を表す。
RB4、RB5、RB7〜RB9、RB10〜RB12、RB23、RB24、RB26〜RB28、RB29〜RB31は、各々独立して、水素原子、ヒドロキシ基、ハロゲン原子、直鎖又は分岐の炭素原子数1〜8のアルキル基、直鎖又は分岐の炭素原子数2〜8のアルケニル基、直鎖又は分岐の炭素原子数1〜20のアルコキシ基、炭素原子数6〜20のアリール基を表し、nは8〜14の整数を表す。ただし、トリアジン環と連結する3つのベンゼン環のうち、2つのベンゼン環のパラ位は、水素原子、直鎖又は分岐の炭素原子数1〜20のアルキル基、若しくは、直鎖又は分岐の炭素原子数1〜20のアルコキシ基を表し、且つ、オルト位の一つは、水素原子またはヒドロキシ基を表す。
上記アルコール成分としては、一価カルボン酸のエステル誘導性化合物(一価カルボン酸、一価カルボン酸ハライド又は一価カルボン酸エステル)、二価カルボン酸のエステル誘導性化合物(二価カルボン酸、二価カルボン酸ハライド又は二価カルボン酸のエステル等が挙げられる
ここで、極大ピークとは、粉末X線回折測定における走査範囲内(例えば、回折角2θ=3゜〜60゜または3゜〜90゜)で得られたX線回折パターンにおいて、最大ピーク強度を有するものである。
上記熱可塑性樹脂として、例えば、ポリプロピレン、高密度ポリエチレン、低密度ポリエチレン、直鎖低密度ポリエチレン、架橋ポリエチレン、超高分子量ポリエチレン、ポリブテン−1、ポリ−3−メチルペンテン等のα−オレフィン重合体又はエチレン−酢酸ビニル共重合体、エチレン−エチルアクリレート共重合体、エチレン−プロピレン共重合体等のポリオレフィン及びこれらの共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン、塩素化ポリプロピレン、ポリフッ化ビニリデン、塩化ゴム、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−エチレン共重合体、塩化ビニル−塩化ビニリデン共重合体、塩化ビニル−塩化ビニリデン−酢酸ビニル三元共重合体、塩化ビニル−アクリル酸エステル共重合体、塩化ビニル−マレイン酸エステル共重合体、塩化ビニル−シクロヘキシルマレイミド共重合体等の含ハロゲン樹脂;石油樹脂、クマロン樹脂、ポリスチレン、ポリ酢酸ビニル、アクリル樹脂、ポリメチルメタクリレート、ポリビニルアルコール、ポリビニルホルマール、ポリビニルブチラール;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリシクロヘキサンジメチレンテレフタレート等のポリアルキレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等のポリアルキレンナフタレート等の芳香族ポリエステル及びポリテトラメチレンテレフタレート等の直鎖ポリエステル;ポリヒドロキシブチレート、ポリカプロラクトン、ポリブチレンサクシネート、ポリエチレンサクシネート、ポリ乳酸樹脂、ポリリンゴ酸、ポリグリコール酸、ポリジオキサン、ポリ(2−オキセタノン)等の分解性脂肪族ポリエステル;ポリフェニレンオキサイド、ポリカプロラクタム及びポリヘキサメチレンアジパミド等のポリアミド、ポリカーボネート、分岐ポリカーボネート、ポリアセタール、ポリフェニレンサルファイド、ポリウレタン、繊維素系樹脂等が挙げられる。
より具体的なエラストマーとしては、例えば、オレフィン系熱可塑性エラストマー、スチレン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ニトリル系熱可塑性エラストマー、ナイロン系熱可塑性エラストマー、塩化ビニル系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマー等が挙げられる。
本明細書中、「〜」は、特に明示しない限り、上限値と下限値を含むことを表す。
上記プレートアウト防止剤としては、例えば、二酸化ケイ素、エチレン−飽和カルボン酸ビニルエステル共重合体けん化物のアルキレンオキサイド付加物を有効成分にしたものが挙げられる。
また各成分を予め混合せずに、又は一部の成分のみ予め混合して、フィーダーを用いて押出機に供給し溶融混練して、樹脂組成物を製造してもよい。更には、一部の成分を予め混合し押出機に供給して溶融混練することで得られる樹脂組成物をマスターバッチとし、再度、他の成分と混合し溶融混練することによって樹脂組成物を製造することもできる。
また、上記の混合・混練工程に用いる合成樹脂は、粉状、ペレット状等の所定形状、または繊維状を有するものであってもよい。
成形方法としては、特に限定されるものではなく、射出成形法、押出成形法、ブロー成形法、回転成形、真空成形法、インフレーション成形法、カレンダー成形法、スラッシュ成形法、ディップ成形法、発泡成形法等が挙げられる。
上記樹脂ワニスは、例えば、キャストフィルム法を用いて、フィルムやシートに加工することもできる。また上記樹脂ワニスは、所定の基材上にコーティングするための塗料材料として用いることもできる。
また、医薬品、ビタミン剤、ドリンク剤、目薬等の薬品容器;化粧水、乳液、日焼け止め等の化粧品容器;食品容器、酒、ワイン、ビール、フルーツジュース、ソフトドリンク、お茶、紅茶、コーヒー等の飲料容器;シャンプー、リンス、うがい液、歯磨き剤、消毒液等の日用品容器等の用途も挙げられる。
以下、参考形態の例を付記する。
1. トリアジン系化合物を含む粒状紫外線吸収剤であって、
湿式のレーザー回折式粒度分布測定法による当該粒状紫外線吸収剤の、体積基準の粒子径分布における累積10%粒子径をD 10 (μm)とし、累積90%粒子径をD 90 (μm)としたとき、
D 10 /D 90 が0.01以上0.25以下の範囲にある、粒状紫外線吸収剤。
2. 1.に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物が、上記一般式(I)で表される化合物を含む、粒状紫外線吸収剤。
[上記一般式(I)中、
R 1 は、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、炭素原子数3〜20のシクロアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアルキルアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜8のアルケニル基、又は上記一般式(II)で表される置換基を表し、
R 2 及びR 3 は、それぞれ独立に、水素原子、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、または−O−Rを表し、このRは、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、炭素原子数3〜20のシクロアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアルキルアリール基、又は炭素原子数7〜20のアリールアルキル基を表し、
R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 及びR 12 は、それぞれ独立に、水素原子、ハロゲン原子、置換又は無置換の、直鎖又は分岐の炭素原子数1〜8のアルキル基又は直鎖又は分岐の炭素原子数2〜8のアルケニル基を表し、
R 13 及びR 14 は、それぞれ独立に、水素原子またはヒドロキシ基を表す。
ただし、R 1 、R 2 、R 3 及びRで表される置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 及びR 12 で表される置換又は無置換の、直鎖又は分岐の炭素原子数1〜8のアルキル基中のメチレン基は、酸素原子、硫黄原子、炭素−炭素二重結合、−CO−、−CO−O−、−OC−O−、−CO−NH−、−NH−CO−、−CR 01 =N−および−N=CR 02 −から選択される少なくとも一以上の構造で置換されていてもよく、前記構造中のR 01 及びR 02 は、それぞれ独立に、直鎖又は分岐の炭素原子数1〜8のアルキル基を表す。]
[上記一般式(II)中、
R 21 及びR 22 は、それぞれ独立に、水素原子、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、または、−O−Rを表し、このRは、置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、炭素原子数3〜20のシクロアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアルキルアリール基、又は炭素原子数7〜20のアリールアルキル基を表し、
R 23 、R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 及びR 31 は、それぞれ独立に、水素原子、ハロゲン原子、置換又は無置換の、直鎖又は分岐の炭素原子数1〜8のアルキル基、又は直鎖又は分岐の炭素原子数2〜8のアルケニル基を表し、
R 32 及びR 33 は、それぞれ独立に、水素原子またはヒドロキシ基を表し、
X 1 は、置換又は無置換の、直鎖又は分岐の炭素原子数8以上30以下のアルキレン基を表し、
Y 1 及びY 2 は、それぞれ独立に、−CO−O−、−O−CO−、−L 1 −、−O−L 1 O−、−O−L 1 −、−L 1 −O−CO−、−L 1 −CO−O−、−CO−CH=CH−、−CH=CH−CO−、−CH=CH−CO−O−、−CH=CH−O−CO−、−CO−O−CH=CH−を表し、
L 1 は、直鎖又は分岐の炭素原子数1〜8のアルキレン基であり、
m及びnは、それぞれ独立に、0〜8の整数を表し、
*は、式(I)中のR 1 と連結する酸素原子との結合手を表す。
ただし、R 21 、R 22 及びRで表される置換又は無置換の、直鎖又は分岐の炭素原子数1〜20のアルキル基、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 及びR 31 で表される前記置換又は無置換の、直鎖又は分岐の炭素原子数1〜8のアルキル基およびX 1 で表される直鎖又は分岐の炭素原子数8以上30以下のアルキレン基中のメチレン基は、酸素原子、硫黄原子、炭素−炭素二重結合、−CO−、−CO−O−、−OC−O−、−CO−NH−、−NH−CO−、−CR 03 =N−および−N=CR 04 −から選択される少なくとも一以上の構造で置換されていてもよく、R 03 及びR 04 は、それぞれ独立に、直鎖又は分岐の炭素原子数1〜8のアルキル基を表す。]
3. 1.または2.に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物が、上記一般式(A)で表される化合物を含む、粒状紫外線吸収剤。
(上記一般式(A)中、
R A1 は、直鎖又は分岐の炭素原子数1〜12のアルキル基、炭素原子数3〜8のシクロアルキル基、直鎖又は分岐の炭素原子数3〜8のアルケニル基、炭素原子数6〜18のアリール基、炭素原子数7〜18のアルキルアリール基または炭素原子数7〜18のアリールアルキル基を表し、
R A2 及びR A3 は、互いに同一でも異なっていてもよく、水素原子、直鎖又は分岐の炭素原子数1〜12のアルキル基、若しくは、直鎖又は分岐の炭素原子数1〜12のアルコキシ基を表し、
R A4 、R A7 、R A10 は、互いに同一でも異なっていてもよく、水素原子、直鎖又は分岐の炭素原子数1〜8のアルキル基または直鎖又は分岐の炭素原子数3〜8のアルケニル基を表し、
R A13 及びR A17 は、互いに同一で異なっていてもよく、水素原子またはヒドロキシ基を表す。
ただし、R A1 、R A2 及びR A3 で表される直鎖又は分岐の炭素原子数1〜12のアルキル基、R A2 及びR A3 で表される直鎖又は分岐の炭素原子数1〜12のアルコキシ基中のメチレン基は、酸素原子、硫黄原子、炭素−炭素二重結合、−CO−、−CO−O−、−OC−O−、−CO−NH−、−NH−CO−、−CR 05 =N−および−N=CR 06 −から選択される少なくとも一以上の構造で置換されていてもよく、前記構造中のR 05 及びR 06 は、それぞれ独立に、直鎖又は分岐の炭素原子数1〜8のアルキル基を表す。)
4. 1.または2.に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物が、上記の化合物No.1Aから化合物No.8Aのいずれかで表される一または二以上の化合物を含む、粒状紫外線吸収剤。
5. 1.または2.に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物が、上記一般式(B)で表される化合物を含む、粒状紫外線吸収剤。
(上記一般式(B)中、R B4 、R B5 、R B7 〜R B9 、R B10 〜R B12 、R B23 、R B24 、R B26 〜R B28 、R B29 〜R B31 は、各々独立して、水素原子、ヒドロキシ基、ハロゲン原子、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数1〜20のアルコキシ基、炭素原子数6〜20のアリール基を表し、nは8〜14の整数を表す。ただし、トリアジン環と連結する三つのベンゼン環のうち二つのベンゼン環のパラ位は、水素原子、炭素原子数1〜20のアルキル基または炭素原子数1〜20のアルコキシ基を表し、且つ、オルト位の一つは、水素原子またはヒドロキシ基を表す。)
6. 5.に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物が、上記の化合物No.1Bから化合物No.4Bのいずれかで表される一または二以上の化合物を含む、粒状紫外線吸収剤。
(上記化合物No.1Bから化合物No.4B中、R A1 、R A2 、R B1 、R B2 、R C1 、R C2 、R D1 及びR D2 は、互いに同一でも異なってもよく、水素原子、直鎖または分岐の炭素原子数1〜4のアルキル基、若しくは、直鎖または分岐の炭素原子数1〜4のアルコキシ基を表す。)
7. 1.〜6.のいずれか1つに記載の粒状紫外線吸収剤であって、
湿式のレーザー回折式粒度分布測定法による当該粒状紫外線吸収剤の、体積基準の粒子径分布における体積平均粒子径をMV(μm)とし、個数平均粒子径をMN(μm)としたとき、
MV/MNが5.0以上30.0以下の範囲にある、粒状紫外線吸収剤。
8. 1.〜7.のいずれか1つに記載の粒状紫外線吸収剤であって、
湿式のレーザー回折式粒度分布測定法による当該粒状紫外線吸収剤の、体積基準の粒子径分布における累積98%粒子径をD 98 (μm)としたとき、
D 98 /D 90 が1.70以上5.00以下の範囲にある、粒状紫外線吸収剤。
9. 2.〜4.のいずれか1つに記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物が、粉末X線回折分析パターンにおいて、回折角2θが5.00°以上6.50°以下の範囲内に極大ピークを有することを特徴とする、粒状紫外線吸収剤。
10. 9.に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物の極大ピークの半値幅が、0.05°以上0.20°以下である、粒状紫外線吸収剤。
11. 9.または10.に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物の極大ピークの相対強度を100としたとき、当該相対強度30以上60以下の回折ピークが、回折角2θが3.0°以上45.0°以下の範囲内に存在しないことを特徴とする、粒状紫外線吸収剤。
12. 9.〜11.のいずれか1つに記載の粒状紫外線吸収剤であって、
請求項トリアジン系化合物の極大ピークの相対強度を100としたとき、当該相対強度1以上5以下の回折ピークが、回折角2θが45.0°超60.0°以下の範囲内に存在しないことを特徴とする、粒状紫外線吸収剤。
13. 1.〜12.のいずれか1つに記載の粒状紫外線吸収剤を含有する、樹脂組成物。
14. 13.に記載の樹脂組成物であって、合成樹脂を含有する樹脂組成物。
(実施例1)
以下の手順により2,4,6−トリス[2−ヒドロキシ−3−メチル−4−ヘキシルオキシフェニル]トリアジンを合成した。
300mlの四つ口フラスコに2,4,6−トリス(2,4−ジヒドロキシ−3−メチルフェニル)トリアジンを10.00g、水酸化ナトリウムを22.68g、ジメチルホルムアミドを80.00g、1−ブロモヘキサンを11.07g加え80℃まで昇温し、9時間反応させた。塩酸を用いて中和処理を行った後、水洗、減圧脱溶媒し、残渣をトルエン:イソプロピルアルコール=1:1から再結晶することにより、結晶を得た。その後、金属製プレートに溶融させた目的物(結晶)を滴下し、冷却することでフレークを得た(溶融固化処理)。得られたフレークを乳鉢粉砕することで、融点145℃の淡黄色粉末11.89g(収率76%)を得た。
得られた化合物(淡黄色粉末)について、1H−NMR測定を行った。下記分析結果により得られた淡黄色粉末は、下記式No.1で表される粉状の化合物(粒状紫外線吸収剤)と同定された。
実施例1と同様にして、異なるロットである、上記式No.1で表される粉状の化合物No.1(粒状紫外線吸収剤)を得た。
以下の手順により、2−(4−(4,6−ジフェニル−1,3,5−トリアジン−2−イル)−3−ヒドロキシフェノキシ)エチル 2−エチルヘキサノエートを合成した。
300mlの四つ口フラスコに2−(4,6−ジフェニル−1,3,5−トリアジン−2−イル)−5−(2−ヒドロキシエトキシ)フェノールを10.00g、パラトルエンスルホン酸一水和物を0.25g、トルエンを70.00g、2−エチルヘキサン酸を4.12g加え還流下、10時間反応させた。水洗し、トルエン:イソプロピルアルコール=1:2から再結晶することにより、結晶を得た。その後、金属製プレートに溶融させた目的物(結晶)を滴下し、冷却することでフレークを得た(溶融固化処理)。得られたフレークを乳鉢粉砕することで、融点108℃の淡黄色粉末9.56g(収率72%)を得た。
得られた化合物(淡黄色粉末)について、1H−NMR測定を行った。下記分析結果により得られた淡黄色粉末は、下記式No.2で表される粉状の化合物(粒状紫外線吸収剤)と同定された。
実施例1で得られた結晶を、溶融固化処理を実施せずに、乳鉢粉砕することで、上記式No.1で表される粉状の化合物(粒状紫外線吸収剤)を得た。
比較例1と同様にして、異なるロットである、上記式No.1で表される粉状の化合物(粒状紫外線吸収剤)を得た。
実施例11において得られたフレークを、粗粉砕することで、上記式No.2で表される顆粒状の化合物(粒状紫外線吸収剤)を得た。
累積10%粒子径D10、累積90%粒子径D90、累積98%粒子径D98、体積平均粒子径MV、および個数平均粒子径MNは、メタノールに、得られた粒状紫外線吸収剤を加えて混合した溶液に対して、超音波で分散させながら、湿式条件下で、レーザー回折式粒度分布測定器(Microtrac MT3000II)を用いて測定した。
ブリケットマシンを用いて、得られた粒状紫外線吸収剤を圧縮造粒し、アーモンド形状のブリケットを成形した。得られたブリケットの外観を観察し、以下の評価基準に基づいて圧縮造粒性を評価した。
○:ラミネーティング(ブリケットが層状に割れる現象)が生じていなかった。
×:ラミネーティングが一部または全体に生じていた。
アクリル樹脂100質量部に対して、得られた粒状紫外線吸収剤を1質量部の配合量にて配合し、二軸押出機(L/D=30)を用いて、250℃で溶融混練して造粒し、ペレットを得た。吐出量を0.3kg/hに設定したときのペレットを観察し、以下の評価基準に基づいて溶融混練性を評価した。
○:樹脂と粒状紫外線吸収剤とが均一に分散し、溶融混練をすることができた。
△:樹脂と粒状紫外線吸収剤とがやや分離したが、溶融混練をすることができた。
×:樹脂と粒状紫外線吸収剤とが分離し、溶融混練をすることができなかった。
得られた粒状紫外線吸収剤に対して、UltimaIV(株式会社リガク)を用い、以下の測定条件で、粉末X線回折測定を実施した。
(測定条件)
X線管球:CuKα線(CuKα1=1.540562Å、CuKα2=1.544398Å、CuKα2除去なし)
管電圧/管電流:40kV/40mA
アタッチメント:多目的薄膜試料台
モノクロメータ:固定
フィルタ:なし
発散スリット:2/3°
発散縦制限スリット:10mm
散乱スリット:1.17mm
受光スリット:0.3mm
スキャンタイプ:連続スキャン
スキャンスピード:4°/min
サンプリング幅:0.02°
走査軸:2θ/ω
走査範囲:=3゜〜90゜
ただし、実施例11の粉末X線回折測定の測定条件として、下記の条件を採用した以外は実施例1と同様にした。
発散スリット:1/2°
発散縦制限スリット:10mm
散乱スリット:0.93mm
走査範囲:=2゜〜60゜
得られた粒状紫外線吸収剤1kgをホッパーに投入し、重量式フィーダー(K−トロン社製、縦:25cm×外径:1.4cm、溝の幅:2.0cm、溝の深さ:0.3cmのTwin spiral typeの二軸スクリュー)を用いて、フィーダー排出量:0.3kg/hの条件で、30分間排出した(フィード性試験)。
・定量性
重量式フィーダーから排出された量(フィーダー量)を、10分間隔で経時的に測定した。フィード量のバラツキが小さい場合を○、フィード量のバラツキが大きい場合を×とした。
・ロングラン性
排出時間の条件を30分間から3時間に変更した以外は同様にして、上記のフィード試験を実施した。3時間排出し続けた場合を○、3時間の経過前に運転が停止した場合を×とした。
(フィルムの作製)
合成樹脂(ポリカーボネート樹脂:三菱エンジニアリングプラスチックス(株)製、製品名E−2000)100質量部に対して、得られた各実施例の粒状紫外線吸収剤を0.2質量部配合したものを、溶媒(トルエン/シクロヘキサン=9/1)230質量部に溶解することにより、樹脂組成物を調製した。得られた樹脂組成物で、キャスト法により厚さ40μmのフィルムを作製し、1辺2cmの正方形のフィルム試験片を得た。
得られたフィルム試験片を、サンシャインウェザオメーター(83℃、雨なし、光源カーボンアーク)にて、240、360及び480時間後の全光線透過率(%)の保持率(%)を測定し、耐光性を評価した。
240、360及び480時間後の保持率(%)が高い値を示した結果から、各実施例の粒状紫外線吸収剤を使用することにより、優れた耐光性を実現できることが分かった。
また、合成樹脂として、ポリカーボネート樹脂に代えて、メタクリル樹脂、ノルボルネン樹脂、ポリエチレンテレフタレート樹脂、又はポリスチレン樹脂を用いた場合でも、同様に優れた耐光性を実現できることが分かった。
ポリエチレンテレフタレート(固有粘度:0.8dL/g)100質量部に対して、得られた各実施例の粒状紫外線吸収剤を0.3質量部加えて混合し、樹脂組成物を得た。得られた樹脂組成物について、160℃のギヤーオーブンで4時間乾燥後、射出成形機にて、射出温度280℃の成形温度で、プリフォーム(口外径25mm、重量23g)を成形した。次に、得られたプリフォームについて、金型温度130℃で二軸延伸ブロー成形し、容量500mL、厚さ0.7mmのプラスチックボトルを作製した。得られたプラスチックボトルについて、波長500nmの可視光線の透過率、波長400nmの紫外線の透過率を測定した。波長500nmの透過率が高く、波長400nmの透過率が低い結果から、得られたプラスチックボトル(容器)は、紫外線を効率的に吸収し、また、可視光線の透過性も十分確保できていることが分かった。
・紫外線吸収層
ノルボルネン樹脂(JSR(株)製、製品名:ARTON F5023)100質量部に対して、得られた各実施例の粒状紫外線吸収剤を0.5質量部、並びに溶媒としてジクロロメタン2000質量部を混合し、樹脂溶液(樹脂組成物)を得た。得られた樹脂溶液を、表面研磨したガラス板上にバーコーターを用いて流延し、50℃で20分の予備乾燥、90℃で30分の乾燥を経て、膜厚80〜90μmのフィルムを作製した後、1辺2cmの正方形のフィルム試験片(紫外線吸収層)を得た。
・NIR吸収層の作製
ノルボルネン樹脂(JSR(株)製、製品名:ARTON F5023)100質量部に対して、近赤外線吸収剤としてジイモニウム系化合物(日本化薬(株)製、製品名:IRG−068)0.3質量部、溶媒としてジクロロメタン2000質量部からなる樹脂溶液を、表面研磨したガラス板上にバーコーターを用いて流延し、50℃で20分の予備乾燥、90℃で30分の乾燥を経て、膜厚50〜60μmのフィルムを作製した後、1辺2cmの正方形のフィルム試験片を得た。
得られたNIR吸収層及び紫外線吸収層を重ね合わせた試験片につき、サンシャインウェザーメーター(スガ試験機株式会社製;83℃、雨なし、光源カーボンアーク)にて、紫外線吸収層側から試験光が当たるようにして、360(又は540)時間曝露した。耐光試験前後のNIR領域の極大波長(NIR吸収層:1100nm)における透過率を測定し、透過率の減衰率(Δ透過率)により耐光性評価を行った。
各実施例において、Δ透過率を低減できた結果から、近赤外線吸収剤の光劣化に対して効果を示すことが確かめられた。これにより、近赤外線吸収層における近赤外線吸収剤の光劣化防止に優れることが分かった。
Claims (9)
- トリアジン系化合物を含む粒状紫外線吸収剤であって、
前記トリアジン系化合物が、下記化合物No.1および化合物No.2のいずれかで表される一または二の化合物を含み、
湿式のレーザー回折式粒度分布測定法による当該粒状紫外線吸収剤の、体積基準の粒子径分布における累積10%粒子径をD10(μm)とし、累積90%粒子径をD90(μm)としたとき、
D10/D90が0.040以上0.104以下の範囲にある、
湿式のレーザー回折式粒度分布測定法による当該粒状紫外線吸収剤の、体積基準の粒子径分布における体積平均粒子径をMV(μm)とし、個数平均粒子径をMN(μm)としたとき、
MV/MNが11.1以上21.6以下の範囲にある、
粒状紫外線吸収剤。
- 請求項1に記載の粒状紫外線吸収剤であって、
D90が120.0μm以上500.0μm以下である、粒状紫外線吸収剤。 - 請求項1または2に記載の粒状紫外線吸収剤であって、
湿式のレーザー回折式粒度分布測定法による当該粒状紫外線吸収剤の、体積基準の粒子径分布における累積98%粒子径をD98(μm)としたとき、
D98/D90が1.70以上5.00以下の範囲にある、粒状紫外線吸収剤。 - 請求項1〜3のいずれか1項に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物が、粉末X線回折分析パターンにおいて、回折角2θが5.00°以上6.50°以下の範囲内に極大ピークを有することを特徴とする、粒状紫外線吸収剤。 - 請求項4に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物の極大ピークの半値幅が、0.05°以上0.20°以下である、粒状紫外線吸収剤。 - 請求項4または5に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物の極大ピークの相対強度を100としたとき、当該相対強度30以上60以下の回折ピークが、回折角2θが3.0°以上45.0°以下の範囲内に存在しないことを特徴とする、粒状紫外線吸収剤。 - 請求項4〜6のいずれか1項に記載の粒状紫外線吸収剤であって、
前記トリアジン系化合物の極大ピークの相対強度を100としたとき、当該相対強度1以上5以下の回折ピークが、回折角2θが45.0°超60.0°以下の範囲内に存在しないことを特徴とする、粒状紫外線吸収剤。 - 請求項1〜7のいずれか1項に記載の粒状紫外線吸収剤を含有する、樹脂組成物。
- 請求項8に記載の樹脂組成物であって、合成樹脂を含有する樹脂組成物。
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