JP2019066827A - Photochromic lens - Google Patents

Abstract

To provide a photochromic lens capable of sufficiently cutting glare and harmful light in the HEV range from sunlight and transmitting light that is effective in maintaining the circadian rhythm.SOLUTION: A photochromic lens of the present invention exhibits a luminous transmittance of 90% or greater in a wavelength range of 400-780 nm when decolored, and the transmittance at 23°C after being irradiated with light of 50000 lux from a xenon lamp for 15 minutes satisfies the following conditions: (1) the luminous transmittance in the wavelength range of 400-780 nm is 20% or less; (2) a value obtained by subtracting an average transmittance in a wavelength range of 400-420 nm from 100% is 90% or greater; and (3) a value obtained by subtracting the luminous transmittance in the wavelength range of 400-780 nm from a luminous transmittance in a wavelength range of 460-500 nm is 10% or greater.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photochromic lens.

  Since plastic lenses are lighter in weight and harder to break than inorganic lenses, they are rapidly spreading to optical elements such as spectacle lenses and camera lenses. In recent years, development of plastic lenses having photochromic performance has been advanced.

Patent Documents 1 to 3 disclose a photochromic lens that includes an isocyanate compound, an active hydrogen compound having two or more functions, and a predetermined alcohol compound.
Patent Document 4 describes a photochromic lens composed of a photochromic compound and a compound having a (meth) acrylic group.
Patent Document 5 describes a photochromic lens composed of a photochromic compound and a compound having an allyloxycarbonyl group.

  In recent years, the influence on eyes has become a problem such as causing eyestrain due to blue light included in light emitted from natural light, liquid crystal display of office equipment, display of portable equipment such as smart phone or mobile phone etc. . In particular, light with a wavelength of 400 nm to 420 nm called HEV is harmful, and it is known that exposure to the wavelength for a long time causes age-related macular degeneration. Therefore, it is desirable to protect the eyes from light of wavelengths 400 nm to 420 nm in the HEV region.

  In recent years, attention has been focused on the effects of light on circadian rhythms. Light at a wavelength of 460 nm to 480 nm promotes secretion of serotonin, maintains wakefulness, and functions to regulate circadian rhythm. Also, it is suggested that the higher the amount of secretion, the more secretion of melatonin, which has the effect of being introduced into sleep, at night, and that good quality sleep can be obtained.

International Publication No. 2015/115648 International Publication No. 2017/047744 International Publication No. 2017/047745 International Publication No. 2017/047742 International Publication No. 2017/047743

The photochromic lens is colored in sunlight, so the transmittance is lowered, and glare from sunlight can be suppressed. The darker the color, the more light can be cut, and thus the glare can be suppressed, but the light with a wavelength of 460 nm to 480 nm necessary for maintaining the circadian rhythm has also been cut.
When the transmittance of the short wavelength light is increased so as not to cut the above wavelength, the light in the HEV region which is harmful to the eye may also be transmitted.

  Therefore, as a result of intensive investigations, the present inventors have found that the luminous transmittance from 400 nm to 780 nm at color development is 20% or less, and the average cut rate from 400 nm to 420 nm (the average transmittance of the region is 100% A photochromic lens having a value obtained by subtracting 90% or more and a value obtained by subtracting the luminous transmittance from 400 nm to 780 nm from 10% or more and 10% or more from the luminous transmittance from 460 nm to 500 nm is glare from sunlight. We found that it is possible to transmit effective light for circadian rhythm while sufficiently cutting off harmful HEV light.

（一般式（３）および一般式（４）中、Ｒ_１およびＲ_２は同一でも異なっていてもよく、独立して、水素；
炭素数１〜１２の直鎖または分岐アルキル基；
炭素数３〜１２のシクロアルキル基；
置換または無置換である、炭素数６〜２４のアリール基または炭素数４〜２４のヘテロアリール基；
アラルキルまたはヘテロアラルキル基（炭素数１〜４の直鎖または分岐アルキル基が前記のアリール基またはヘテロアリール基で置換されている。）を示す。
置換された炭素数６〜２４のアリール基または置換された炭素数４〜２４のヘテロアリール基の置換基は、ハロゲン原子、水酸基、炭素数１〜１２の直鎖または分枝のアルキル基、炭素数１〜１２の直鎖または分枝のアルコキシ基、少なくとも１つのハロゲン原子で置換された炭素数１〜１２の直鎖または分枝のハロアルキル基、少なくとも１つのハロゲン原子で置換された炭素数１〜１２の直鎖または分枝のハロアルコキシ基、少なくとも一つの炭素数１〜１２の直鎖または分枝のアルキル基またはアルコキシ基により置換されたフェノキシ基またはナフトキシ基、炭素数２〜１２の直鎖または分枝のアルケニル基、−ＮＨ_２基、−ＮＨＲ基、−Ｎ(Ｒ)_２基（Ｒは炭素数１〜６の直鎖または分枝のアルキル基である。Ｒが２つ存在する場合、２つのＲは同一でも異なっていてもよい。）、およびメタクリロイル基またはアクリロイル基から少なくとも１つ選択される。
Ｒ_３は同一でも異なっていてもよく、独立して、ハロゲン原子；
炭素数１〜１２の直鎖または分岐アルキル基；
炭素数３〜１２のシクロアルキル基；
炭素数１〜１２の直鎖または分岐アルコキシ基；
少なくとも１つのハロゲン原子で置換された炭素数１〜１２の直鎖または分枝のハロアルキル基、少なくとも１つのハロゲン原子で置換された炭素数３〜１２のハロシクロアルキル基、少なくとも１つのハロゲン原子で置換された炭素数１〜１２の直鎖または分岐ハロアルコキシ基；
置換または無置換である、炭素数６〜２４のアリール基または炭素数４〜２４のヘテロアリール基（置換基として、ハロゲン原子、水酸基、炭素数１〜１２の直鎖または分枝のアルキル基、炭素数１〜１２の直鎖または分枝のアルコキシ基、少なくとも１つのハロゲン原子で置換された炭素数１〜１２の直鎖または分枝のハロアルキル基、少なくとも１つのハロゲン原子で置換された炭素数１〜１２の直鎖または分枝のハロアルコキシ基、少なくとも一つの炭素数１〜１２の直鎖または分枝のアルキル基またはアルコキシ基により置換されたフェノキシ基またはナフトキシ基、炭素数２〜１２の直鎖または分枝のアルケニル基、およびアミノ基、から選択される少なくとも１つの置換基を有する。）；
アラルキルまたはヘテロアラルキル基（炭素数１〜４の直鎖または分岐アルキル基が前記のアリール基またはヘテロアリール基で置換されている。）；
置換または無置換のフェノキシまたはナフトキシ基（置換基として、炭素数１〜６の直鎖または分岐アルキル基またはアルコキシ基から選択される少なくとも１つの置換基を有する。）；
−ＮＨ₂、−ＮＨＲ、−ＣＯＮＨ₂、または−ＣＯＮＨＲ
（Ｒが、炭素数１〜６の直鎖または分枝のアルキル基である。）；
−ＯＣＯＲ₈または−ＣＯＯＲ₈（ここで、Ｒ₈が、炭素数１〜６の直鎖または分枝のアルキル基、または炭素数３〜６のシクロアルキル基、またはＲ₁、Ｒ₂において、置換アリールまたは置換ヘテロアリール基の置換基の少なくとも１つにより置換されているフェニル基または無置換のフェニル基である。）；
を表す。
少なくとも２つの隣接するＲ_３同士が結合し、Ｒ_３が結合している炭素原子を含んで、１つ以上の芳香環基または非芳香環基を形成することができる。芳香環基または非芳香環基は、酸素、硫黄、及び窒素からなる群より選択されるヘテロ原子を含んでいてもよい１つの環または２つのアネル化された環を含む。
ｌは、０〜２までの整数である。ｍは、０〜４までの整数である。）
［３］ 下記一般式（５）で表される調光色素を含む、［１］または［２］に記載のフォトクロミックレンズ。

（一般式（５）中、Ｒ^１、Ｒ^２、Ｒ^３、ｍは、一般式（３）と同じであり、Ａは、下記式（Ａ_１）〜（Ａ_５）のアネル化環を表す。

（これらのアネル化環（Ａ₁）〜（Ａ₅）において、点線が、一般式（５）のナフトピラン環の炭素Ｃ₅炭素Ｃ₆結合を表す。アネル化環（Ａ₄）または（Ａ₅）のα結合が、一般式（５）のナフトピラン環の炭素Ｃ₅または炭素Ｃ₆に結合される。
Ｒ₄が、同じかまたは異なり、独立して、ＯＨ、炭素数１〜６の直鎖または分枝のアルキル基またはアルコキシ基を表し、もしくは２つのＲ₄がカルボニル（ＣＯ）を形成する。
Ｒ₅、Ｒ₆およびＲ₇が、独立して、ハロゲン原子；
炭素数１〜１２の直鎖または分枝のアルキル基；
少なくとも１つのハロゲン原子により置換された、炭素数１〜６の直鎖または分枝のハロアルキル基；
炭素数３〜１２のシクロアルキル基；
炭素数１〜６の直鎖または分枝のアルコキシ基；
置換または無置換のフェニルまたはベンジル基（置換基として、一般式（５）のＲ_１、Ｒ_２基が独立してアリールまたはヘテロアリール基に対応する場合、Ｒ_１、Ｒ_２基の定義において上述した置換基の少なくとも１つを有する。）；
−ＮＨ₂、−ＮＨＲ
（ここで、Ｒが、炭素数１〜６の直鎖または分枝のアルキル基である。）；
置換または無置換であるフェノキシまたはナフトキシ基（置換基として、少なくとも炭素数１〜６の直鎖または分枝のアルキル基またはアルコキシ基を有する。）；
−ＣＯＲ₉、−ＣＯＯＲ₉または−ＣＯＮＨＲ₉基（ここで、Ｒ₉が、炭素数１〜６の直鎖または分枝のアルキル基、または炭素数３〜６のシクロアルキル基、または置換または無置換のフェニルまたはベンジル基（置換基として、一般式（５）のＲ_１、Ｒ_２基が独立してアリールまたはヘテロアリール基に対応する場合、Ｒ₁、Ｒ₂基の定義において上述した置換基の少なくとも１つを有する。）を表す。）
ｎが０〜６までの整数であり、ｏが０〜２までの整数であり、ｐが０〜４までの整数であり、ｑが０〜３までの整数である。
なお、Ａが（Ａ_４）を示す場合、ｎが０〜２までの整数であり、ｐが０〜４までの整数であり、Ａが（Ａ_２）を示す場合、ｎが０〜２までの整数である。））
［４］ 下記一般式（ａ）または一般式（ｂ）で表される調光色素を含む、［１］から［３］のいずれかに記載のフォトクロミックレンズ。
ＰＣ-Ｌ-Ｃｈａｉｎ （ａ）
ＰＣ-Ｌ-Ｃｈａｉｎ-Ｌ'-ＰＣ' （ｂ）
（ＰＣとＰＣ'は一般式（ｃ）〜（ｆ）のいずれかを示す。ＰＣとＰＣ'は同一でも異なっていても良い。）

（一般式（ｃ）〜（ｆ）中、Ｒ^１〜Ｒ^１８は、水素、ハロゲン原子、カルボキシル基、アセチル基、ホルミル基、置換されてもよいＣ１〜Ｃ２０の脂肪族基、置換されてもよいＣ３〜Ｃ２０の脂環族基、または置換されてもよいＣ６〜Ｃ２０の芳香族有機基を示し、それぞれ同一でも異なってもよい。これら脂肪族基、脂環族基または芳香族有機基は、酸素原子、窒素原子を含んでもよい。一般式（ｃ）〜（ｆ）で表される化合物に含まれる、いずれか１つの基は、２価の有機基であるＬまたはＬ'と結合する。ＬとＬ'は、オキシエチレン鎖、オキシプロピレン鎖、（チオ）エステル基、（チオ）アミド基から選択される1種以上を含む２価の有機基を示す。Ｃｈａｉｎは、ポリシロキサン鎖、ポリオキシアルキレン鎖から選択される1種以上を含む１価または２価の有機基を示す。）
［５］ ポリ（メタ）アクリレート、ポリアリルカーボネート、およびポリ（チオ）ウレタンから選択される少なくとも一種を含む、［１］から［４］のいずれかに記載のフォトクロミックレンズ。
［６］ 前記ポリ（メタ）アクリレートは、下記一般式（ｉ）、一般式（ii）、一般式（iii）および式（iv）で表される化合物から選択される少なくとも２種から誘導される構成単位を含む、［５］に記載のフォトクロミックレンズ。

（式中、Ｒは、水素原子またはメチル基を示し、複数存在するＲは同一でも異なっていてもよい。ｍ、ｎは、０〜２０の整数を示し、同一でも異なっていてもよい。）

（式中、Ｒは、水素原子またはメチル基を示し、複数存在するＲは同一でも異なっていてもよい。ｐは、０〜２０の整数を示す。）

（式中、Ｒは、水素原子またはメチル基を示し、ｑは、０〜２０の整数を示す。）

［７］ フォトクロミックレンズは前記ポリアリルカーボネートと前記ポリ（メタ）アクリレートからなる混合物を含み、
当該混合物は、下記一般式（１１）で表される、アリルオキシカルボニル基を２つ以上含むアリルカーボネート化合物（Ａ）から誘導される構成単位（ａ）と、一般式（１２）で表される、（メタ）アクリル基を２つ以上含む（メタ）アクリレート化合物（Ｂ）から誘導される構成単位（ｂ）とを含んでなり、
構成単位（ａ）および構成単位（ｂ）の合計１００重量％に対して、構成単位（ａ）を５重量％〜３０重量％、構成単位（ｂ）を７０重量％〜９５重量％含む、［５］に記載のフォトクロミックレンズ。

（Ｒ^１は、ヘテロ原子を含んでいてもよい鎖状または分岐したＣ３〜Ｃ３５の脂肪族ポリオール由来の２〜２０価の基またはヘテロ原子を含んでいてもよいＣ５〜Ｃ４０の環状脂肪族ポリオール由来の２〜２０価の基を示す。ｍは、２〜１０の整数を示す。なお、Ｒ^１はアリルオキシカルボニル基を含まない。）

（Ｒ^２は、ヘテロ原子または芳香族基を含んでいてもよい炭素数１〜３０の２〜４価の有機基を示す。Ｒ^３は、水素原子あるいはメチル基を示す。ｎは２〜４の整数を示す。）
［８］ 化合物（Ａ）が、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、テトラエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、３−メチル−１，５−ペンタンジオール、２−メチル−２−エチル−１，３−プロパンジオール、２，２−ジエチル−１，３−プロパンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、１，４−ジメチロールシクロヘキサンおよび４，８−ビス（ヒドロキシメチル）−［５．２．１．０^２，６］トリシクロデカンから選択される少なくとも１種のジオールのビス（アリルカーボネート）化合物、
グリセロール、トリメチロールプロパンおよびトリス（ヒドロキシエチル）イソシアヌレートから選択される少なくとも１種のトリオールのトリス（アリルカーボネート）化合物、
ペンタエリスリトール、ジグリセロールおよびジトリメチロールプロパンから選択される少なくとも１種のテトラオールのテトラ（アリルカーボネート）化合物、
ジペンタエリスリトールのヘキサ（アリルカーボネート）化合物、および
前記ジオール、前記トリオール、前記テトラオールおよび前記ジペンタエリスリトールから選択される少なくとも２種類の化合物の混合ポリ（アリルカーボネート）化合物、から選択される少なくとも一種である、［７］に記載のフォトクロミックレンズ。
［９］ 化合物（Ａ）が、
(i)ジエチレングリコールのビス（アリルカーボネート）化合物およびそのオリゴマーとの混合物、
(ii) ジエチレングリコールとネオペンチルグリコールの混合物のビス（アリルカーボネート）化合物およびそのオリゴマーとの混合物、
(iii) ジエチレングリコールとトリス（ヒドロキシエチル）イソシアヌレートの混合物のポリ（アリルカーボネート）化合物およびそのオリゴマーとの混合物、
(iv) ジエチレングリコールとトリメチロールプロパンの混合物のポリ（アリルカーボネート）化合物およびそのオリゴマーとの混合物、
(v) ジエチレングリコールとペンタエリスリトールの混合物のポリ（アリルカーボネート）化合物およびそのオリゴマーとの混合物、
(vi) ジエチレングリコールとネオペンチルグリコールとペンタエリスリトールの混合物のポリ（アリルカーボネート）化合物およびそのオリゴマーとの混合物、および
(vii) ジエチレングリコールとネオペンチルグリコールとペンタエリスリトールの混合物のポリ（アリルカーボネート）化合物およびそのオリゴマーとの混合物と、
ジエチレングリコールのビス（アリルカーボネート）化合物およびそのオリゴマーとの混合物と、を含むポリ（アリルカーボネート）混合物、から選択される少なくとも一種である、［７］または［８］に記載のフォトクロミックレンズ。
［１０］ 化合物（Ｂ）が、下記一般式（１６）および下記一般式（１７）で表される化合物から選択される少なくとも一種である、［７］から［９］のいずれかに記載のフォトクロミックレンズ。

（ｐは１〜１００の数値を示し、Ｒ^３は水素原子またはメチル基を示し、それぞれ同一でなくても良い。）

（ｑは、それぞれ１以上の数値を示し、２つのｑの合計は２〜１００の数値を示す。Ｒ^３は、水素原子またはメチル基を示し、それぞれ同一でなくても良い。Ｘは、置換または無置換の２価の芳香族基、置換または無置換の炭素数１〜２０の芳香族基を含んでいても良い２価の脂肪族基を示す。）
［１１］ 化合物（Ｂ）が、一般式（１６）において、ｐが２〜４で表される化合物から選択される、［１０］に記載のフォトクロミックレンズ。
［１２］ 化合物（Ｂ）が、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、およびトリエチレングリコールジアクリレートから選択される少なくとも一種である、［１１］に記載のフォトクロミックレンズ。
［１３］ （ａ）ポリイソシアネート化合物から誘導される構成単位と、（ｂ）数平均分子量が１００以上であるポリオール化合物から誘導される構成単位と、（ｃ）二官能以上の活性水素化合物（ただし、前記化合物（ｂ）を除く）から誘導される構成単位とを含む、［５］に記載のフォトクロミックレンズ。
［１４］ ポリイソシアネート化合物（ａ）が、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、ビス（イソシアナトメチル）シクロヘキサン、ジシクロヘキシルメタンジイソシアネート、２，５−ビス（イソシアナトメチル）ビシクロ−[２．２．１]−ヘプタン、２，６−ビス（イソシアナトメチル）ビシクロ−[２．２．１]−ヘプタン、トリレンジイソシアネート、フェニレンジイソシアネート、およびジフェニルメタンジイソシアネートよりなる群から選択される少なくとも１種である、［１３］に記載のフォトクロミックレンズ。
［１５］ ポリオール化合物（ｂ）が、ポリエチレングリコールまたはポリプロピレングリコールのジオール型またはトリオール型である、［１３］または［１４］に記載のフォトクロミックレンズ。
［１６］ ポリオール化合物（ｂ）の数平均分子量が２００〜４０００である、［１５］に記載のフォトクロミックレンズ。
［１７］ ポリオール化合物（ｂ）が、下記一般式（Ｉ）で表される化合物である、［１３］または［１４］に記載のフォトクロミックレンズ。

（一般式（Ｉ）中、Ｒ^１およびＲ^２は、水素原子、メチル基、エチル基を表し、少なくともどちらか一方は水素原子である。Ｒ^１およびＲ^２は、同一でも異なっていてもよい。ｎは３０以上５００以下の整数を示す。）
［１８］ ポリオール化合物（ｂ）が、下記一般式（II）で表される化合物である、［１７］に記載のフォトクロミックレンズ。

（一般式（II）中、Ｒ^３およびＲ^４は、水素原子、メチル基、エチル基を表し、少なくともどちらか一方は水素原子である。Ｒ^３およびＲ^４は、同一でも異なっていてもよい。ａ＋ｃは２以上４００以下の整数であり、bは１以上１００以下の整数を表す。）
［１９］ 一般式（II）で表される化合物の数平均分子量が１０００から１５０００である、［１８］に記載のフォトクロミックレンズ。
［２０］ 一般式（II）で表される化合物の数平均分子量が１５００から７５００である、［１９］に記載のフォトクロミックレンズ。
［２１］ 活性水素化合物（ｃ）が、ポリオール化合物、ポリチオール化合物および水酸基を有するチオール化合物よりなる群から選択される少なくとも１種である、［１３］から［２０］のいずれかに記載のフォトクロミックレンズ。
［２２］ 活性水素化合物（ｃ）が三官能以上の活性水素化合物である、［１３］から［２１］のいずれかに記載のフォトクロミックレンズ。
［２３］ 活性水素化合物（ｃ）が、グリセリン、ペンタエリスリトールテトラキス（２−メルカプトアセテート）、ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、４−メルカプトメチル−１，８−ジメルカプト−３，６−ジチアオクタン、５，７−ジメルカプトメチル−１，１１−ジメルカプト−３，６，９−トリチアウンデカン、４，７−ジメルカプトメチル−１，１１−ジメルカプト−３，６，９−トリチアウンデカン、４，８−ジメルカプトメチル−１，１１−ジメルカプト−３，６，９−トリチアウンデカン、１，１，３，３−テトラキス（メルカプトメチルチオ）プロパン、およびトリメチロールプロパントリス（３−メルカプトプロピオネート）よりなる群から選択される少なくとも１種である、［１３］から［２２］のいずれかに記載のフォトクロミックレンズ。
［２４］ 偏光フィルムと、前記偏光フィルムの少なくとも対物面側の面上に形成された、［１］〜［２３］のいずれかに記載のフォトクロミックレンズからなる基材層とを備える、プラスチック偏光レンズ。 The present invention can be shown below.
[1] The luminous transmittance from 400 nm to 780 nm is 90% or more at the time of decoloring,
A photochromic lens in which the transmittance at 23 ° C. after irradiation for 15 minutes at an illuminance of 50000 lux using a xenon lamp satisfies the following conditions.
(1) The luminous transmittance from 400 nm to 780 nm is 20% or less.
(2) The value obtained by subtracting the average transmittance of 400 nm to 420 nm from 100% is 90% or more.
(3) A value obtained by subtracting the luminous transmittance from 400 nm to 780 nm from the luminous transmittance from 460 nm to 500 nm is 10% or more.
[2] The photochromic lens according to [1], including at least one photochromic dye selected from the compounds represented by the following general formula (3) and the general formula (4).

(In the general formula (3) and the general formula (4), R ₁ and R ₂ may be the same or different, and independently hydrogen;
A linear or branched alkyl group having 1 to 12 carbon atoms;
A cycloalkyl group having 3 to 12 carbon atoms;
A substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a heteroaryl group having 4 to 24 carbon atoms;
An aralkyl or heteroaralkyl group (a linear or branched alkyl group having 1 to 4 carbon atoms is substituted with the above-mentioned aryl group or heteroaryl group) is shown.
The substituent of the substituted aryl group having 6 to 24 carbon atoms or the substituted heteroaryl group having 4 to 24 carbon atoms is a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, carbon A linear or branched alkoxy group of 1 to 12, a linear or branched haloalkyl group of 1 to 12 carbon atoms substituted with at least one halogen atom, a carbon atom 1 substituted with at least one halogen atom To 12 linear or branched haloalkoxy groups, at least one linear or branched alkyl group having 1 to 12 carbon atoms, or a phenoxy group or naphthoxy group substituted by an alkoxy group, a straight chain having 2 to 12 carbon atoms A chain or branched alkenyl group, -NH ₂ group, -NHR group, -N (R) ₂ group (R is a linear or branched alkyl group having 1 to 6 carbon atoms. There are two R groups. If And two R's may be the same or different) and at least one selected from a methacryloyl group or an acryloyl group.
R ₃ may be the same or different, and independently, a halogen atom;
A linear or branched alkyl group having 1 to 12 carbon atoms;
A cycloalkyl group having 3 to 12 carbon atoms;
A linear or branched alkoxy group having 1 to 12 carbon atoms;
A linear or branched haloalkyl group having 1 to 12 carbon atoms substituted with at least one halogen atom, a halocycloalkyl group having 3 to 12 carbon atoms substituted with at least one halogen atom, at least one halogen atom A substituted linear or branched haloalkoxy group having 1 to 12 carbon atoms;
A substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a heteroaryl group having 4 to 24 carbon atoms (as a substituent, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, C1-C12 linear or branched alkoxy group, C1-C12 linear or branched haloalkyl group substituted by at least one halogen atom, carbon number substituted by at least one halogen atom 1 to 12 linear or branched haloalkoxy group, at least one linear or branched alkyl group having 1 to 12 carbon atoms, or phenoxy or naphthoxy group substituted by an alkoxy group, having 2 to 12 carbon atoms A linear or branched alkenyl group, and an amino group, having at least one substituent selected from
An aralkyl or heteroaralkyl group (a linear or branched alkyl group having 1 to 4 carbon atoms is substituted with the above aryl group or heteroaryl group);
A substituted or unsubstituted phenoxy or naphthoxy group (having at least one substituent selected from a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxy group as a substituent);
-NH _2, -NHR, -CONH ₂ or -CONHR,
(R is a linear or branched alkyl group having 1 to 6 carbon atoms.);
—OCOR ₈ or —COOR ₈ (wherein, R ₈ is a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, or substituted at R ₁ and R ₂ A phenyl group substituted by at least one of the substituents of the aryl or substituted heteroaryl group or an unsubstituted phenyl group);
Represents
At least two adjacent R ₃ bonded to each other include a carbon atom to which R ₃ is attached, can form one or more aromatic ring group or non-aromatic ring group. The aromatic or non-aromatic ring group comprises one ring or two annelated rings which may contain heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen.
l is an integer of 0 to 2; m is an integer from 0 to 4; )
[3] The photochromic lens according to [1] or [2], which contains a photochromic dye represented by the following general formula (5).

(In the general formula (5), R ¹ , R ² , R ³ and m are the same as the general formula (3), and A represents an annelated ring of the following formulas (A ₁ ) to (A ₅ ) .

(In these anelized rings (A ₁ ) to (A ₅ ), the dotted line represents a carbon C ₅ carbon C ₆ bond of the naphthopyran ring of the general formula (5). Anodized ring (A ₄ ) or (A ₅ ) The α bond of) is bonded to carbon ₅ or carbon ₆ of the naphthopyran ring of the general formula (5).
R ₄ is the same or different and independently represent OH, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkoxy group, or two R ₄ form a carbonyl (CO).
R ₅ , R ₆ and R ₇ independently represent a halogen atom;
A linear or branched alkyl group having 1 to 12 carbon atoms;
A linear or branched haloalkyl group having 1 to 6 carbon atoms, which is substituted by at least one halogen atom;
A cycloalkyl group having 3 to 12 carbon atoms;
A linear or branched alkoxy group having 1 to 6 carbon atoms;
A substituted or unsubstituted phenyl or benzyl group (when R ₁ and R _{2 in} the general formula (5) independently correspond to an aryl or heteroaryl group as a substituent, they are as defined above in the definition of R ₁ and R ₂₎ With at least one of the
-NH _2, -NHR
(Wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms);
A substituted or unsubstituted phenoxy or naphthoxy group (having a linear or branched alkyl group having at least 1 to 6 carbon atoms or an alkoxy group as a substituent);
-COR ₉ , -COOR ₉ or -CONHR ₉ group (wherein R ₉ is a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, or substituted or non-substituted A substituted phenyl or benzyl group (when the R ₁ and R ₂ groups in the general formula (5) independently correspond to an aryl or heteroaryl group as a substituent, the substituents described above in the definition of R ₁ and R ₂ groups Have at least one of the
n is an integer from 0 to 6, o is an integer from 0 to 2, p is an integer from 0 to 4, and q is an integer from 0 to 3.
In addition, when A shows (A ₄ ), n is an integer from 0 to 2, p is an integer from 0 to 4, and when A shows (A ₂ ), n is from 0 to 2 Is an integer of )))
[4] The photochromic lens according to any one of [1] to [3], which contains a photochromic dye represented by the following general formula (a) or (b).
PC-L-Chain (a)
PC-L-Chain-L'-PC '(b)
(PC and PC ′ each represent any of the general formulas (c) to (f). PC and PC ′ may be the same or different.)

(In the general formulas (c) to (f), R ^{1 to} R ^{18 each} represent a hydrogen, a halogen atom, a carboxyl group, an acetyl group, a formyl group, a C1 to C20 aliphatic group which may be substituted, or a substituted one It is a good C3 to C20 alicyclic group, or an optionally substituted C6 to C20 aromatic organic group, which may be the same or different, and these aliphatic group, alicyclic group or aromatic organic group is And any one of the groups contained in the compounds represented by formulas (c) to (f) is bonded to L or L 'which is a divalent organic group. L and L ′ each represent a divalent organic group containing one or more selected from an oxyethylene chain, an oxypropylene chain, a (thio) ester group, and a (thio) amide group, and a chain is a polysiloxane chain, One or more selected from polyoxyalkylene chains Represents a monovalent or divalent organic group containing
[5] The photochromic lens according to any one of [1] to [4], including at least one selected from poly (meth) acrylates, polyallyl carbonates, and poly (thio) urethanes.
[6] The poly (meth) acrylate is derived from at least two selected from the compounds represented by the following general formula (i), general formula (ii), general formula (iii) and formula (iv) The photochromic lens as described in [5] which contains a structural unit.

(In the formula, R represents a hydrogen atom or a methyl group, and a plurality of R may be the same or different. M and n represent an integer of 0 to 20 and may be the same or different.)

(In the formula, R represents a hydrogen atom or a methyl group, and a plurality of R may be the same or different. P represents an integer of 0 to 20.)

(Wherein, R represents a hydrogen atom or a methyl group, and q represents an integer of 0 to 20).

[7] A photochromic lens comprises a mixture of the polyallyl carbonate and the poly (meth) acrylate,
The mixture is represented by a structural unit (a) represented by the following general formula (11) and a structural unit (a) derived from an allyl carbonate compound (A) containing two or more allyloxycarbonyl groups, and a general formula (12) And a structural unit (b) derived from a (meth) acrylate compound (B) containing two or more (meth) acrylic groups,
5% by weight to 30% by weight of the structural unit (a) and 70% by weight to 95% by weight of the structural unit (b) with respect to a total of 100% by weight of the structural unit (a) and the structural unit (b) The photochromic lens as described in 5].

(R ¹ is a C5 to C40 cycloaliphatic polyol which may contain a heterovalent group or a divalent group derived from a chained or branched C3 to C35 aliphatic polyol which may contain a hetero atom M represents an integer of 2 to 10. Note that R ¹ does not contain an allyloxycarbonyl group.)

(R ² represents a hetero atom or a divalent to tetravalent organic group having 1 to 30 carbon atoms which may contain an aromatic group. R ³ represents a hydrogen atom or a methyl group. N is 2 to 4) Indicates an integer of
[8] Compound (A) is diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol Neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4- At least one selected from trimethyl-1,3-pentanediol, 1,4-dimethylol cyclohexane and 4,8-bis (hydroxymethyl)-[5.2.1.0 ^2,6 ] tricyclodecane Bis (allyl carbonate) compounds of diols,
A tris (allyl carbonate) compound of at least one triol selected from glycerol, trimethylolpropane and tris (hydroxyethyl) isocyanurate,
At least one tetraol tetra (allyl carbonate) compound selected from pentaerythritol, diglycerol and ditrimethylolpropane;
At least one selected from a hexa (allyl carbonate) compound of dipentaerythritol and a mixed poly (allyl carbonate) compound of at least two compounds selected from the diol, the triol, the tetraol, and the dipentaerythritol. The photochromic lens according to [7], which is
[9] The compound (A) is
(i) mixtures of diethylene glycol with bis (allyl carbonate) compounds and their oligomers,
(ii) bis (allyl carbonate) compounds of mixtures of diethylene glycol and neopentyl glycol and mixtures thereof with oligomers,
(iii) a mixture of diethylene glycol and tris (hydroxyethyl) isocyanurate with a poly (allyl carbonate) compound and its oligomer,
(iv) mixtures of diethylene glycol and trimethylolpropane with poly (allyl carbonate) compounds and their oligomers,
(v) Mixtures of diethylene glycol and pentaerythritol with poly (allyl carbonate) compounds and their oligomers,
(vi) mixtures of poly (allyl carbonate) compounds of mixtures of diethylene glycol, neopentyl glycol and pentaerythritol and their oligomers, and
(vii) a mixture of diethylene glycol, neopentyl glycol and pentaerythritol and a mixture of poly (allyl carbonate) compounds and their oligomers;
The photochromic lens according to [7] or [8], which is at least one selected from a poly (allyl carbonate) mixture including a mixture of diethylene glycol with a bis (allyl carbonate) compound and an oligomer thereof.
[10] The photochromic according to any one of [7] to [9], wherein the compound (B) is at least one selected from the compounds represented by the following general formula (16) and the following general formula (17) lens.

(P represents a numerical value of 1 to 100, R ³ represents a hydrogen atom or a methyl group, and may not be identical to each other.)

(Q represents a numerical value of 1 or more, respectively, and the sum of two q represents a numerical value of 2 to 100. R ³ represents a hydrogen atom or a methyl group, which may not be identical to each other. X is a substitution Or a divalent aliphatic group which may contain a substituted or unsubstituted divalent aromatic group or a substituted or unsubstituted C1 to C20 aromatic group.
[11] The photochromic lens according to [10], wherein the compound (B) is selected from compounds represented by p in the general formula (16), 2 to 4.
[12] The photochromic lens according to [11], wherein the compound (B) is at least one selected from diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate.
[13] (a) a structural unit derived from a polyisocyanate compound, (b) a structural unit derived from a polyol compound having a number average molecular weight of 100 or more, and (c) an active hydrogen compound having two or more functional groups The photochromic lens according to [5], comprising a constituent unit derived from the compound (b)).
[14] The polyisocyanate compound (a) is hexamethylene diisocyanate, pentamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, tolylene diisocyanate, phenylene diisocyanate, and at least one selected from the group consisting of diphenylmethane diisocyanate The photochromic lens as described in [13] which is 1 type.
[15] The photochromic lens according to [13] or [14], wherein the polyol compound (b) is a diol type or triol type of polyethylene glycol or polypropylene glycol.
[16] The photochromic lens according to [15], wherein the number average molecular weight of the polyol compound (b) is 200 to 4000.
[17] The photochromic lens according to [13] or [14], wherein the polyol compound (b) is a compound represented by the following general formula (I).

(In general formula (I), R ¹ and R ^{2 each} represent a hydrogen atom, a methyl group or an ethyl group, at least one of which is a hydrogen atom. R ¹ and R ² may be the same or different) N is an integer of 30 or more and 500 or less)
[18] The photochromic lens according to [17], wherein the polyol compound (b) is a compound represented by the following general formula (II).

(In general formula (II), R ³ and R ^{4 each} represent a hydrogen atom, a methyl group or an ethyl group, and at least one of them is a hydrogen atom. R ³ and R ⁴ may be the same or different. A + c is an integer of 2 or more and 400 or less, and b is an integer of 1 or more and 100 or less.)
[19] The photochromic lens according to [18], wherein the number average molecular weight of the compound represented by the general formula (II) is from 1,000 to 15,000.
[20] The photochromic lens according to [19], wherein the number average molecular weight of the compound represented by the general formula (II) is from 1500 to 7500.
[21] The photochromic lens according to any one of [13] to [20], wherein the active hydrogen compound (c) is at least one selected from the group consisting of a polyol compound, a polythiol compound and a thiol compound having a hydroxyl group. .
[22] The photochromic lens according to any one of [13] to [21], wherein the active hydrogen compound (c) is a trifunctional or higher active hydrogen compound.
[23] Active hydrogen compound (c) is glycerin, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6- Dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, and trimethylolpropane tris (3-mercaptopropio) At least one member selected from the group consisting of ] The photochromic lens in any one of [22].
[24] A plastic polarized lens comprising: a polarizing film; and a base layer composed of the photochromic lens according to any one of [1] to [23], formed on at least the surface on the objective side of the polarizing film. .

  In the present invention, for example, “a bis (allyl carbonate) compound of a diol” means a compound having a structure in which two hydroxyl groups of the diol are replaced by an allyl carbonate group. The diol may be used alone or in combination of two or more.

In the present invention, for example, “a bis (allyl carbonate) compound of a mixture of diethylene glycol and neopentyl glycol” means
(1) a compound having a structure in which two hydroxyl groups of diethylene glycol are replaced by allyl carbonate group,
(2) It means a compound having a structure in which two hydroxyl groups of neopentyl glycol are replaced by allyl carbonate groups.
Further, in the present invention, for example, “an oligomer of a bis (allyl carbonate) compound of a mixture of diethylene glycol and neopentyl glycol” is
The following (3), (4), or any one of (5), or a mixture of two or more selected from these is meant.
(3) Oligomer of bis (allyl carbonate) compound of diethylene glycol A compound having a structure in which two or more molecules of diethylene glycol are oligomerized via a carbonate bond, and the terminal hydroxyl group is replaced by an allyl carbonate group.
(4) Oligomer of Bis (allyl carbonate) Compound of Neopentyl Glycol A compound having a structure in which two or more molecules of neopentyl glycol are oligomerized via a carbonate bond, and the terminal hydroxyl group is replaced by an allyl carbonate group.
(5) Oligomer of bis (allyl carbonate) compound of diethylene glycol and neopentyl glycol One or more molecules of diethylene glycol and one or more molecules of neopentyl glycol are oligomerized in the same molecule in a random combination via carbonate bond, The compound which has a structure where the terminal hydroxyl group was substituted by the allyl carbonate group.
The same applies to the case of “a bis (allyl carbonate) compound of a trifunctional or higher functional polyol” and a “bis (allyl carbonate) compound using two or more types of a diol and a trifunctional or higher functional polyol”.
In the case of “oligomer of bis (allyl carbonate) compound of polyol having trifunctional or higher functionality” and “oligomer of bis (allyl carbonate) compound using two or more types of diol and trifunctional or higher polyol”, all terminal hydroxyl groups are The structure substituted by the allyloxy carbonate group, the structure by which one part hydroxyl groups were substituted by the aryloxy carbonate group are included.
In the present invention, for example, “1 to 10” means “1 or more and 10 or less”.
In the present invention, hetero atoms mean atoms other than C and H.

  Further, in the present invention, “at the time of decoloring” means a method according to ISO / DIS 8980-3 (JIS T7333), storing the sample in a dark place at 65 ° C. for 2 hours, and then in a dark place at 23 ° C. It means that it has been stored for at least 12 hours.

  According to the molded article of the present invention, it is possible to provide a photochromic lens which transmits light effective for circadian rhythm while sufficiently cutting glare from sunlight and harmful HEV region light.

It is a chart which shows the transmittance | permeability curve (spectral transmittance | permeability) of the resin flat plate obtained in Example 1. FIG. It is a chart which shows the transmittance | permeability curve (spectral transmittance | permeability) of the resin flat plate obtained in Example 2. FIG. It is a chart which shows the transmittance | permeability curve (spectral transmittance | permeability) of the resin flat plate obtained in Example 3. FIG.

First, the photochromic lens of the present invention will be described based on the following embodiments.
The photochromic lens of this embodiment has a luminous transmittance of 90% or more from 400 nm to 780 nm at the time of color erasing, and a transmittance at 23 ° C. after irradiation for 15 minutes at an illuminance of 50000 lux using a xenon lamp. But the following conditions.
(1) The luminous transmittance from 400 nm to 780 nm is 20% or less.
(2) The value obtained by subtracting the average transmittance of 400 nm to 420 nm from 100% is 90% or more.
(3) A value obtained by subtracting the luminous transmittance from 400 nm to 780 nm from the luminous transmittance from 460 nm to 500 nm is 10% or more.
In addition, about the conditions irradiated with the illumination intensity 50000 lux using a xenon lamp, it is based on ISO8980-3.
The luminous transmittance is calculated based on ISO 8980-3 from the measured value of the spectral transmittance at the time of decoloring or color development of a 2 mm thick photochromic lens.

When the photochromic lens satisfies the above conditions, it is possible to transmit light effective for circadian rhythm while sufficiently cutting off glare from sunlight and light in harmful HEV regions.
The photochromic lens of the present embodiment comprises a photochromic dye and a resin.
Each component will be described below.

[Light control dye]
In the present embodiment, the photochromic dye (photochromic compound) is not particularly limited, and any photochromic compound can be appropriately selected and used from conventionally known compounds which can be used for the photochromic lens. For example, one or two or more kinds of spiropyran compounds, spirooxazine compounds, fulgide compounds, naphthopyran compounds, bisimidazole compounds can be used depending on the desired color, and may be a general formula (a) described later. And at least one selected from general formula (b) can also be used.
The photochromic lens of the present embodiment can contain 100 to 3000 ppm, preferably 100 to 2500 ppm, and more preferably 1100 to 2200 ppm of the photochromic dye relative to 100% by weight of the resin from the viewpoint of the effect of the present invention.

  Examples of the above-mentioned spiropyran compounds include indole ring and benzene ring of indolinospirobenzopyran substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group etc., indole ring of indolinospironaphthopyran, Each substituted form in which the naphthalene ring is substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group etc., each substitution in which the indole ring of indolinospiroquinolinopyran is substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group etc. And each substituted form in which the indole ring of indolinospiropyridopyran is substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group etc., and the like. At least one selected from these compounds can be used.

  Examples of the spirooxazine compounds include halogens in which indolinospirobenzoxazine is substituted with an indole ring and a benzene ring, and substituted substances each substituted with methyl, ethyl, methylene, ethylene, hydroxyl group, etc., indolinospironaphthoxazine Indole ring and naphthalene ring of the above are each substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group etc., indole ring of indolinospirophenanthrooxazine is halogen, methyl, ethyl, methylene, ethylene, hydroxyl group etc. Each substituted form of indino ring, each substituted form of indole ring of indolinospiroquinolinoxazine substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group etc., piperidine ring and naphthalene ring of piperidino spironaphthoxazine Halogen, methyl Ethyl, methylene, ethylene, substitution products substituted by a hydroxyl group or the like, and the like. At least one selected from these compounds can be used.

Examples of the fulgide compounds include N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophene dicarboximide-7,2′-tricyclo [3. 3.1.1 ^3,7 ! Decane], N-cyanomethyl-6,7-dihydro-2- (p-methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophene dicarboximide-7, 2'-tricyclo [3.3.1.1 ^3,7 ] decane), 6,7-dihydro-N-methoxycarbonylmethyl-4-methyl-2-phenylspiro (5,6-benzo [b] thiophenedi) Carboximido-7,2'-tricyclo [3.3.1.1 ^3,7 ] decane), 6,7-dihydro-4-methyl-2- (p-methylphenyl) -N-nitromethyl spiro (5 , 6-benzo [b Thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 ^{3, 7]} decane), N- cyanomethyl-6,7-dihydro-4-cyclopropyl-3- methylspiro (5,6-benzo [B] Thiophene dicarboximide-7,2'-tricyclo [3.3.1.1 ^3,7 ] decane), N-cyanomethyl-6,7-dihydro-4-cyclopropyl spiro (5,6-benzo) [B] Thiophene dicarboximide-7,2'-tricyclo [3.3.1.1 ^3,7 ] decane), N-cyanomethyl-6,7-dihydro-2- (p-methoxyphenyl) -4- And cyclopropyl spiro (5,6-benzo [b] thiophene dicarboximide-7,2'-tricyclo [3.3.1.1 ^3,7 ] decane), etc., etc. It is selected from these compounds. At least one It can be used.

  Examples of the naphthopyran-based compound include spiro [norbornane-2,2 ′-[2H] benzo [h] chromen] and spiro [bicyclo [3.3.1] nonane-9,2 ′-[2H] benzo [ h) chromene], 7'-methoxyspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [h] chromen], 7'-methoxyspi [norbornane-2,2'-[2H] ] 2, 2-Dimethyl-7-octoxy [2H] benzo [h] chromene, spiro [2- bicyclo [3.3.1] nonene-9, 2'- [2 H] benzo [] h) chromene], spiro [2-bicyclo [3.3.1] nonene-9,2 '-[2H] benzo [f] chromen], 6-morpholino-3,3-bis (3-fluoro-4-) Methoxyphenyl) -3H-benzo (f) chromene 5-isopropyl-2,2-diphenyl -2H- benzo (h) chromene, etc. and include compounds represented by the compound represented by and the following formula by the following general formula (3) (4). At least one selected from these compounds can be used.

In the general formula (3) and the general formula (4), R ₁ and R ₂ may be the same or different, and independently hydrogen.
A linear or branched alkyl group having 1 to 12 carbon atoms;
A cycloalkyl group having 3 to 12 carbon atoms;
A substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a heteroaryl group having 4 to 24 carbon atoms;
An aralkyl or heteroaralkyl group (a linear or branched alkyl group having 1 to 4 carbon atoms is substituted with the above-mentioned aryl group or heteroaryl group) is shown.

The substituent of the substituted aryl group having 6 to 24 carbon atoms or the substituted heteroaryl group having 4 to 24 carbon atoms is a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, carbon A linear or branched alkoxy group of 1 to 12, a linear or branched haloalkyl group of 1 to 12 carbon atoms substituted with at least one halogen atom, a carbon atom 1 substituted with at least one halogen atom To 12 linear or branched haloalkoxy groups, at least one linear or branched alkyl group having 1 to 12 carbon atoms, or a phenoxy group or naphthoxy group substituted by an alkoxy group, a straight chain having 2 to 12 carbon atoms A chain or branched alkenyl group, -NH ₂ group, -NHR group, -N (R) ₂ group (R is a linear or branched alkyl group having 1 to 6 carbon atoms. There are two R groups. If And two R's may be the same or different) and at least one selected from a methacryloyl group or an acryloyl group.

R ₃ may be the same or different, and independently, a halogen atom;
A linear or branched alkyl group having 1 to 12 carbon atoms;
A cycloalkyl group having 3 to 12 carbon atoms;
A linear or branched alkoxy group having 1 to 12 carbon atoms;
A linear or branched haloalkyl group having 1 to 12 carbon atoms substituted with at least one halogen atom, a halocycloalkyl group having 3 to 12 carbon atoms substituted with at least one halogen atom, at least one halogen atom A substituted linear or branched haloalkoxy group having 1 to 12 carbon atoms;
A substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a heteroaryl group having 4 to 24 carbon atoms (as a substituent, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, C1-C12 linear or branched alkoxy group, C1-C12 linear or branched haloalkyl group substituted by at least one halogen atom, carbon number substituted by at least one halogen atom 1 to 12 linear or branched haloalkoxy group, at least one linear or branched alkyl group having 1 to 12 carbon atoms, or phenoxy or naphthoxy group substituted by an alkoxy group, having 2 to 12 carbon atoms A linear or branched alkenyl group, and an amino group, having at least one substituent selected from
An aralkyl or heteroaralkyl group (a linear or branched alkyl group having 1 to 4 carbon atoms is substituted with the above aryl group or heteroaryl group);
A substituted or unsubstituted phenoxy or naphthoxy group (having at least one substituent selected from a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxy group as a substituent);
-NH _2, -NHR, -CONH ₂ or -CONHR,
(R is a linear or branched alkyl group having 1 to 6 carbon atoms.);
—OCOR ₈ or —COOR ₈ (wherein, R ₈ is a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, or substituted at R ₁ and R ₂ A phenyl group substituted by at least one of the substituents of the aryl or substituted heteroaryl group or an unsubstituted phenyl group);
Represents

At least two adjacent R ₃ bonded to each other include a carbon atom to which R ₃ is attached, can form one or more aromatic ring group or non-aromatic ring group. The aromatic or non-aromatic ring group comprises one ring or two annelated rings which may contain heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen.
l is an integer of 0 to 2; m is an integer from 0 to 4;

  In addition, as a naphthopyran-based compound, at least one of the polysiloxane oligomer, the polyalkylene oxide, and the polyalkyl ester described in WO2013 / 78086, WO2012 / 149599, WO2010 / 020770, WO2009 / 146509 is a light control dye molecule And compounds having the structure represented by the general formula (3) or the general formula (4) described above linked by a linking group and having two or more naphthopyran rings in one molecule, and the like.

  Among the naphthopyran-based compounds represented by the general formula (3), a compound represented by the following general formula (5) (hereinafter also referred to as a compound (5)) is mentioned as a preferred example.

R ₁ , R ₂ , R ₃ and m are the same as in the general formula (3), and A represents an annelated ring of the following formulas (A ₁ ) to (A ₅ ).

In these anylated rings (A ₁ ) to (A ₅ ), the dotted line represents a carbon C ₅ carbon C ₆ bond of the naphthopyran ring of the general formula (5). The α bond of the annelated ring (A ₄ ) or (A ₅ ) is bonded to carbon C ₅ or carbon C ₆ of the naphthopyran ring of general formula (5).

R ₄ is the same or different and independently represent OH, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkoxy group, or two R ₄ form a carbonyl (CO).
R ₅ , R ₆ and R ₇ independently represent a halogen atom (preferably fluorine, chlorine or bromine);
A linear or branched alkyl group having 1 to 12 carbon atoms (preferably, a linear or branched alkyl group having 1 to 6 carbon atoms);
A linear or branched haloalkyl group having 1 to 6 carbon atoms (preferably a fluoroalkyl group), which is substituted by at least one halogen atom;
A cycloalkyl group having 3 to 12 carbon atoms;
A linear or branched alkoxy group having 1 to 6 carbon atoms;
A substituted or unsubstituted phenyl or benzyl group (when R ₁ and R _{2 in} the general formula (5) independently correspond to an aryl or heteroaryl group as a substituent, they are as defined above in the definition of R ₁ and R ₂₎ With at least one of the
-NH _2, -NHR
(Wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms);
A substituted or unsubstituted phenoxy or naphthoxy group (having a linear or branched alkyl group having at least 1 to 6 carbon atoms or an alkoxy group as a substituent);
-COR ₉ , -COOR ₉ or -CONHR ₉ group (wherein R ₉ is a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, or substituted or non-substituted A substituted phenyl or benzyl group (when the R ₁ and R ₂ groups in the general formula (5) independently correspond to an aryl or heteroaryl group as a substituent, the substituents described above in the definition of R ₁ and R ₂ groups With at least one of

n is an integer from 0 to 6, o is an integer from 0 to 2, p is an integer from 0 to 4, and q is an integer from 0 to 3.
In addition, when A shows (A ₄ ), n is an integer from 0 to 2, p is an integer from 0 to 4, and when A shows (A ₂ ), n is from 0 to 2 Is an integer of

  The photochromic compounds of the general formula (5), combined with the discoloration kinetics applied for the required application, have high colorability even at 40 ° C. The colors that can be easily achieved range from orange to blue.

In this embodiment, the compound (5) where A = (A ₁ ), the compound (5) where A = (A ₂ ), the compound (5) where A = (A ₃ ), A = (A ₂ ) _{Also included} are compounds (5) which are ₄ ), and mixtures of compounds (5) which belong to at least one different kind selected from the group consisting of compounds ( ₅ ) where A = (A ₅ ).
In the present embodiment, a compound represented by the following general formula (6) can be preferably used as the compound (5).

Ar ₁ and Ar ₂ are aromatic groups, which may be the same or different and each represent a benzene ring or a thiophene ring which may be substituted. As a substituent of the benzene ring or thiophene ring, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a linear or branched chain having 1 to 6 carbon atoms Alkyl mono (or di) substituted amino groups can be mentioned. R ₃ , R ₄ , R ₅ , m, n and p are as defined above.
As the compound (5), a compound represented by the following general formula (7) can be more preferably used.

In formula (7), R ₁₀ and R ₁₁ may be the same as or different from each other, and are a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, This represents a linear or branched alkyl mono (or di) substituted amino group having 1 to 6 carbon atoms. when m is 2, bonded to adjacent R ₃ together can form a ring structure containing a carbon atom R ₃ is attached. r and s are integers of 0 to 4; The above ring structure is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a heteroaryl group having 3 to 24 carbon atoms.
R ₃ , R ₄ , R ₅ , m, n and p are as defined above.

  As a specific example of a compound shown by General formula (7), the compound shown by following formula (8) or following formula (9) is mentioned. In the present embodiment, the compounds represented by Formula (8) and Formula (9) are preferable.

The compound represented by General formula (5) which is a photochromic compound can be synthesize | combined by a well-known method. For example, it can also be synthesized by the method described in JP-A-2004-500319.
Further, as a specific example of the naphthopyran type compound represented by the general formula (3), a compound represented by the following formula (10) can be mentioned as a preferable example.

  As the naphthopyran-based compound, one or more compounds selected from the compounds described above can be used.

  The photochromic lens of the present embodiment can contain 100 to 3000 ppm, preferably 100 to 2500 ppm, more preferably 1100 to 2200 ppm, and particularly preferably 1600 to 2200 ppm of a naphthopyran compound relative to 100% by weight of the resin. The addition amount can not be generally limited because the performance varies depending on the type of naphthopyran compound, but is appropriately selected depending on the performance of the naphthopyran compound and the type and addition amount of the tetraazaporphyrin compound.

As the photochromic compound in the present embodiment, at least one selected from General Formula (a) and General Formula (b) can also be used.
PC-L-Chain (a)
PC-L-Chain-L'-PC '(b)
PC and PC ′ represent monovalent groups derived from the compounds of the general formulas (c) to (f). PC and PC 'may be the same or different.

In formulas (c) to (f), R _{1 to} R ₁₈ each independently represent hydrogen, a halogen atom, a carboxyl group, an acetyl group, a formyl group, an optionally substituted C1 to C20 aliphatic group, optionally substituted C3 -C20 alicyclic group or C6-C20 aromatic organic group which may be substituted is shown, and may be same or different, respectively. These aliphatic group, alicyclic group or aromatic organic group may contain an oxygen atom or a nitrogen atom. Any one group contained in the compounds represented by the general formulas (c) to (f) is bonded to L or L ′ which is a divalent organic group.

As the C1 to C20 aliphatic group which may be substituted, a linear or branched C1 to C10 alkyl group, a linear or branched C1 to C10 alkoxy group, a linear or branched group C2 to C10 alkenyl group, C1 to C10 hydroxyalkyl group, C1 to C10 hydroxyalkoxy group, C1 to C10 alkyl group substituted by C1 to C10 alkoxy group, C1 to C10 alkoxy group substituted by C1 to C10 alkoxy group , C1-C5 haloalkyl group, C1-C5 dihaloalkyl group, C1-C5 trihaloalkyl group, C1-C10 alkylamino group, C1-C10 aminoalkyl group, linear or branched C1-C20 alkoxycarbonyl group, etc. Can be mentioned.
As a C3-C20 alicyclic group which may be substituted, a C3-C20 cycloalkyl group, a C6-C20 bicycloalkyl group, etc. can be mentioned.

  The C6 to C20 aromatic organic group which may be substituted includes phenyl group, C7 to C16 alkoxyphenyl group, arylamino group, diarylamino group, aryl C1 to C5 alkylamino group, cyclic amino group, arylcarbonyl group, Aroyl group etc. can be mentioned.

As R ₁ and R ₂ , preferably, a hydrogen atom; a halogen atom;
A linear or branched C1-C10 alkyl group, a linear or branched C1-C10 alkoxy group, a C1-C10 hydroxyalkoxy group, a C1-C10 alkoxy group substituted with a C1-C10 alkoxy group, C1 to C20 aliphatic group which may be substituted, such as C1 to C5 haloalkyl group, C1 to C5 dihaloalkyl group, C1 to C5 trihaloalkyl group, C1 to C5 alkylamino group;
An optionally substituted C6-C20 aromatic such as phenyl group, C7-C16 alkoxyphenyl group, C1-C5 dialkylamino group, arylamino group, diarylamino group, aryl C1-C5 alkylamino group, cyclic amino group and the like Organic groups; etc. can be mentioned. R ₁ and R ₂ may be the same or different.

As R ₃ , preferably, a hydrogen atom; a halogen atom; a carboxyl group; an acetyl group;
Linear or branched C1 to C10 alkyl group, linear or branched C2 to C10 alkynyl group, linear or branched C1 to C10 alkoxy group, C1 to C10 hydroxyalkyl group And optionally substituted C1-C20 fatty acid such as C1-C10 alkyl group substituted with C1-C10 alkoxy group, C1-C10 aminoalkyl group, linear or branched C1-C20 alkoxycarbonyl group, etc. Group group;
An optionally substituted C3 to C20 alicyclic group such as a C3 to C20 cycloalkyl group, a C6 to C20 bicycloalkyl group;
And C6-C20 aromatic organic groups which may be substituted, such as arylcarbonyl group, formyl group and aroyl group; and the like.

As R ₄ , preferably, a hydrogen atom; a halogen atom; a carboxyl group; an acetyl group; a formyl group;
Linear or branched C1 to C10 alkyl group, linear or branched C2 to C10 alkynyl group, linear or branched C1 to C10 alkoxy group, C1 to C10 hydroxyalkyl group And optionally substituted C1-C20 fatty acid such as C1-C10 alkyl group substituted with C1-C10 alkoxy group, C1-C10 aminoalkyl group, linear or branched C1-C20 alkoxycarbonyl group, etc. Group group;
An optionally substituted C3 to C20 alicyclic group such as a C3 to C20 cycloalkyl group, a C6 to C20 bicycloalkyl group;
Optionally substituted C 6 to C 20 of arylcarbonyl group, aroyl group, phenyl group, C 7 to C 16 alkoxyphenyl group, C 1 to C 10 dialkoxyphenyl group, C 1 to C 10 alkylphenyl group, C 1 to C 10 dialkylphenyl group, etc. Aromatic organic groups; and the like can be mentioned.

R ₃ and R ₄ may be bonded to each other. When R ₃ and R ₄ bond to each other to form a ring structure, general formula (g) or (h) can be mentioned. The dotted line represents the bond between the carbon atom to which R ₃ is attached and the carbon atom to which R ₄ is attached.

R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₄ , R ₁₅ and R _{16 each} have the same functional group as R ₁ and R ₂ . A plurality of R _{5 to} R ₇ may be the same or different.

As R ₁₁ , preferably, a hydrogen atom; a halogen atom;
C1 to C20 aliphatic group which may be substituted, such as linear or branched C1 to C20 alkyl group, C1 to C5 haloalkyl group, C1 to C5 dihaloalkyl group, C1 to C5 trihaloalkyl group;
C3-C20 cycloalkyl group, C6-C20 bicycloalkyl group, C3-C20 cycloalkyl group substituted with C1-C5 alkyl group, C6-C20 bicycloalkyl group substituted with C1-C5 alkyl group, etc. And an optionally substituted C3 to C20 alicyclic group;
The C6-C20 aromatic organic group which may be substituted, such as an aryl group substituted with a C1-C5 alkyl group;

As R ₁₂ and R ₁₃ , preferably, a hydrogen atom; a halogen atom;
An optionally substituted C1 to C20 aliphatic group such as a C1 to C10 alkyl group or a C1 to C5 alkyl alkoxycarbonyl group; an optionally substituted C3 to C20 alicyclic group such as a C5 to C7 cycloalkyl group Group; and the like.

As R ₁₇ and R ₁₈ , preferably, a hydrogen atom; a halogen atom;
A linear or branched C1 to C10 alkyl group, a C1 to C10 hydroxyalkyl group or the like, an optionally substituted C1 to C20 aliphatic group; a C5 to C7 cycloalkyl group or the like; Good C3 to C20 alicyclic group; and the like.

L and L ′ in the general formula (a) or (b) are a divalent organic containing at least one group selected from an oxyethylene chain, an oxypropylene chain, a (thio) ester group, and a (thio) amide group Indicates a group.
Specifically, L and L 'are represented by general formulas (i) to (o). L and L 'may be the same or different.

In formulas (i) to (o),
Y shows oxygen and sulfur.
R ₁₉ represents hydrogen or a linear or branched C1 to C10 alkyl group.
R ₂₀ represents a linear or branched C1-C10 alkyl group.
p shows the integer of 0-15, r shows the integer of 0-10.

Q represents a linear or branched C1 to C10 alkylene group, a C1 to C10 alkenylene group, or a divalent group derived from a substituted aryl group at 1,2-, 1,3-, or 1,4-position And a divalent group etc. derived from a substituted heteroaryl group.
* 1 and * 2 represent a bond, * 1 is bonded to a monovalent or divalent organic group represented by "Chain", and * 2 is a monovalent organic group represented by PC or PC ' Join.

“Chain” in the general formula (a) or (b) represents a monovalent or divalent organic group containing one or more selected from a polysiloxane chain and a polyoxyalkylene chain.
Examples of polysiloxane chains include polydimethylsiloxane chains, polymethylphenylsiloxane chains, polymethylhydrosiloxane chains and the like.

Examples of polyoxyalkylene chains include polyoxyethylene chains, polyoxypropylene chains, polyoxyhexamethylene chains and the like.
In particular,
"Chain" shows the monovalent organic group of general formula (p) or (q), when a photochromic compound is general formula (a).

  "Chain" shows the bivalent organic group of general formula (r) or (s), when a photochromic compound is general formula (b).

In formulas (p) to (s),
R ₂₁ represents a linear or branched C1-C10 alkyl group.
R ₂₂ represents a linear or branched C1-C10 alkyl group.
R ₂₃ represents hydrogen, a methyl group or an ethyl group.
n shows the integer of 4-75, m shows the integer of 1-50.
q is an integer of 1 to 3;
* 3 and * 4 each represent a bond, * 3 is bonded to the divalent organic group represented by L, and * 4 is bonded to the divalent organic group represented by L '.

From the viewpoint of the effect of the present invention, the photochromic lens of the present embodiment contains 100 to 3000 ppm, preferably 100 to 3000 ppm of the photochromic compound represented by the general formula (a) or (b) with respect to 100% by weight of the resin. It can contain 2500 ppm, more preferably 1100 to 2200 ppm. The addition amount can not be uniquely limited because the performance varies depending on the type of photochromic compound represented by the general formula (a) or the general formula (b), but in the general formula (a) or the general formula (b) It is appropriately selected according to the performance of the photochromic compound to be represented.
It is preferable to use two or more compounds selected from the photochromic compounds represented by the general formula (a) or the general formula (b) in combination.

  The photochromic compound of the present embodiment is obtained by the method described in WO2009 / 146509, WO2010 / 20770, WO2012 / 149599, WO2012 / 162725.

  As the photochromic compound in this embodiment, Reversacol Humber Blue (polydimethylsiloxane chain, naphthopyran type chromophore (general formula (c)), Reversacol Calder Blue (polydimethylsiloxane chain, naphthopyran type chromophore (general formula c) Reversacol Trent Blue (polydimethylsiloxane chain, naphthopyran-based chromophore (general formula (c)), Reversacol Pennine Green (polydimethylsiloxane chain, naphthopyran-based chromophore (general formula (c)), Reversacol Heath Green ( Polyoxyalkylene chain, naphthopyran type chromophore (general formula (c)), Reversacol Chilli Red (polydimethylsiloxane chain, naphtho Carbon-based chromophore (general formula (c)), Reversacol Wembley Gray (polyoxyalkylene chain, naphthopyran-based chromophore (general formula (c)), Reversacol Cayenne Red (polyoxyalkylene chain, naphthopyran-based chromophore (general formula c)) Reversacol Wilson Blue (polyoxyalkylene chain, naphthopyran-based chromophore (general formula (c)), Reversacol Peacock Blue (polyoxyalkylene chain, naphthopyran-based chromophore (general formula (c))) (Polyoxyalkylene chains, naphthopyran based chromophores (general formula (c)) and the like can be mentioned.

[resin]
The resin constituting the photochromic lens (base material) is at least one selected from poly (meth) acrylates, polyallyl carbonates and poly (thio) urethanes.

(Poly (meth) acrylate)
The poly (meth) acrylate which is a resin constituting the photochromic lens (base material) of the present embodiment is represented, for example, by the general formula (i), the general formula (ii), the general formula (iii) and the formula (iv) And a structural unit derived from at least two polymerizable monomers selected from

  In the formula, R represents a hydrogen atom or a methyl group, and a plurality of R may be the same or different. m and n each represent an integer of 0 to 20 and may be the same or different.

  In the formula, R represents a hydrogen atom or a methyl group, and a plurality of R may be the same or different. p shows the integer of 0-20.

  In formula, R shows a hydrogen atom or a methyl group, q shows the integer of 0-20.

  As a polymerizable monomer having a (meth) acrylic group represented by the general formula (i), bisphenol A dimethacrylate, methylene-bis (4,1-phenylene) -bis (2-methacrylate), bisphenol A dimethacrylate Acrylate, methylene-bis (4,1-phenylene) -bis (2-acrylate), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-acryloyloxyphenyl) propane, 2- (4-methacryloyloxyphenyl) -2- (4-methacryloyloxyethoxyphenyl) propane, 2- (4-acryloyloxyphenyl) -2- (4-acryloyloxyethoxyphenyl) propane, 2,2-bis (4-) Methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxyethoxy) Phenyl) propane, 2- (4-methacryloyloxyethoxyphenyl) -2- (4- (methacryloyloxyethoxy) ethoxyphenyl) propane, 2- (4-acryloyloxyethoxyphenyl) -2- (4- (acryloyloxyethoxy) ) Ethoxyphenyl) propane, 2,2-bis (4- (methacryloyloxyethoxy) ethoxyphenyl) propane, 2,2-bis (4- (acryloyloxyethoxy) ethoxyphenyl) propane and the like can be mentioned.

  As a polymerizable monomer having a (meth) acrylic group represented by the general formula (ii), ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol diacrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate and the like can be mentioned.

  As a polymerizable monomer having a (meth) acrylic group represented by the general formula (iii), methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2- (2-hydroxyethoxy) Ethyl methacrylate, 2- (2-hydroxyethoxy) ethyl acrylate and the like can be mentioned.

  As polymerizable monomers having a (meth) acrylic group other than the above, butanediol dimethacrylate, hexamethylene dimethacrylate, 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane, 2 , 2-Bis (4-methacryloyloxypentaethoxyphenyl) propane, pentaerythritol tree acrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, bisphenol A-diglycidyl ether diacrylate, bisphenol A- Diglycidyl ether dimethacrylate type, tetrabromobisphenol A-diglycidyl ether diacrylate type, tetrabromobisphenol A diglycidyl It can include one or more compounds selected from a group consisting of such as ether dimethacrylate.

  As monomers other than polymerizable monomers having a (meth) acrylic group (except for compounds represented by the formula (iv)), styrene, alpha methyl styrene, alpha methyl styrene dimer, benzyl methacrylate, chlorostyrene Bromostyrene, Methoxystyrene, Monobenzylmalic acid, Dibenzylmalic acid, Monobenzylfumarlate, Dibenzylfumarlate, Methylbenzylmalic acid, Dimethylmalic acid, Diethylmalic acid, Dibutylmalic acid, Dibutylfumarate, Monobutyl One or more compounds selected from the group consisting of malic acid, monopentyl malic acid, dipentyl malic acid, monopentyl fumarate, dipentyl fumarate, diethylene glycol bisaryl carbonate can be used.

In 100% by weight of poly (meth) acrylate, 20 to 70% by weight, preferably 30 to 60% by weight of a constitutional unit derived from the polymerizable monomer represented by formula (i) can be contained. ,
The structural unit derived from the polymerizable monomer represented by the general formula (ii) can be contained in an amount of 10 to 60% by weight, preferably 20 to 50% by weight.
The structural unit derived from the polymerizable monomer represented by the general formula (iii) can be contained in an amount of 2 to 20% by weight, preferably 5 to 15% by weight,
The structural unit derived from the compound represented by the formula (iv) can be contained in an amount of 1 wt% to 20 wt%, preferably 3 wt% to 15 wt%, more preferably 5 wt% to 10 wt%.
The polymerizable composition of the present embodiment can contain these polymerizable monomers in the above amounts.
As the poly (meth) acrylate, for example, SunSensors-55 monomer can be mentioned as a trade name.

(A mixture of polyallyl carbonate and poly (meth) acrylate)
The mixture of polyallyl carbonate and poly (meth) acrylate which is a resin constituting the photochromic lens (base material) of the present embodiment contains two or more allyloxycarbonyl groups represented by the following general formula (11) Configuration derived from a structural unit (a) derived from an allyl carbonate compound (A) and a (meth) acrylate compound (B) containing two or more (meth) acrylic groups represented by the general formula (12) And 5% by weight to 30% by weight of the structural unit (a) and 100% by weight of the structural unit (a) and the structural unit (b). It contains 70% by weight to 95% by weight.
The polymerizable composition of the present embodiment can contain these polymerizable monomers in the above amounts.

R ¹ is derived from a C 5 to C 16 cyclic aliphatic polyol which may contain a hetero atom or a chain or branched C 3 to C 20 aliphatic polyol which may contain a hetero atom; And a divalent to hexavalent group of m shows the integer of 2-10.

R ² represents a divalent to tetravalent organic radical heteroatom or aromatic 1 to 30 carbon atoms which may contain a group. R ³ represents a hydrogen atom or a methyl group. n is an integer of 2 to 4;

  The allyl carbonate compound (A) can contain the oligomer. The oligomer is a poly (allyl carbonate) in which two or more molecules of polyol are linked via a carbonate bond produced by transesterification between allyl carbonate and polyol produced in the production process. The allyl carbonate compound is a poly (allyl carbonate) of a linear or branched aliphatic polyol having 3 to 12 carbon atoms. Poly (allyl carbonates) of cyclic aliphatic polyols having 5 to 16 carbon atoms in the molecule are also suitable for this purpose. These polyols can usually have 2 to 6, preferably 2 to 4 hydroxyl groups in the molecule. Mixed poly (allyl carbonate), ie derived from two or more polyols and obtainable by mechanical mixing of poly (allyl carbonate) of a single polyol, or chemical starting from mixtures of polyols and diallyl carbonate It is also possible to use those which can be obtained directly by reaction. Finally, all these poly (allyl carbonates) can be in the form of monomers or mixtures of monomers and oligomers.

Specific examples of the polyol constituting R ¹ of the general formula (11) are diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5. -Pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3 Propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane, 4,8-bis (hydroxymethyl)-[5.2.1.0 ^2,6 ] tri Cyclodecane, glycerol, trimethylolpropane, tris (hydroxyethyl) isocyanurate, penta Risuritoru, diglycerol, ditrimethylolpropane, and di pentaerythritol.

Accordingly, examples of the allyl carbonate compound (A) include, for example, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2 Selected from 2,4-trimethyl-1,3-pentanediol, 1,4-dimethylol cyclohexane and 4,8-bis (hydroxymethyl)-[5.2.1.0 ^2,6 ] tricyclodecane Bis (allyl carbonate) compounds of at least one diol,
A tris (allyl carbonate) compound of at least one triol selected from glycerol, trimethylolpropane and tris (hydroxyethyl) isocyanurate,
At least one tetraol tetra (allyl carbonate) compound selected from pentaerythritol, diglycerol and ditrimethylolpropane;
At least one compound selected from a hexa (allyl carbonate) compound of dipentaerythritol and a mixed poly (allyl carbonate) compound of at least two compounds selected from the diol, the triol, the tetraol and the dipentaerythritol. Including species.

The following are preferred examples of allyl carbonate polymerizable compounds suitable for the purpose of the present invention.
(i) Mixture of Di (ethylene glycol) with Bis (allyl carbonate) Compound and Its Oligomer Diethylene glycol bis (allyl carbonate) can be defined by the formula (13).

  Moreover, the oligomer of diethylene glycol bis (allyl carbonate) can be defined by Formula (14).

  In the formula, r is 2 or more.

  The compound (13) can be produced by reacting diethylene glycol bis (chloroformate) with allyl alcohol as described, for example, in "Encyclopedia of Chemical Technology", Kirk-Othmer, Edition III, Volume 2, pp. 111-112. It can be manufactured by A mixture of diethylene glycol bis (allyl carbonate) (formula (13)) and its oligomer (formula (14)) is, for example, in the presence of a basic catalyst as described in EP 35,304. The reaction can be conveniently carried out by transesterification of diallyl carbonate and diethylene glycol. These mixtures usually contain up to about 80% by weight of oligomers.

(ii) Mixture of bis (allyl carbonate) compound of a mixture of diethylene glycol and neopentyl glycol and its oligomer This bis (allyl carbonate) compound is the same as described above except that diethylene glycol is replaced by a mixture of diethylene glycol and neopentyl glycol. It is the same as bis (allyl carbonate) in (i) of

(iii) Poly (allyl carbonate) compound of a mixture of diethylene glycol and tris (hydroxyethyl) isocyanurate and a mixture thereof with an oligomer thereof This poly (allyl carbonate) compound is described, for example, in US Pat. No. 4,812,545. As obtained, it can be obtained by transesterification of diallyl carbonate of a mixture of diethylene glycol and tris (hydroxyethyl) isocyanurate.

(iv) Mixture of poly (allyl carbonate) compound of a mixture of diethylene glycol and trimethylolpropane and its oligomer This poly (allyl carbonate) compound is obtained by replacing tris (hydroxyethyl) isocyanurate with trimethylolpropane It is the same as the poly (allyl carbonate) of (iii) above.

(v) Mixture of poly (allyl carbonate) compound of a mixture of diethylene glycol and pentaerythritol and its oligomer This poly (allyl carbonate) compound is the same as described above except that tris (hydroxyethyl) isocyanurate is substituted by pentaerythritol. It is the same as the poly (allyl carbonate) compound of (iii).

(vi) Mixture of poly (allyl carbonate) compound of a mixture of diethylene glycol, neopentyl glycol and pentaerythritol and its oligomer This poly (allyl carbonate) compound was obtained by replacing diethylene glycol with two diols of diethylene glycol and neopentyl glycol Other than the above, it is the same as the poly (allyl carbonate) of (v) above.

(vii) a mixture of poly (allyl carbonate) compounds of mixtures of diethylene glycol, neopentyl glycol and pentaerythritol and oligomers thereof,
Mixtures of poly (allyl carbonate) comprising diethylene glycol in mixtures with bis (allyl carbonate) compounds and their oligomers

  The (meth) acrylate compound (B) can be represented by the following formula.

R ² represents a divalent to tetravalent organic radical heteroatom or aromatic 1 to 30 carbon atoms which may contain a group. R ³ represents a hydrogen atom or a methyl group. n is an integer of 2 to 4;
Moreover, the (meth) acrylate compound (B) can mention the compound represented by General formula (16) and General formula (17).

p represents a numerical value of 1 to 100, and R ³ represents a hydrogen atom or a methyl group, which may not be identical to each other. n is preferably a numerical value of 1 to 50, more preferably a numerical value of 1 to 20, still more preferably a numerical value of 2 to 10, and particularly preferably a numerical value of 2 to 4.

  The (meth) acrylate compound represented by the general formula (16) is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate Acrylate, tetraethylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene Glycoldia It can include at least one selected from the relations.

Each q represents a numerical value of 1 or more, and the sum of two qs represents a numerical value of 2 to 100. R ³ represents a hydrogen atom or a methyl group, which may not be identical to each other. X represents a substituted or unsubstituted divalent aromatic group, or a substituted or unsubstituted divalent aliphatic group which may contain an aromatic group having 1 to 20 carbon atoms.

  As the (meth) acrylate compound represented by the general formula (17), bisphenol A dimethacrylate, methylene-bis (4,1-phenylene) -bis (2-methacrylate), bisphenol A diacrylate, methylene-bis (4) 1,1-phenylene) -bis (2-acrylate), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-acryloyloxyphenyl) propane, 2- (4-methacryloyloxyphenyl) 2- (4-methacryloyloxyethoxyphenyl) propane, 2- (4-acryloyloxyphenyl) -2- (4-acryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxy Toxiphenyl) propane, 2- (4-methacryloyloxyethoxyphenyl) -2- (4- (methacryloyloxyethoxy) ethoxyphenyl) propane, 2- (4-acryloyloxyethoxyphenyl) -2- (4- (acryloyloxy) At least one selected from ethoxy) ethoxyphenyl) propane, 2,2-bis (4- (methacryloyloxyethoxy) ethoxyphenyl) propane and 2,2-bis (4- (acryloyloxyethoxy) ethoxyphenyl) propane be able to.

  As (meth) acrylate compounds other than the above, butanediol dimethacrylate, hexamethylene dimethacrylate, 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane, 2,2-bis (4-) Methacryloyloxypentaethoxyphenyl) propane, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, bisphenol A-diglycidyl ether diacrylate, bisphenol A-diglycidyl ether dimethacrylate , Tetrabromobisphenol A-diglycidyl ether diacrylate system, tetrabromobisphenol A-diglycidyl ether dime It can include at least one selected from a group consisting of such acrylates.

  Among these exemplified compounds, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate Or more preferably at least one selected from diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate, and more preferably diethylene glycol dimethacrylate, triethylene glycol dimethacrylate Selected from methacrylate At least one are particularly preferred are.

The allyl carbonate compound (A) is contained in an amount of 5 to 30% by weight, preferably 5 to 28% by weight, more preferably 5 to 25% by weight in the polymerizable composition described later. The (meth) acrylate compound (B) is contained in 70% by weight to 95% by weight, preferably 72% by weight to 95% by weight, and more preferably 75% by weight to 95% by weight in the polymerizable composition described later.
As a mixture of polyallyl carbonate and poly (meth) acrylate, for example, SunSensors-50 monomer can be mentioned as a trade name.

(Poly (thio) urethane)
The poly (thio) urethane which is a resin constituting the photochromic lens (base material) of the present embodiment is a polyol compound having a structural unit derived from (a) a polyisocyanate compound and (b) a number average molecular weight of 100 or more. And a structural unit derived from (c) an active hydrogen compound having two or more functional groups (excluding the compound (b)).

  As the polyisocyanate compound (a), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanato methyl ester, lysine triisocyanate, m Xylylene diisocyanate, o-xylylene diisocyanate, p-xylylene diisocyanate, xylylene diisocyanate, α, α, α ′, α′-tetramethyl xylylene diisocyanate, bis (isocyanatomethyl) naphthalene, 1,3,5 -Tris (isocyanatomethyl) benzene, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatomethyl) disulfide, bis (isocyanate) Aliphatic polyisocyanate compounds such as tolyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, isophorone diisocyanate, bis ( Isocyanatomethyl) cyclohexane, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, dicyclohexylmethane-4 , 4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethyl Methane isocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 3,8 -Bis (isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tri Alicyclic polyisocyanate compounds such as cyclodecane; Aromatic polyisocyanate compounds such as diphenyl sulfide-4,4-diisocyanate, tolylene diisocyanate, phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, diphenylmethane diisocyanate and the like 2,5-diisocyanatothio Fen, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) Heterocyclic polyisocyanate compounds such as 1,3-dithialane etc. can be mentioned. As a polyisocyanate compound (a), at least 1 sort (s) selected from these can be used.

  The polyisocyanate compound (a) includes, in addition to the monomer, a modified body and / or a mixture with a modified body, and as a modified isocyanate, for example, a multimer, a biuret modified body, an allophanate modified body, Oxadiazine trione modified products, polyol modified products and the like can be mentioned. Examples of the multimer include dimers of uretdione, uretimine, carbodiimide and the like, and multimers of trimers or more such as isocyanurate, iminooxadiandione and the like.

As the polyisocyanate compound (a), hexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate is preferred, and isophorone diisocyanate, m-xylyl Diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [ .2.1] - heptane, 2,6-bis (isocyanatomethyl) bicyclo - [2.2.1] - heptane is more preferred. These polyisocyanate compounds may be used alone or as a mixture of two or more.
As the polyol compound (b), at least one compound selected from compounds having a number average molecular weight of 100 or more can be used.

  Examples of the polyol compound (b) include polyethylene glycol and polypropylene glycol, which may contain low molecular weight oligomers such as ethylene glycol, diethylene glycol and triethylene glycol, and two or more of them may be used alone. It may be used as a mixture of Also, in the present embodiment, polyethylene glycol or polypropylene glycol includes these diol types or triol types.

  Moreover, as a polyol compound (b), the compound which added the alcohol of trifunctional or more and ethylene oxide, a propylene oxide, and (epsilon) -caprolactone may be sufficient. For example, ethylene oxide adduct of glycerol, ethylene oxide adduct of trimethylolpropane, ethylene oxide adduct of pentaerythritol, propylene oxide adduct of glycerol, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of pentaerythritol, Examples thereof include caprolactone modified glycerol, caprolactone modified trimethylolpropane, and caprolactone modified pentaerythritol.

  The lower limit of the number average molecular weight of the polyol compound (b) is 100 or more, preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, particularly preferably 600 or more, and the upper limit is 4000 or less, more preferably 3000 The following is more preferably 2000 or less, particularly preferably 1500 or less. The upper and lower limits can be combined as appropriate.

  When the number average molecular weight of the polyol compound (b) is in the above range, photochromic performance can be effectively exhibited without impairing excellent properties such as mechanical strength of the poly (thio) urethane resin.

  For example, when the polyol compound (b) is polyethylene glycol, when the number average molecular weight is 400 to 2000, the coloring performance is further improved, and the clouding of the resin molded product is further suppressed.

  Moreover, when a polyol compound (b) is a polypropylene glycol, color development performance is improved more as a number average molecular weight is 400-2000, and the cloudiness of a resin molding is suppressed more.

  Moreover, the resin molding obtained from polypropylene glycol can exhibit higher heat resistance and rigidity compared with the resin molding obtained from polyethylene glycol. Thus, polypropylene glycol may be more preferable than polyethylene glycol for applications used in a variety of environments and conditions, such as ophthalmic lenses.

  As the polyol compound (b), 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,4-bis (hydroxyethoxy) benzene, 1,3-bis (b) Examples thereof include polyethylene glycol adducts such as m-hydroxyethoxy) benzene and 2,2-[(1,1-biphenyl) -4,4-diylbis (oxy)] bisethanol or polypropylene glycol adducts, etc. Or as a mixture of two or more.

  The lower limit of the number average molecular weight of these compounds is 200 or more, preferably 300 or more, more preferably 400 or more, more preferably 500 or more, particularly preferably 600 or more, and the upper limit is 4000 or less, preferably 3000 or less Preferably it is 2000 or less, More preferably, it is 1500 or less, Especially preferably, it is 1000 or less. The upper and lower limits can be combined as appropriate. When the number average molecular weight is in the above range, photochromic performance can be effectively exhibited without impairing excellent properties such as mechanical strength of the poly (thio) urethane resin.

  Examples of the polyol compound (b) include polyethylene glycol adducts of bisphenol A and polypropylene glycol adducts of bisphenol A. These may be used alone or as a mixture of two or more.

  The lower limit of the number average molecular weight of these compounds is 200 or more, preferably 300 or more, more preferably 400 or more, more preferably 500 or more, particularly preferably 600 or more, and the upper limit is 4000 or less, preferably 3000 or less Preferably it is 2000 or less, More preferably, it is 1500 or less. The upper and lower limits can be combined as appropriate. When the number average molecular weight is in the above range, photochromic performance can be effectively exhibited without impairing excellent properties such as mechanical strength of the poly (thio) urethane resin.

As a polyol compound (b), the polyester compound which consists of a diol compound and dicarboxylic acid can be mentioned.
The diol compound constituting the polyester compound is not particularly limited, but aliphatic diols having 2 to 12 carbon atoms in the main chain are suitably used, and examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, Examples include 3-methyl-1,5-pentanediol, 1,9-nonanediol and the like.

Also, there is no particular limitation on the dicarboxylic acid constituting the polyester compound, but aliphatic dicarboxylic acids having 2 to 12 carbon atoms in the main chain and aromatic dicarboxylic acids are suitably used, and examples thereof include succinic acid and adipic acid Sebacic acid, isophthalic acid, terephthalic acid and the like.
A polyester compound can be used combining suitably 1 type or 2 types or more of these diol compounds, and 1 type or 2 types or more of dicarboxylic acid.

  In addition, a polyester compound obtained by ring-opening polymerization of lactone can also be used in the present embodiment. Examples of lactone compounds include α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone and the like. The lower limit of the number average molecular weight of these compounds is 600 or more, preferably 800 or more, more preferably 1000 or more, and the upper limit is 4000 or less, more preferably 3000 or less, still more preferably 2000 or less, particularly preferably 1500 or less. is there. The upper and lower limits can be combined as appropriate. When the number average molecular weight is in the above range, photochromic performance can be effectively exhibited without impairing excellent properties such as mechanical strength of the poly (thio) urethane resin.

  As a polyol compound (b), the compound represented by general formula (I) can be used.

In formula (I), R ¹ and R ^{2 each} represent a hydrogen atom, a methyl group or an ethyl group, and at least one of them is a hydrogen atom. R ¹ and R ² may be the same or different. n represents an integer of 30 or more and 500 or less.
Specifically, a compound represented by general formula (II) can be used.

In formula (II), R ³ and R ^{4 each} represent a hydrogen atom, a methyl group or an ethyl group, and at least one of them is a hydrogen atom. R ³ and R ⁴ may be the same or different. a + c is an integer of 2 or more and 400 or less, and b represents an integer of 1 or more and 100 or less.
The number average molecular weight of the compounds represented by the general formula (I) and the general formula (II) is from 1000 to 15000, preferably from 1500 to 7500.

  Examples of the compounds represented by the general formula (I) and the general formula (II) include Adeka Pulronic Series manufactured by Adeka Co., Ltd. and Pluronic Series manufactured by BASF.

Examples of the compounds represented by the general formula (I) and the general formula (II) include Adeka's Adeka Pulronic L-44, L-62, L-64, L-72, P-84, P-85, BASF Pluronic L-43, L-44, L-62, L-64, L-72, P-65, P-84, P-85, F-68, F-77 are preferred, Adeka Adeka Pululonic L-62, L-64, P-84, P-85, BASF PLURONIC L-62, L-64, L-72, P-65, P-84, P-85, F-77 Is more preferred. These compounds may be used alone or as a mixture of two or more.
Photochromic performance can be effectively exhibited by using the polyol compound (b) consisting of the above-mentioned compounds.

  As the polyol compound (b), at least one compound selected from the above-described exemplified compounds can be used. In this embodiment, it is preferable to use a diol or triol type of polyethylene glycol or polypropylene glycol, a compound represented by the general formula (I), a compound represented by the general formula (II), and a diol type of polypropylene glycol It is more preferable to use a compound represented by or a triol type and general formula (II).

  In the polymerizable composition, the polyol compound (b) can be contained in a range of 0.05 times by weight to 90 times by weight with respect to the weight of the bifunctional or higher functional hydrogen compound (c). In this embodiment, it is used within the range so as to obtain resin performance required by the application while maintaining high photochromic performance. It is preferably in the range of 0.1 times by weight to 50 times by weight, and more preferably in the range of 0.1 times by weight to 5 times by weight.

  When the weight ratio of the polyol compound (b) to the active hydrogen compound (c) is in the above range, high light control performance, that is, high color density and fast change in density can be suitably exhibited. Furthermore, since the crosslink density is in the optimum range, it is possible to obtain an optical material more excellent in rigidity, surface hardness, heat resistance and the like.

  The bifunctional or higher active hydrogen compound (c) (hereinafter simply referred to as "active hydrogen compound (c)") is not particularly limited, and examples include polyol compounds, polythiol compounds, thiol compounds having a hydroxyl group, etc. Can. These can be used in combination as appropriate. The active hydrogen compound (c) does not contain the polyol compound (b).

Examples of the polyol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, butanetriol, and 1,2- Methyl glucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, threitol, ribitol, arabitol, xylitol, allitol, mannitol, dulcitol, iditol, glycol, inositol, hexanetriol, triglycerides, diglycerol, triethylene Glycol, polyethylene glycol, tris 2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentane diol, cyclohexane diol, cycloheptane diol, cyclooctane diol, cyclohexane dimethanol, hydroxypropyl cyclohexanol, tricyclo [5.2.1.0 ^{2, 6]} decane - Dimethanol, bicyclo [4.3.0] -nonanediol, dicyclohexanediol, tricyclo [5.3.1.1] dodecanediol, bicyclo [4.3.0] nonanedimethanol, tricyclo [5.3. 1.1] Dodecane-diethanol, hydroxypropyltricyclo [5.3.1.1] dodecanol, spiro [3.4] octanediol, butylcyclohexanediol, 1,1′-bicyclohexylidenediol, cyclohexane Aliphatic polyols such as liol, maltitol, lactose; dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F , Aromatic polyols such as xylylene glycol, di (2-hydroxyethoxy) benzene, bisphenol A-bis (2-hydroxyethyl ether), tetrabromo bisphenol A, tetrabromo bisphenol A-bis (2-hydroxyethyl ether); Halogenated polyols such as dibromo neopentyl glycol; Ethylene oxide adduct of glycerol, trimethylol propa! Oxide adduct of propylene, ethylene oxide adduct of pentaerythritol, propylene oxide adduct of glycerol, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of pentaerythritol, caprolactone modified glycerol, caprolactone modified trimethylolpropane, caprolactone Compounds obtained by adding ethylene oxide, propylene oxide, ε-caprolactone and a trifunctional or higher alcohol such as modified pentaerythritol;
Polymeric polyols such as epoxy resins are mentioned. In the present embodiment, at least one selected from these can be used in combination.

  In addition, as a polyol compound, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2 -A condensation reaction product of an organic acid such as bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid or bromophthalic acid with the above-mentioned polyol; an addition reaction product of the above-mentioned polyol with an alkylene oxide such as ethylene oxide or propylene oxide An addition reaction product of an alkylene polyamine and an ethylene oxide or an alkylene oxide such as propylene oxide; and further, bis [4- (hydroxyethoxy) phenyl] sulfide, bis [4- (2-) Droxypropoxy) phenyl] sulfide, bis [4- (2,3-dihydroxypropoxy) phenyl] sulfide, bis [4- (4-hydroxycyclohexyloxy) phenyl] sulfide, bis [2-methyl-4- (hydroxyethoxy) 6) 6-Butylphenyl] sulfide and compounds in which ethylene oxide and / or propylene oxide is added on an average of 3 molecules or less on average per hydroxyl group to these compounds; di- (2-hydroxyethyl) sulfide, 1,2-bis (2-) Hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithiane-2,5-diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, Bis (4-hydroxy Nil) sulfone (trade name: bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 1,3-bis (2-hydroxyethylthiol) Examples thereof include polyols containing a sulfur atom such as ethyl) -cyclohexane. In the present embodiment, at least one selected from these can be used in combination.

  Examples of polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, Diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercapto) Acetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptoprote) Onate), pentaerythritol tetrakis (2-mercapto acetate), pentaerythritol tetrakis (3-mercapto propionate), bis (mercapto methyl) sulfide, bis (mercapto methyl) disulfide, bis (mercapto ethyl) sulfide, bis (mercapto ethyl) ) Disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,1 2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropylthio) ethane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-merca) (Ethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto -3,6,9-Trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3 6,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide 2,5-Dimercaptomethyl-1,4-dithiane 2,5-Dimerca Hept-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate ), Hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), Hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), 2-mel Pttoethyl ether bis (2-mercaptoacetate), 2-mercaptoethylether bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester) Dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2 Aliphatic polythiol compounds such as tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, etc .; Mercapto benzene, 1,3-di Lucapto benzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (Mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,3,5-trimercaptobenzene, 1,3,5-tris (mercaptomethyl) benzene 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, Aromatic polythiol compounds such as 2,6-naphthalene dithiol; 2-methylamino-4,6- Dithiol-sym-triazine, 3,4-thiophenedithiol, bismuthiol, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3- Examples thereof include heterocyclic polythiol compounds such as dithietane; compounds represented by the following general formula (18), and the like, but are not limited to these exemplified compounds. In the present embodiment, at least one selected from these can be used in combination.

  In formula, a and b show the integer of 1-4 independently, and c shows the integer of 1-3. Z is hydrogen or a methyl group, and when there are a plurality of Z, they may be the same or different.

  As the thiol compound having a hydroxyl group, for example, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glucerin bis (mercaptoacetate), 4-mercaptophenol, 2,3-dimercapto-1-propanol, pentaerythritol tris Although (3-mercapto propionate), pentaerythritol tris (thio glycolate), etc. can be mentioned, it is not limited only to these exemplary compounds.

Furthermore, oligomers of these active hydrogen compounds and halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds may be used. These active hydrogen compounds may be used alone or in combination of two or more.
From the viewpoint of physical properties such as mechanical strength of the resulting molded body, it is preferable to use an active hydrogen compound having three or more functions as the active hydrogen compound (c).

  Specifically, glycerin, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7- Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercapto At least one selected from methyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis (mercaptomethylthio) propane and trimethylolpropane tris (3-mercaptopropionate) One type is preferably used.

Moreover, as a preferable combination of a polyol compound (b) and an active hydrogen compound (c),
A combination of polyethylene glycol and at least one selected from glycerin, pentaerythritol tetrakis (2-mercaptoacetate), and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane;
A combination of polypropylene glycol and at least one selected from pentaerythritol tetrakis (2-mercaptoacetate) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane;
Combinations of polypropylene glycol adducts of bisphenol A with 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
A combination of at least one selected from polyester compounds consisting of 3-methyl-1,5-pentanediol, adipic acid and isophthalic acid, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
The triol type of polypropylene glycol and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9 In combination with a composition comprising trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
A diol form of polypropylene glycol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9 In combination with a composition comprising trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
A combination of the diol form of polypropylene glycol and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
A combination of a compound represented by the general formula (II) and at least one selected from pentaerythritol tetrakis (2-mercaptoacetate) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane;
A compound represented by the general formula (II), 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto- In combination with a composition comprising 3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
And the like, but it is not limited to these combinations.

  In the polymerizable composition, the molar ratio of NCO groups contained in the polyisocyanate compound (a) to the total of OH groups and SH groups contained in the active hydrogen compound (c) and the polyol compound (b) (NCO group / (OH The group + SH group) is usually in the range of 0.8 to 1.2, preferably in the range of 0.85 to 1.15, and more preferably in the range of 0.9 to 1.1. is there.

  If the molar ratio of NCO group / (OH group + SH group) is 0.8 or more, unreacted OH group and SH group do not remain, the composition is sufficiently cured, and the heat resistance, moisture resistance and light resistance are excellent. A resin is obtained, and if the ratio of NCO group / (OH group + SH group) is 1.2 or less, a resin excellent in heat resistance, moisture resistance and light resistance is obtained without any unreacted NCO group remaining, and unreacted It is not necessary to raise the reaction temperature to reduce the NCO group in the resin, and no defects such as coloring are observed, which is preferable as a resin material.

(Other ingredients)
In the present embodiment, a polymerization catalyst, an ultraviolet absorber, a resin modifier, an internal mold release agent and the like may be further included.
As the polymerization catalyst, in the case of poly (thio) urethane, tertiary amine compounds and their inorganic acid salts or organic acid salts, metal compounds, quaternary ammonium salts, organic sulfonic acids and the like can be mentioned.

  In the case of poly (meth) acrylate and polyallyl carbonate, peroxy ester radical polymerization initiator as radical polymerization initiator, peroxy ketal radical polymerization initiator, peroxy monocarbonate radical polymerization initiator or azo radical polymerization Initiators can be mentioned.

  Examples of peroxy ester radical polymerization initiators include t-hexyl peroxy neodecanoate, 1,1,3,3-tetramethyl butyl peroxy neo decanoate, t-hexyl peroxy- 2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy neodecanoate, cumylperoxy neodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate T-Hexyl peroxypivalate, t-butyl-peroxy neodecanoate, t-butyl peroxy laurate, t-butyl peroxy nonanoate, t-butyl peroxy isobutyrate, t-butyl peroxy -3,3,5-trimethylhexanoate, t-butyl peroxy acetate, t-butyl peroxyacetate Oxy isononaate, t-butyl peroxybenzoate, t-amyl peroxy-2-ethylhexanoate, t-amyl peroxy normal octoate, t-amyl peroxy acetate, t-amyl peroxy isononaate, Examples thereof include t-amyl peroxybenzoate, t-hexyl peroxybenzoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate and the like.

  As peroxy ketal radical polymerization initiators, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) ) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5 -Trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, ethyl-3,3-bis (t-butylperoxy) ) Valerate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1 -Bis (t-amylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis [4,4- (di-t-butylperper) Oxy) cyclohexyl] propane and the like.

As a peroxy monocarbonate-based radical polymerization initiator, O, O- (t-butyl) -O-isopropyl monoperoxy carbonate, O, O- (t-amyl) -O-isopropyl monoperoxy carbonate, O, O- (t-butyl) -O- (2-ethylhexyl) monoperoxy carbonate, O, O- (t-amyl) -O- (2-ethylhexyl) monoperoxy carbonate, etc. are mentioned.
Examples of the azo radical polymerization initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile and the like.
These can be used 1 type or in mixture of 2 or more types. Furthermore, other radical polymerization initiators may be used in combination as needed.

  The addition amount of the radical polymerization initiator is in the range of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymerizable composition. If the amount is less than 0.01 parts by weight, curing tends to be insufficient, and if it exceeds 10 parts by weight, the molded article tends to be distorted.

  Examples of UV absorbers include benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, cyanoacrylate-based UV absorbers, diphenyl acrylate-based UV absorbers, phenol-based UV absorbers, oxaanilide-based UV absorbers And malonic acid ester-based ultraviolet absorbers.

  The addition amount of the UV absorber can not be uniquely limited because the UV range to be absorbed varies depending on the type of UV absorber, but 0.01 to 5 parts by weight, preferably 0 based on 100 parts by weight of the polymerizable composition. It is in the range of .02 to 2 parts by weight.

  As a resin modifier, an olefin compound including an episulfide compound, an alcohol compound, an amine compound, an epoxy compound, an organic acid and an anhydride thereof, a (meth) acrylate compound and the like other than the above description as long as the effects of the present invention are not impaired Etc.

<Manufacturing method of polymerizable composition and resin molded product>
The polymerizable composition of the present embodiment is at least one selected from the photochromic dyes represented by the general formula (5), the general formula (6), the general formula (a) and the general formula (b), and And the above-described polymerizable compound constituting the resin. Furthermore, the other components described above can be included. The polymerizable composition can be prepared by mixing these components all at once or mixing them and finally mixing them into one.

  The polymerizable composition of the present embodiment can contain 100 to 3000 ppm, preferably 10 to 2000 ppm, of a photochromic dye with respect to a total of 100% by weight of the polymerizable compound. The addition amount of the photochromic dye can not be generally limited because the performance varies depending on the type, but is appropriately selected depending on the type and the addition amount of each.

  The mixing temperature is usually 25 ° C. or less. From the viewpoint of the pot life of the polymerizable composition, it may be preferable to further lower the temperature. However, when the solubility of the catalyst and the additive in the monomer is not good, the catalyst and the additive may be dissolved in the monomer and the resin modifier by heating in advance.

  In the present embodiment, the method for producing the resin molded product is not particularly limited, but cast polymerization may be mentioned as a preferred production method. First, the polymerizable composition is injected between molding molds held by a gasket or a tape or the like. At this time, depending on the physical properties required for the plastic lens to be obtained, it is often preferable to carry out defoaming treatment under reduced pressure, filtration treatment such as pressurization, reduced pressure, etc., as necessary.

  The polymerization conditions are not limited because the conditions largely vary depending on the composition of the polymerizable composition, the type and amount of the catalyst used, the shape of the mold, etc., but the temperature is about 1 to 50 at a temperature of about -50 to 150 ° C. It takes place over time. In some cases, it is preferable to cure in a temperature range of 10 to 150 ° C. or gradually raise the temperature for 1 to 48 hours.

  The resin molded product may be subjected to a treatment such as annealing, if necessary. Although processing temperature is normally performed between 50-150 degreeC, it is preferable to carry out at 90-140 degreeC, and it is more preferable to carry out at 100-130 degreeC.

  In the present embodiment, when the resin is molded, in addition to the above-mentioned “other components”, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, and the like according to the purpose according to the purpose. Various additives such as bluing agents, oil soluble dyes, fillers and adhesion improvers may be added.

<Use>
The resin molded product of the present embodiment can be formed into various shapes by changing the type of mold during cast polymerization.

  A molded body obtained from the polymerizable composition for an optical material of the present embodiment can obtain a material having both excellent surface hardness and light control performance without impairing the transparency, so It is possible to use for various optical materials. In particular, it can be suitably used as a photochromic lens or a plastic polarized lens.

[Photochromic lens]
The photochromic lens using the lens base material which consists of a molded object of this embodiment may apply | coat and use a coating layer in single side | surface or both surfaces as needed.
The photochromic lens of the present embodiment comprises a lens substrate made of the above-described polymerizable composition and a coating layer.

  Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflective layer, an antifogging layer, an antifouling layer, a water repellent layer and the like. Each of these coating layers can be used alone or as multiple coating layers can be used. When coating layers are applied to both sides, the same coating layer may be applied to each side or different coating layers may be applied.

Each of these coating layers is an infrared absorber for the purpose of protecting eyes from infrared rays, a light stabilizer or an antioxidant for the purpose of improving the weather resistance of the lens, and a dye or pigment for the purpose of enhancing the fashion of the lens Other known additives for enhancing the performance of the lens may be used in combination.
With respect to the layer to be coated by coating, various leveling agents may be used for the purpose of improving the coatability.

  The primer layer is usually formed between the hard coat layer described later and the lens substrate. The primer layer is a coating layer for the purpose of improving the adhesion between the hard coat layer formed thereon and the lens substrate, and in some cases it is possible to improve the impact resistance. Any material may be used for the primer layer as long as it has high adhesion to the obtained lens, but a primer mainly composed of a urethane resin, an epoxy resin, a polyester resin, a melanin resin and a polyvinyl acetal is usually used. A composition or the like is used. The primer composition may use a suitable solvent which does not affect the lens in order to adjust the viscosity of the composition. Of course, you may use it without a solvent.

  The primer layer can be formed by any of a coating method and a dry method. When a coating method is used, the primer composition is applied to a lens by a known coating method such as spin coating or dip coating, and then solidified to form a primer layer. When it is carried out by a dry method, it is formed by a known dry method such as a CVD method or a vacuum evaporation method. When forming the primer layer, the surface of the lens may be subjected to pretreatment such as alkali treatment, plasma treatment, ultraviolet treatment and the like, as necessary, for the purpose of improving adhesion.

The hard coat layer is a coating layer for the purpose of imparting functions such as scratch resistance, abrasion resistance, moisture resistance, warm water resistance, heat resistance and weather resistance to the lens surface.
The hard coat layer is generally composed of a curable organosilicon compound and an element selected from the group of elements of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In and Ti. A hard coat composition containing one or more kinds of fine particles composed of a composite oxide of one or more kinds of oxide fine particles and / or two or more kinds of elements selected from these element groups is used.

  Hard coat compositions include, in addition to the above components, at least amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, salts of perchloric acids, acids, metal chlorides and polyfunctional epoxy compounds It is preferable to include either. The hard coat composition may use a suitable solvent that does not affect the lens, or may be used without a solvent.

  The hard coat layer is usually formed by applying a hard coat composition by a known coating method such as spin coat or dip coat and then curing. As a curing method, a curing method by thermal curing, energy beam irradiation such as ultraviolet light and visible light, and the like can be mentioned. In order to suppress the generation of interference fringes, the refractive index of the hard coat layer is preferably such that the difference in refractive index with the lens is in the range of ± 0.1.

An antireflective layer is usually formed on the hard coat layer as needed. There are inorganic and organic antireflective layers, and in the case of inorganic type, inorganic oxides such as SiO ₂ and TiO ₂ are used, and vacuum deposition, sputtering, ion plating, ion beam assist, CVD Formed by a dry process such as In the case of an organic type, it is formed by a wet process using a composition containing an organosilicon compound and silica-based fine particles having an internal cavity.

The antireflection layer has a single layer and a multilayer, and when used as a single layer, it is preferable that the refractive index is lower by at least 0.1 or more than the refractive index of the hard coat layer. In order to effectively exhibit the antireflective function, it is preferable to use a multilayer antireflective film, in which case low refractive index films and high refractive index films are alternately laminated. Also in this case, the refractive index difference between the low refractive index film and the high refractive index film is preferably 0.1 or more. Examples of the high refractive index film include films of ZnO, TiO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ZrO ₂ , Ta ₂ O _{5 and the} like, and examples of the low refractive index film include SiO ₂ film and the like. .

  An antifogging layer, an antifouling layer, and a water repellent layer may be formed on the antireflective layer, if necessary. As a method of forming an antifogging layer, an antifouling layer, and a water repellent layer, as long as it does not adversely affect the antireflective function, the treatment method, treatment material and the like are not particularly limited, and known antifogging treatment Methods, pollution control methods, water repellent methods, materials can be used. For example, in the anti-fogging treatment method and the anti-soiling treatment method, a method of covering the surface with a surfactant, a method of adding a hydrophilic film to the surface to make it absorb water, a method of covering the surface with fine irregularities and enhancing the water absorption The method of making it water absorbency using a photocatalytic activity, the method of giving super water repellent treatment, and preventing adhesion of a water droplet etc. are mentioned. In the water repellent method, a method of forming a water repellent layer by vapor deposition or sputtering of a fluorine-containing silane compound or the like, or a method of forming a water repellent layer by coating after dissolving the fluorine-containing silane compound in a solvent Etc.

[Plastic polarized lens]
The plastic polarized lens of the present embodiment includes a polarizing film and a molded product formed on at least one surface of the polarizing film and cured of the polymerizable composition for an optical material of the present embodiment (photochromic lens of the present embodiment And (d) no base layer).

  The polarizing film in the present embodiment can be composed of a thermoplastic resin. Examples of the thermoplastic resin include polyester resin, polycarbonate resin, polyolefin resin, polyimide resin, polyvinyl alcohol resin, polyvinyl chloride resin and the like. From the viewpoint of water resistance, heat resistance, and moldability, polyester resins and polycarbonate resins are preferable, and polyester resins are more preferable.

  Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. From the viewpoints of water resistance, heat resistance and molding processability, polyethylene terephthalate is preferable.

Specifically as a polarizing film, a dichroic dye containing polyester polarizing film, an iodine containing polyvinyl alcohol polarizing film, a dichroic dye containing polyvinyl alcohol polarizing film etc. are mentioned.
The polarizing film may be used after being subjected to heat treatment for drying and stabilization.
Furthermore, in order to improve adhesion with an acrylic resin, the polarizing film is subjected to primer coating treatment, chemical treatment (chemical treatment such as gas or alkali), corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment You may use, after performing 1 type, or 2 or more types of pre-processing chosen from roughening treatment, a flame treatment, etc. Among such pretreatments, one or more selected from primer coating treatment, chemical treatment, corona discharge treatment and plasma treatment are particularly preferable.

  The plastic polarized lens of the present embodiment is formed on one of the objective surface side or the ocular surface side of such a polarizing film, or on both the objective surface side and the ocular surface side. A substrate layer obtained by curing the polymerizable composition for an optical material of the present embodiment is laminated.

  From the viewpoint of light control performance, it is preferable that a substrate layer obtained by curing the polymerizable composition for an optical material of the present embodiment is laminated on at least the surface on the objective surface side of the polarizing film. When the base material layer in the present embodiment is formed only on the surface on the objective surface side of the polarizing film, the base material layer formed on the other surface of the polarizing film does not contain the photochromic dye. It can be formed from a plastic material such as acrylic resin, allyl carbonate resin, polycarbonate resin, polyurethane resin, polythiourethane resin, polysulfide resin and the like.

  The plastic polarized lens of the present embodiment is not particularly limited, and examples thereof include a method of bonding a lens substrate to both sides of a polarizing film, and a method of casting and polymerizing a polymerizable composition on both sides of a polarizing film. In the present embodiment, an example formed by a cast polymerization method will be described.

The method for producing a plastic polarized lens of the present embodiment is, for example,
Forming a first polymerizable composition layer on the surface on the objective side of the polarizing film in a mold, and forming a second polymerizable composition layer on the other surface of the polarizing film;
And D. polymerizing and curing the polymerizable composition layer, and laminating a substrate layer on both sides of the polarizing film.
The first polymerizable composition layer is formed from the polymerizable composition for an optical material of the present embodiment. When the layer of the first polymerizable composition and the layer of the second polymerizable composition have the same resin composition, the temperature control of the polymerization step becomes easy, so the layer of the second polymerizable composition is adjusted. It forms from the polymeric composition for optical materials of this embodiment which does not contain a photo pigment.

The lens casting mold is generally composed of two substantially disk-shaped glass molds held by gaskets. A polarizing film is placed in the space of the lens casting mold so that the film surface is parallel to the inner surface of the opposing mold on the front side. An air gap is formed between the polarizing film and the mold. The polarizing film may be shaped in advance.
Then, the first polymerizable composition is injected between the mold and the surface on the objective surface side of the polarizing film to form a layer of the first polymerizable composition, and then the surface on the ocular surface side of the polarizing film and the mold The second polymerizable composition can be injected into the gap between the two to form a layer of the second polymerizable composition.

  In the step, the first polymerizable composition is placed on the formation surface of the mold for forming the objective surface of the lens, and the first polymerizable composition is covered with the polarizing film over the entire surface of the formation surface. In order to form the ocular surface of the lens of the mold and the polarizing film, the mold and the surface of the objective surface side of the polarizing film are separated by a predetermined distance through the layer of the first polymerizable composition which is spread and spread. The second polymerizable composition may be injected into a gap between the second polymerizing composition and the forming surface to form a layer of the second polymerizable composition.

The polymerization conditions of the polymerizable composition may vary depending on the composition of the polymerizable composition, the type and amount of the catalyst used, the shape of the mold, etc. In some cases, it is preferable to cure in 1 to 25 hours while maintaining or gradually raising the temperature in the temperature range of 5 to 130 ° C.
The laminate cured by polymerization can be released from the mold to obtain the plastic polarized lens of the present embodiment.

In the present embodiment, the laminated body after polymerization and release may be subjected to heat treatment such as annealing, if necessary. Although processing temperature is performed between 90-150 degreeC from a viewpoint of the effect of this invention, it is preferable to carry out at 110-130 degreeC, and it is more preferable to carry out at 115-125 degreeC. The treatment time is in the range of 1 to 10 hours, preferably 2 to 5 hours, from the viewpoint of the effect of the present invention.
In addition, you may form the said coating layer similar to a plastic spectacle lens on the surface of the obtained base material layer.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In Examples and Comparative Examples, the methods used for the evaluation and the devices used are as follows.

Transparency at the time of decoloring: using Otsuka Electronics Co., Ltd., using the instantaneous multiphotometric system MSPD-7700, measure the spectral transmittance of the molded body sample processed to a thickness of 2 mm at a temperature of 23 ° C. to ISO 8980-3 Based on the above, the luminous transmittance (% T; 400 nm to 780 nm) at the time of color disappearance was calculated. It was judged that the transparency was high if the luminous transmittance at the time of decoloring was 90% T or more.

Color development performance: 2 mm thick under conditions of temperature 23 ° C. and illumination intensity 50000 lux using Otsuka Electronics moment multiphotometric system MSPD-7700 equipped with excitation light source xenon lamp MS-35 AAA / FB 2000-O made by Ushio Inc. Excitation light was irradiated for 15 minutes to the molded sample obtained by processing to measure the spectral transmittance, and the luminous transmittance .tau.V1 (% T; 400 nm-780 nm) at the time of color development was calculated based on ISO 8980-3. When the luminous transmittance at the time of coloring was 20% T or less, it was judged that the coloring performance was high.

-Average transmittance of 400 nm to 420 nm: Of the transmittance of 400 nm to 780 nm obtained by the measurement based on ISO 8980-3 above, the average value of transmittance of 400 nm to 420 nm is the average transmittance of 400 nm to 420 nm (%) And
-HEV cut ability at color development: With respect to the spectrum at the time of color development, a value obtained by subtracting the average transmittance (%) at 400 nm to 420 nm from 100% was calculated. If this value is 90% or more, it is judged that the HEV cut ability at the time of coloring is high.

Circadian rhythm stabilization ability: A luminous transmittance τV2 (% T; 460 nm-500 nm) at 460 nm to 500 nm at color development was determined, and a value obtained by subtracting the luminous transmittance τV1 at color development was calculated. If this value is 10% T or more, it is judged that the circadian rhythm stabilization ability is high.

(Raw material used)
Photochromic compound:
-Revimsa Rev Wembley Gray (polyoxyalkylene chain, naphthopyran based chromophore (general formula (c))) manufactured by Vivimed
-Revimsa Rev Heatl Green (polyoxyalkylene chain, naphthopyran based chromophore (general formula (c))) manufactured by Vivimed
-Made by Vivimed Reversacol Peacock Blue (polyoxyalkylene chain, naphthopyran based chromophore (general formula (c)))
-Made by Vivimed Reversacol Jalapeno Red (polyoxyalkylene chain, naphthopyran type chromophore (general formula (c)))
monomer:
SunSensors-55 Monomer (Mitsui Chemical Co., Ltd.):
44% by weight of dimethacrylate of general formula (i), 18% by weight of diacrylate of general formula (ii), 15% by weight of dimethacrylate of general formula (ii), 9% by weight of methacrylate of general formula (iii), Polymerizable composition containing as a main component 4.5% by weight of divinylbenzene iv) Sun Sensors-50 monomer (made by Mitsui Chemicals, Inc.):
Polymerizable composition containing 12% by weight of allyl carbonate of general formula (11) and 86% by weight of (meth) acrylate of general formula (12)

Example 1
Acidic phosphorus in 49.6 parts by weight of a mixture of 2,5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane 0.30 parts by weight of JP-506H manufactured by Johoku Chemical Co., Ltd., 2.0 parts by weight of Adeka Pluronic L-64 manufactured by Adeka as acid ester, 0.1118 parts by weight of Reversa Wembley Gray (manufactured by Vivimed) as a photochromic compound, Reversacol Heath Green (Vivimed) Product (0.0915 parts by weight) and 0.075 parts by weight of HOSTAVIN PR-25 as an ultraviolet absorber were added and dissolved by stirring. After 23.4 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) and 25.0 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were added to this mixture and stirred, dimethyltin dichloride 0.040 was added. The parts by weight were added and dissolved uniformly. Degassed for 60 minutes under 5 mmHg. The mixture was filtered with a 1 μm PTFE filter and poured into a mold consisting of a glass mold and a tape. After the mold was put into an oven, the temperature was gradually raised to 30 ° C. to 120 ° C. over 23 hours for polymerization. After completion of polymerization, the mold was taken out of the oven and released to obtain a 2 mm thick resin flat plate. The obtained resin flat was further annealed at 120 ° C. for 1 hour. The obtained evaluation results are shown in Table 1. FIG. 1 shows the transmittance curve (spectral transmittance) of a resin flat plate.

Example 2
Product name SunSensors-55 Monomer (Mitsui Chemical Co., Ltd.) 100.0 parts by weight as a photochromic compound, Reversacol Wembley Gray (Vivimed) 0.0810 parts by weight, Reversacol Heath Green (Vivimed) 0.0323 parts by weight, and then 2 0.25 parts by weight of 2,2′-azobis [2,4-dimethylvaleronitrile] and 0.03 parts by weight of 1,1-bis (t-butylperoxy) cyclohexane were added and dissolved by stirring. Degassed for 60 minutes under 5 mmHg. The mixture was filtered with a 1 μm PTFE filter and poured into a mold consisting of a glass mold and a tape. After the mold was put into an oven, the temperature was gradually raised to 35 ° C. to 95 ° C. over 23 hours to polymerize. After completion of polymerization, the mold was taken out of the oven and released to obtain a 2 mm thick resin flat plate. The obtained resin flat was further annealed at 110 ° C. for 1 hour. The obtained evaluation results are shown in Table 1. FIG. 2 shows the transmittance curve (spectral transmittance) of the resin flat plate.

[Example 3]
After adding 0.1060 parts by weight of Reversa Wembley Gray (manufactured by Vivimed) and 0.0570 parts by weight of Reversa Heath Green (manufactured by Vivimed) as photochromic compounds to 100.0 parts by weight of a product named SunSensors-50 monomer (manufactured by Mitsui Chemicals) 0.55 parts by weight of -butyl-peroxyneodecanoate and 0.15 parts by weight of 1,1,3,3-tetramethylbutyl-2-ethylperoxyhexanoate were added and dissolved by mixing and stirring. Degassed for 60 minutes under 5 mmHg. The mixture was filtered with a 1 μm PTFE filter and poured into a mold consisting of a glass mold and a tape. After the mold was put into an oven, the temperature was gradually raised to 30 ° C. to 85 ° C. over 23 hours for polymerization. After completion of polymerization, the mold was taken out of the oven and released to obtain a 2 mm thick resin flat plate. The obtained resin flat was further annealed at 110 ° C. for 1 hour. The obtained evaluation results are shown in Table 1. FIG. 3 shows the transmittance curve (spectral transmittance) of a resin flat plate.

[Comparative Examples 1 to 7]
The evaluation results obtained by evaluating the commercially available dimming lenses are shown in Table 1. The commercially available dimming lenses are as follows. DEAMYUNG OPTICAL's DAGAS PHOTOCHROMIC LENS, CONANT OPTICAL's PHOTOCHROMIC GRAY, GKB-O's DAYNITE PHOTOCHROMIC LENS, TOKAI OPTICAL's PHOTOG RAY EXTRA, CHEMILENS's Acclimates, YOUNGER OPTICS's Transitions SignatureVII,

The light control dyes in Table 1 are as follows.
Dye A: Reversacol Wembley Gray (manufactured by Vivimed)
Dye B: Reversacol Heath Green (manufactured by Vivimed)

Example 4
0.0600 parts by weight of Reversacol Wembley Gray (manufactured by Vivimed) as a photochromic compound, 0.1000 parts by weight of Reversacol Heath Green (manufactured by Vivimed), 0.0500 parts by weight of Reversa Peacock Blue (manufactured by Vivimed), 0.0050 parts by weight of Reversacol Jalapeno Red (manufactured by Vivimed) The procedure was carried out in the same manner as in Example 1 except for changing to. The evaluation results obtained are shown in Table-2.

[Example 5]
Same as Example 1 except that 0.0600 parts by weight of Reversacol Wembley Gray (manufactured by Vivimed), 0.0800 parts by weight of Reversacol Heath Green (manufactured by Vivimed), and 0.0300 parts by weight of Reversa Peacock Blue (manufactured by Vivimed) as photochromic compounds are used. Went in the The evaluation results obtained are shown in Table-2.

[Example 6]
49.3 parts by weight of 1,3-xylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1 0.20 parts by weight of JP-506H manufactured by Johoku Kagaku Kogyo Co., Ltd. as acid phosphate ester, 0.2 parts by weight of CAPA 2302A manufactured by Perstorp Co., and 2.0 parts by weight of CAPA 2302A manufactured by Perstorp Co. A portion, 0.0670 parts by weight of Reversacol Heath Green (manufactured by Vivimed), and 0.10 parts by weight of HOSTAVIN PR-25 as a UV absorber were added and dissolved by stirring. This mixture contains 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithia After adding and stirring 48.0 parts by weight of a mixture of undecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 0.0050 parts by weight of dimethyltin dichloride is added and homogeneously dissolved did. Degassed for 60 minutes under 5 mmHg. The mixture was filtered with a 1 μm PTFE filter and poured into a mold consisting of a glass mold and a tape. After the mold was put into an oven, the temperature was gradually raised to 30 ° C. to 120 ° C. over 23 hours for polymerization. After completion of polymerization, the mold was taken out of the oven and released to obtain a 2 mm thick resin flat plate. The obtained resin flat was further annealed at 120 ° C. for 1 hour. The evaluation results obtained are shown in Table-2.

[Example 7]
0.0400 parts by weight of Reversacol Wembley Gray (manufactured by Vivimed), 0.0800 parts by weight of Reversacol Heath Green (manufactured by Vivimed) as a photochromic compound, 0.0300 parts by weight of Reversacol Peacock Blue (manufactured by Vivimed), 0.0030 parts by weight of Reversacol Jalapeno Red (manufactured by Vivimed) The procedure was carried out in the same manner as in Example 3 except for changing to. The evaluation results obtained are shown in Table-2.

In Table 2, Dyes A and B are the same as Table 1, and Dyes C and D are as follows.
Dye C: Reversacol Peacock Blue (manufactured by Vivimed)
Dye D: Reversacol Jalapeno Red (manufactured by Vivimed)

  As described above, in Examples 1 to 7, the luminous transmittance at the time of decoloring exhibits high transparency of 90% T or more, and the luminous transmittance at the time of color development is as high as 20% T or less , And the cut rate of 400 nm to 420 nm shows high HEV cut ability of 90% or more, and further the value of visual transmittance of 460 nm to 500 nm minus the luminous transmittance of 400 nm to 780 nm is 10% or more It was confirmed that it was able to transmit the wavelength necessary for circadian rhythm.

Claims (24)

The luminous transmittance from 400 nm to 780 nm is 90% or more at the time of decoloring,
A photochromic lens in which the transmittance at 23 ° C. after irradiation for 15 minutes at an illuminance of 50000 lux using a xenon lamp satisfies the following conditions.
(1) The luminous transmittance from 400 nm to 780 nm is 20% or less.
(2) The value obtained by subtracting the average transmittance of 400 nm to 420 nm from 100% is 90% or more.
(3) A value obtained by subtracting the luminous transmittance from 400 nm to 780 nm from the luminous transmittance from 460 nm to 500 nm is 10% or more. The photochromic lens according to claim 1, comprising at least one photochromic dye selected from the compounds represented by the following general formula (3) and the general formula (4).

(In the general formula (3) and the general formula (4), R ₁ and R ₂ may be the same or different, and independently hydrogen;
A linear or branched alkyl group having 1 to 12 carbon atoms;
A cycloalkyl group having 3 to 12 carbon atoms;
A substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a heteroaryl group having 4 to 24 carbon atoms;
An aralkyl or heteroaralkyl group (a linear or branched alkyl group having 1 to 4 carbon atoms is substituted with the above-mentioned aryl group or heteroaryl group) is shown.
The substituent of the substituted aryl group having 6 to 24 carbon atoms or the substituted heteroaryl group having 4 to 24 carbon atoms is a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, carbon A linear or branched alkoxy group of 1 to 12, a linear or branched haloalkyl group of 1 to 12 carbon atoms substituted with at least one halogen atom, a carbon atom 1 substituted with at least one halogen atom To 12 linear or branched haloalkoxy groups, at least one linear or branched alkyl group having 1 to 12 carbon atoms, or a phenoxy group or naphthoxy group substituted by an alkoxy group, a straight chain having 2 to 12 carbon atoms A chain or branched alkenyl group, -NH ₂ group, -NHR group, -N (R) ₂ group (R is a linear or branched alkyl group having 1 to 6 carbon atoms. There are two R groups. If And two R's may be the same or different) and at least one selected from a methacryloyl group or an acryloyl group.
R ₃ may be the same or different, and independently, a halogen atom;
A linear or branched alkyl group having 1 to 12 carbon atoms;
A cycloalkyl group having 3 to 12 carbon atoms;
A linear or branched alkoxy group having 1 to 12 carbon atoms;
A linear or branched haloalkyl group having 1 to 12 carbon atoms substituted with at least one halogen atom, a halocycloalkyl group having 3 to 12 carbon atoms substituted with at least one halogen atom, at least one halogen atom A substituted linear or branched haloalkoxy group having 1 to 12 carbon atoms;
A substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a heteroaryl group having 4 to 24 carbon atoms (as a substituent, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, C1-C12 linear or branched alkoxy group, C1-C12 linear or branched haloalkyl group substituted by at least one halogen atom, carbon number substituted by at least one halogen atom 1 to 12 linear or branched haloalkoxy group, at least one linear or branched alkyl group having 1 to 12 carbon atoms, or phenoxy or naphthoxy group substituted by an alkoxy group, having 2 to 12 carbon atoms A linear or branched alkenyl group, and an amino group, having at least one substituent selected from
An aralkyl or heteroaralkyl group (a linear or branched alkyl group having 1 to 4 carbon atoms is substituted with the above aryl group or heteroaryl group);
A substituted or unsubstituted phenoxy or naphthoxy group (having at least one substituent selected from a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxy group as a substituent);
-NH _2, -NHR, -CONH ₂ or -CONHR,
(R is a linear or branched alkyl group having 1 to 6 carbon atoms.);
—OCOR ₈ or —COOR ₈ (wherein, R ₈ is a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, or substituted at R ₁ and R ₂ A phenyl group substituted by at least one of the substituents of the aryl or substituted heteroaryl group or an unsubstituted phenyl group);
Represents
At least two adjacent R ₃ bonded to each other include a carbon atom to which R ₃ is attached, can form one or more aromatic ring group or non-aromatic ring group. The aromatic or non-aromatic ring group comprises one ring or two annelated rings which may contain heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen.
l is an integer of 0 to 2; m is an integer from 0 to 4; ) The photochromic lens in any one of Claim 1 or 2 containing the photochromic pigment represented by following General formula (5).

(In the general formula (5), R ¹ , R ² , R ³ and m are the same as the general formula (3), and A represents an annelated ring of the following formulas (A ₁ ) to (A ₅ ) .

(In these anelized rings (A ₁ ) to (A ₅ ), the dotted line represents a carbon C ₅ carbon C ₆ bond of the naphthopyran ring of the general formula (5). Anodized ring (A ₄ ) or (A ₅ ) The α bond of) is bonded to carbon ₅ or carbon ₆ of the naphthopyran ring of the general formula (5).
R ₄ is the same or different and independently represent OH, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkoxy group, or two R ₄ form a carbonyl (CO).
R ₅ , R ₆ and R ₇ independently represent a halogen atom;
A linear or branched alkyl group having 1 to 12 carbon atoms;
A linear or branched haloalkyl group having 1 to 6 carbon atoms, which is substituted by at least one halogen atom;
A cycloalkyl group having 3 to 12 carbon atoms;
A linear or branched alkoxy group having 1 to 6 carbon atoms;
A substituted or unsubstituted phenyl or benzyl group (when R ₁ and R _{2 in} the general formula (5) independently correspond to an aryl or heteroaryl group as a substituent, they are as defined above in the definition of R ₁ and R ₂₎ With at least one of the
-NH _2, -NHR
(Wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms);
A substituted or unsubstituted phenoxy or naphthoxy group (having a linear or branched alkyl group having at least 1 to 6 carbon atoms or an alkoxy group as a substituent);
-COR ₉ , -COOR ₉ or -CONHR ₉ group (wherein R ₉ is a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, or substituted or non-substituted A substituted phenyl or benzyl group (when the R ₁ and R ₂ groups in the general formula (5) independently correspond to an aryl or heteroaryl group as a substituent, the substituents described above in the definition of R ₁ and R ₂ groups Have at least one of the
n is an integer from 0 to 6, o is an integer from 0 to 2, p is an integer from 0 to 4, and q is an integer from 0 to 3.
In addition, when A shows (A ₄ ), n is an integer from 0 to 2, p is an integer from 0 to 4, and when A shows (A ₂ ), n is from 0 to 2 Is an integer of ))) The photochromic lens according to any one of claims 1 to 3, comprising a photochromic dye represented by the following general formula (a) or (b).
PC-L-Chain (a)
PC-L-Chain-L'-PC '(b)
(PC and PC ′ each represent any of the general formulas (c) to (f). PC and PC ′ may be the same or different.)

(In the general formulas (c) to (f), R ^{1 to} R ^{18 each} represent a hydrogen, a halogen atom, a carboxyl group, an acetyl group, a formyl group, a C1 to C20 aliphatic group which may be substituted, or a substituted one It is a good C3 to C20 alicyclic group, or an optionally substituted C6 to C20 aromatic organic group, which may be the same or different, and these aliphatic group, alicyclic group or aromatic organic group is And any one of the groups contained in the compounds represented by formulas (c) to (f) is bonded to L or L 'which is a divalent organic group. L and L ′ each represent a divalent organic group containing one or more selected from an oxyethylene chain, an oxypropylene chain, a (thio) ester group, and a (thio) amide group, and a chain is a polysiloxane chain, One or more selected from polyoxyalkylene chains Represents a monovalent or divalent organic group containing   The photochromic lens according to any one of claims 1 to 4, comprising at least one selected from poly (meth) acrylates, polyallyl carbonates, and poly (thio) urethanes. The poly (meth) acrylate is a structural unit derived from at least two selected from the compounds represented by the following general formula (i), general formula (ii), general formula (iii) and formula (iv) The photochromic lens according to claim 5, comprising.

(In the formula, R represents a hydrogen atom or a methyl group, and a plurality of R may be the same or different. M and n represent an integer of 0 to 20 and may be the same or different.)

(In the formula, R represents a hydrogen atom or a methyl group, and a plurality of R may be the same or different. P represents an integer of 0 to 20.)

(Wherein, R represents a hydrogen atom or a methyl group, and q represents an integer of 0 to 20).

The photochromic lens comprises a mixture of the polyallyl carbonate and the poly (meth) acrylate,
The mixture is represented by a structural unit (a) represented by the following general formula (11) and a structural unit (a) derived from an allyl carbonate compound (A) containing two or more allyloxycarbonyl groups, and a general formula (12) And a structural unit (b) derived from a (meth) acrylate compound (B) containing two or more (meth) acrylic groups,
The composition comprises 5 wt% to 30 wt% of the structural unit (a) and 70 wt% to 95 wt% of the structural unit (b) with respect to a total of 100 wt% of the structural unit (a) and the structural unit (b) 6. The photochromic lens according to item 5.

(R ¹ is a C5 to C40 cycloaliphatic polyol which may contain a heterovalent group or a divalent group derived from a chained or branched C3 to C35 aliphatic polyol which may contain a hetero atom M represents an integer of 2 to 10. Note that R ¹ does not contain an allyloxycarbonyl group.)

(R ² represents a hetero atom or a divalent to tetravalent organic group having 1 to 30 carbon atoms which may contain an aromatic group. R ³ represents a hydrogen atom or a methyl group. N is 2 to 4) Indicates an integer of Compound (A) is diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl Glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1 Bis of at least one diol selected from 3, 3-pentanediol, 1,4-dimethylol cyclohexane and 4,8-bis (hydroxymethyl)-[5.2.1.0 ^2,6 ] tricyclodecane (Allyl carbonate) compound,
A tris (allyl carbonate) compound of at least one triol selected from glycerol, trimethylolpropane and tris (hydroxyethyl) isocyanurate,
At least one tetraol tetra (allyl carbonate) compound selected from pentaerythritol, diglycerol and ditrimethylolpropane;
At least one selected from a hexa (allyl carbonate) compound of dipentaerythritol and a mixed poly (allyl carbonate) compound of at least two compounds selected from the diol, the triol, the tetraol, and the dipentaerythritol. The photochromic lens according to claim 7, which is The compound (A) is
(i) mixtures of diethylene glycol with bis (allyl carbonate) compounds and their oligomers,
(ii) bis (allyl carbonate) compounds of mixtures of diethylene glycol and neopentyl glycol and mixtures thereof with oligomers,
(iii) a mixture of diethylene glycol and tris (hydroxyethyl) isocyanurate with a poly (allyl carbonate) compound and its oligomer,
(iv) mixtures of diethylene glycol and trimethylolpropane with poly (allyl carbonate) compounds and their oligomers,
(v) Mixtures of diethylene glycol and pentaerythritol with poly (allyl carbonate) compounds and their oligomers,
(vi) mixtures of poly (allyl carbonate) compounds of mixtures of diethylene glycol, neopentyl glycol and pentaerythritol and their oligomers, and
(vii) a mixture of diethylene glycol, neopentyl glycol and pentaerythritol and a mixture of poly (allyl carbonate) compounds and their oligomers;
The photochromic lens according to claim 7 or 8, which is at least one selected from a poly (allyl carbonate) mixture containing a mixture of diethylene glycol with a bis (allyl carbonate) compound and an oligomer thereof. The photochromic lens according to any one of claims 7 to 9, wherein the compound (B) is at least one selected from the compounds represented by the following general formula (16) and the following general formula (17).

(P represents a numerical value of 1 to 100, R ³ represents a hydrogen atom or a methyl group, and may not be identical to each other.)

(Q represents a numerical value of 1 or more, respectively, and the sum of two q represents a numerical value of 2 to 100. R ³ represents a hydrogen atom or a methyl group, which may not be identical to each other. X is a substitution Or a divalent aliphatic group which may contain a substituted or unsubstituted divalent aromatic group or a substituted or unsubstituted C1 to C20 aromatic group.   The photochromic lens according to claim 10, wherein the compound (B) is selected from compounds represented by p in the general formula (16), 2 to 4.   The photochromic lens according to claim 11, wherein the compound (B) is at least one selected from diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate.   (A) a structural unit derived from a polyisocyanate compound, (b) a structural unit derived from a polyol compound having a number average molecular weight of 100 or more, and (c) an active hydrogen compound having two or more functions (here, the compound The photochromic lens according to claim 5, comprising the structural units derived from (b).   Polyisocyanate compounds (a) are hexamethylene diisocyanate, pentamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2. 2.1] at least one member selected from the group consisting of heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, tolylene diisocyanate, phenylene diisocyanate, and diphenylmethane diisocyanate The photochromic lens according to claim 13.   The photochromic lens according to claim 13 or 14, wherein the polyol compound (b) is a diol or triol type of polyethylene glycol or polypropylene glycol.   The photochromic lens according to claim 15, wherein the number average molecular weight of the polyol compound (b) is 200 to 4,000. The photochromic lens according to claim 13 or 14, wherein the polyol compound (b) is a compound represented by the following general formula (I).

(In general formula (I), R ¹ and R ^{2 each} represent a hydrogen atom, a methyl group or an ethyl group, at least one of which is a hydrogen atom. R ¹ and R ² may be the same or different) N is an integer of 30 or more and 500 or less) The photochromic lens according to claim 17, wherein the polyol compound (b) is a compound represented by the following general formula (II).

(In general formula (II), R ³ and R ^{4 each} represent a hydrogen atom, a methyl group or an ethyl group, and at least one of them is a hydrogen atom. R ³ and R ⁴ may be the same or different. A + c is an integer of 2 or more and 400 or less, and b is an integer of 1 or more and 100 or less.)   The photochromic lens according to claim 18, wherein the number average molecular weight of the compound represented by the general formula (II) is 1,000 to 15,000.   The photochromic lens according to claim 19, wherein the number average molecular weight of the compound represented by formula (II) is from 1,500 to 7,500.   The photochromic lens according to any one of claims 13 to 20, wherein the active hydrogen compound (c) is at least one selected from the group consisting of a polyol compound, a polythiol compound and a thiol compound having a hydroxyl group.   The photochromic lens according to any one of claims 13 to 21, wherein the active hydrogen compound (c) is a trifunctional or higher active hydrogen compound.   Active hydrogen compound (c) is glycerin, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5 , 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 4,8 -Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, and trimethylolpropane tris (3-mercaptopropionate) 14. from at least one selected from the group consisting of The photochromic lens according to any one of 2.   The plastic polarizing lens provided with the polarizing film and the base material layer which consists of a photochromic lens in any one of the Claims 1-23 formed on the surface of the at least objective surface side of the said polarizing film.

Images