JP2008120862A - Photochromic microcapsule - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photochromic microcapsule capable of improving light resistance which cannot be achieved by a conventional photochromic material and regulating a color tone and having excellent applicability in usability for all fields. <P>SOLUTION: The photochromic microcapsule is obtained by encapsulating a photochromic compound selected from a spiroxazine derivative or a spiropyran derivative, a styrenic oligomer having 200-6,000 weight-average molecular weight and a compound having a phenolic hydroxy group in a capsule wall membrane. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photochromic microcapsule. More specifically, the present invention relates to a photochromic microcapsule with improved light fastness and color tone adjustment.

Conventionally, as a photochromic material with improved light fastness, a material obtained by adding a styrene oligomer to a photochromic compound has been disclosed (for example, see Patent Document 1).
JP 2005-48159 A

  When practicality of the above-described conventional photochromic material was confirmed, it had an effect of improving light fastness, but it was difficult to adjust the color tone because the color tone was determined by the structure of the photochromic compound.

（式中、Ｘ_１、Ｘ_２、Ｘ_３はそれぞれ水素原子、ハロゲン、有機残基から選ばれる置換基を示す。）
ヒンダードアミン系光安定剤を含んでなること、
前記ヒンダードアミン系光安定剤が下記一般式（２）で示される化合物であること等を要件とする。

（式中、Ｒ_１は炭素数１乃至３０のアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５はそれぞれ炭素数１乃至５のアルキル基を示し、ｎは１以上の整数を示し、Ｒ_６はｎ価の有機残基を示す。） As a result of studying photochromic materials that are excellent in light fastness and adjustable in color tone, the present inventors have adjusted the color tone without impairing light fastness by using a compound having a phenolic hydroxyl group together with a styrene oligomer. It has been found that possible photochromic materials are obtained.
That is, the present invention provides a photochromic microcapsule in which a photochromic compound selected from spirooxazine derivatives or spiropyran derivatives, a styrene oligomer having a weight average molecular weight of 200 to 6000, and a compound having a phenolic hydroxyl group are encapsulated in a capsule wall film. As a requirement.
Furthermore, the weight ratio of the photochromic compound to the styrene oligomer is 1: 1 to 1: 10000, and the weight ratio of the photochromic compound to the compound having a phenolic hydroxyl group is 0.5: 1 to 10,000: 1. The compound having a phenolic hydroxyl group is a compound represented by the following general formula (1),

(In the formula, X ₁ , X ₂ and X ₃ each represent a substituent selected from a hydrogen atom, a halogen and an organic residue.)
Comprising a hindered amine light stabilizer,
It is a requirement that the hindered amine light stabilizer is a compound represented by the following general formula (2).

(In the formula, R ₁ represents an alkyl group having 1 to 30 carbon atoms, R ₂ , R ₃ , R ₄ and R ₅ each represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 or more. , R ₆ represents an n-valent organic residue.)

  INDUSTRIAL APPLICABILITY The present invention can provide a photochromic microcapsule having excellent applicability that can be used in various fields, as well as improved light resistance, which could not be achieved with conventional photochromic materials, and can be adjusted in color tone.

In the present invention, a photochromic compound selected from spirooxazine derivatives or spiropyran derivatives is practically used after being dissolved in a medium composed of a styrene oligomer having a weight average molecular weight of 200 to 6000 and a compound having a phenolic hydroxyl group.
The present inventors use a styrene-based oligomer as a main medium for dissolving the photochromic compound, and add a compound having a phenolic hydroxyl group as a compound having a different polarity to the medium to adjust the color tone. I found it.
Specifically, if the amount of the compound having a phenolic hydroxyl group is increased, the color tone of the photochromic compound is shifted to the longer wavelength side, and if the amount of the compound having the phenolic hydroxyl group is decreased, the color tone of the photochromic compound is increased. Color tone can be adjusted by shifting the color tone to the short wavelength side.
In addition, although this invention can adjust a color tone by adding the compound from which polarity differs in a styrene-type oligomer, a highly polar compound (for example, an ester compound, an ether compound, a ketone compound) is used. If it is used, light resistance is likely to be impaired, and if a low-polarity compound (for example, saturated hydrocarbon such as octadecane) is used, the solubility of the photochromic compound is lowered, and a reduction in color density is inevitable.

The styrene oligomer has a weight average molecular weight of 200 to 6000, preferably 200 to 4000.
When the weight average molecular weight of the styrene-based oligomer is less than 200, the amount of the monomer is increased and the stability is insufficient, so that it is difficult to exhibit the effect of improving light resistance.
On the other hand, if the weight average molecular weight exceeds 6000, a color residue is generated by light irradiation, the color density is lowered, and the discoloration sensitivity becomes dull.
The weight average molecular weight is measured by GPC method (gel permeation chromatography).

Examples of the styrene oligomer include low molecular weight polystyrene, styrene-α-methylstyrene copolymer, α-methylstyrene polymer, copolymer of α-methylstyrene and vinyltoluene, α-pinene polymer, β-pinene. Examples thereof include a polymer and a d-limonene polymer.
As the low molecular weight polystyrene, Sanyo Chemical Industries, Ltd., trade names: Hymer SB-75 (weight average molecular weight 2000), Hemer ST-95 (weight average molecular weight 4000) and the like are used.
As the styrene-α-methylstyrene-based copolymer, Rika Hercules Co., Ltd., trade names: Picolastic A5 (weight average molecular weight 317), Picolastic A75 (weight average molecular weight 917), and the like are used.
Examples of the α-methylstyrene polymer include Rika Hercules Co., Ltd., trade names: Crystallex 3085 (weight average molecular weight 664), Crystallex 3100 (weight average molecular weight 1020), Crystallex 1120 (weight average molecular weight 2420), and the like. Used.
As the copolymer of α-methylstyrene and vinyltoluene, Rika Hercules Co., Ltd., trade names: Picotex LC (weight average molecular weight 950), Picotex 100 (weight average molecular weight 1740) and the like are used.
As the α-pinene polymer, Rika Hercules Co., Ltd., trade name: Picolite A115 (weight average molecular weight 833) is used.
As the β-pinene polymer, Rika Hercules Co., Ltd., trade name: Picolite S115 (weight average molecular weight 1710) is used.
As the d-limonene polymer, Rika Hercules Co., Ltd., trade name: Picolite C115 (weight average molecular weight 902) is used.
The styrene oligomers may be used alone or in combination of two or more.

（式中、Ｘ_１、Ｘ_２、Ｘ_３はそれぞれ水素原子、ハロゲン、有機残基から選ばれる置換基を示す。）
前記一般式（１）で示される化合物として具体的には、４−（１−メチル−１−フェニルエチル）フェノール、４−（１，１−ジメチル−エチル）フェノール、４−ドデシルフェノール、３，５−ジメチルフェノール、３−メチル−４−（１−メチルエチル）フェノール、１，１′−ビフェニル−４−オール、４−シクロヘキシルフェノール、４′−オクチロキシ〔（１，１′−ビフェニル）−４−オール〕、４′−テトラデシロキシ〔１，１´−ビフェニル−４−オール〕、４，４′−メチレンビスフェノール、２，２−ビス（４−ヒドロキシフェニル）プロパン、４−ヒドロキシアセトフェノン、ｐ−ヒドロキシ安息香酸、ｐ−ヒドロキシ安息香酸エステル、５−ヒドロキシイソフタル酸、５−ヒドロキシイソフタル酸エステル、５−ヒドロキシ−１−テトラロン、６−ヒドロキシ−２−ナフトエ酸、６−ヒドロキシ−２−ナフトエ酸エステル、４−ヒドロキシビフェニル−４′−カルボン酸、４−ヒドロキシビフェニル−４′−カルボン酸エステル、ｐ−ヒドロキシフェニルアセトアミド、ｐ−ヒドロキシフェニル酢酸、ｐ−ヒドロキシフェニル酢酸メチルエステル、ｐ−ヒドロキシフェニルプロピオン酸、ｐ−ヒドロキシフェネチルアルコール、４−ヒドロキシプロピオフェノン、ｍ−フェニルフェノール、ｐ−フェニルフェノール、４−フェノキシフェノール、ｐ−ｔ−ブチルフェノール、ｐ−メトキシメチルフェノール、４−メトキシフェノール、４，４′−エチリデンビスフェノール、４，４′−プロピリデンビスフェノール、４，４′−（２−メチル−プロピリデン）ビスフェノール、４，４′−（３−メチルブチリデン）ビスフェノール、４，４′−（２−エチルヘキシリデン）ビスフェノール、４，４′−デシリデンビスフェノール、４，４′−ドデシリデンビスフェノール、４，４′−（１，３−ジメチルブチリデン）ビスフェノール、４，４′−（１−メチル−プロピリデン）ビスフェノール、４，４′−（１−メチル−ヘプチリデン）ビスフェノール、４，４′−（１−メチル−オクチリデン）ビスフェノール、４，４′−（１−メチル−ノニリデン）ビスフェノール、４，４′−（１−メチル−ドデシリデン）ビスフェノール、４，４′−（１−メチル−テトラデシリデン）ビスフェノール、４，４′−（１，５，９，１３−テトラメチル−テトラデシリデン）ビスフェノール、４，４′−（１−エチルプロピリデン）ビスフェノール、４，４′−（フェニルメチレン）ビスフェノール、４，４′−（１−フェニルエチリデン）ビスフェノール、４，４′−（ジフェニルメチリデン）ビスフェノール、４，４′−シクロペンチリデンビスフェノール、４，４′−シクロヘキシリデンビスフェノール、４，４′−（４−メチル−シクロヘキシリデン）ビスフェノール、４，４′−（４−エチルシクロヘキシリデン）ビスフェノール、４，４′−（４−プロピルシクロヘキシリデン）ビスフェノール、４，４′−〔４−（１−メチルエチル）シクロヘキシリデン〕ビスフェノール、４，４′−（９Ｈ−フルオレン−９−イリデン）ビスフェノール、４，４′−オキシビスフェノール、４，４′−（ジメチルシリレン）ビスフェノール、ビス（４−ヒドロキシフェニル）メタノン、〔１，１′−ビフェニル〕−４，４′−ジオール、４，４′−（１，２−エタンジイル）ビスフェノール、２，２−ビス（４−ヒドロキシフェニル）プロピオン酸、４，４−ビス（４−ヒドロキシフェニル）ペンタノイック酸、２，２−ビス（４−ヒドロキシフェニル）プロピオン酸メチルエステル、２，２−ビス（４−ヒドロキシフェニル）プロピオン酸エチルエステル、４，４−ビス（４−ヒドロキシフェニル）ペンタノイック酸ブチルエステル、４，４′−〔（４−フルオロフェニル）メチレン〕ビスフェノール、４，４′−〔２，２，２−トリフルオロ−１−（トリフルオロメチル）エチリデン〕ビスフェノール、４，４′−〔（４−クロロフェニル）メチレン〕ビスフェノール、４，４′，４″−メチリデントリスフェノール、４−〔ビス（４−ヒドロキシフェニル）メチル〕−２−メトキシフェノール、４−〔ビス（４−ヒドロキシフェニル）メチル〕−２−エトキシフェノール、２，４′，４″−メチリデントリスフェノール、４，４′−〔（２−ヒドロキシフェニル）メチレン〕ビス（３−メチルフェノール）、４，４′，４″−エチリデントリスフェノール、２，６−ビス（４−ヒドロキシフェニルメチル）−４−エチルフェノール、２，４−ビス〔（４−ヒドロキシフェニル）メチル〕−６−シクロヘキシルフェノール、４，４′，４″−（３−メチル−１−プロパニル−３−イリデン）トリスフェノール、４，４′−〔１−〔４−〔１-（４−ヒドロキシフェニル）−１−メチルエチル〕フェニル〕エチリデン〕ビスフェノール、４，４′，４″，４′″−（１，２−エタンジイリデン）テトラキスフェノール、４，４′，４″，４′″−（１，４−フェニレンジメチリデン）テトラキスフェノール、４，４′，４″，４′″−テトラキス〔（１−メチルエチリデン）ビス(１，４−シクロヘキシリデン)〕フェノール等を例示できる。 Examples of the compound having a phenolic hydroxyl group include phenol, 3-methylphenol, 4-methylphenol, 2,5-dimethylphenol, 2,3,5-trimethylphenol, 2- (1-methylpropyl) phenol, 4 -(1-methylpropyl) phenol, 3-methyl-6- (1,1-dimethylethyl) phenol, 4-methyl-2- (1,1-dimethylethyl) phenol, 2- (1,1-dimethyl- Ethyl) phenol, 2-cyclohexylphenol, 2-cyclohexyl-5-methylphenol, 4- (1-methyl-1-phenylethyl) phenol, 2- (2-propenyl) phenol, 4- (1,1-dimethyl-) Ethyl) phenol, 4-dodecylphenol, 3,5-dimethylphenol, 3-methyl-4- (1-me Ruethyl) phenol, 1,1′-biphenyl-4-ol, 4-cyclohexylphenol, 4′-octyloxy [(1,1′-biphenyl) -4-ol], 4′-tetradecyloxy [1,1 ′ -Biphenyl-4-ol], 4,4'-methylenebisphenol, 2,2-bis (4-hydroxyphenyl) propane, 4-hydroxyacetophenone, p-hydroxybenzoic acid, p-hydroxybenzoic acid ester, 5-hydroxy Isophthalic acid, 5-hydroxyisophthalic acid ester, 5-hydroxy-1-tetralone, 6-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid ester, 4-hydroxybiphenyl-4'-carboxylic acid, 4- Hydroxybiphenyl-4'-carboxylic acid ester, p-hydroxyphenylacetate Amide, p-hydroxyphenylacetic acid, p-hydroxyphenylacetic acid methyl ester, p-hydroxyphenylpropionic acid, p-hydroxyphenethyl alcohol, 4-hydroxypropiophenone, m-phenylphenol, p-phenylphenol, 4-phenoxyphenol , Pt-butylphenol, p-methoxymethylphenol, 4-methoxyphenol, 4,4'-ethylidene bisphenol, 4,4'-propylidene bisphenol, 4,4 '-(2-methyl-propylidene) bisphenol, 4, , 4 '-(3-methylbutylidene) bisphenol, 4,4'-(2-ethylhexylidene) bisphenol, 4,4'-decylidene bisphenol, 4,4'-dodecylidene bisphenol, 4,4 '-(1,3-Dimethyl Rubutylidene) bisphenol, 4,4 '-(1-methyl-propylidene) bisphenol, 4,4'-(1-methyl-heptylidene) bisphenol, 4,4 '-(1-methyl-octylidene) bisphenol, 4,4' -(1-methyl-nonylidene) bisphenol, 4,4 '-(1-methyl-dodecylidene) bisphenol, 4,4'-(1-methyl-tetradecylidene) bisphenol, 4,4 '-(1,5,9, 13-tetramethyl-tetradecylidene) bisphenol, 4,4 '-(1-ethylpropylidene) bisphenol, 4,4'-(phenylmethylene) bisphenol, 4,4 '-(1-phenylethylidene) bisphenol, 4,4 '-(Diphenylmethylidene) bisphenol, 4,4'-cyclopentylidenebis Enol, 4,4'-cyclohexylidenebisphenol, 4,4 '-(4-methyl-cyclohexylidene) bisphenol, 4,4'-(4-ethylcyclohexylidene) bisphenol, 4,4 '-(4 -Propylcyclohexylidene) bisphenol, 4,4 '-[4- (1-methylethyl) cyclohexylidene] bisphenol, 4,4'-(9H-fluorene-9-ylidene) bisphenol, 4,4'-oxy Bisphenol, 4,4 '-(dimethylsilylene) bisphenol, bis (4-hydroxyphenyl) methanone, [1,1'-biphenyl] -4,4'-diol, 4,4'-(1,2-ethanediyl) Bisphenol, 2,2-bis (4-hydroxyphenyl) propionic acid, 4,4-bis (4-hydroxypheny ) Pentanoic acid, 2,2-bis (4-hydroxyphenyl) propionic acid methyl ester, 2,2-bis (4-hydroxyphenyl) propionic acid ethyl ester, 4,4-bis (4-hydroxyphenyl) pentanoic acid butyl Ester, 4,4 '-[(4-fluorophenyl) methylene] bisphenol, 4,4'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol, 4,4 '-[ (4-Chlorophenyl) methylene] bisphenol, 4,4 ′, 4 ″ -methylidenetrisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, 4- [bis (4-hydroxyphenyl) Methyl] -2-ethoxyphenol, 2,4 ', 4 "-methylidenetrisphenol, 4 , 4 '-[(2-hydroxyphenyl) methylene] bis (3-methylphenol), 4,4', 4 "-ethylidenetrisphenol, 2,6-bis (4-hydroxyphenylmethyl) -4-ethylphenol 2,4-bis [(4-hydroxyphenyl) methyl] -6-cyclohexylphenol, 4,4 ', 4 "-(3-methyl-1-propanyl-3-ylidene) trisphenol, 4,4'- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″, 4 ′ ″-(1,2-ethanediylidene) tetrakisphenol, 4 4,4 ', 4 ", 4'"-(1,4-phenylenedimethylidene) tetrakisphenol, 4,4 ', 4 ", 4'"-tetrakis [(1-methylethylide ) Bis (1,4-cyclohexylidene)] phenol, and the like.
In addition, the compound shown by following General formula (1) is used suitably as a compound which has the said phenolic hydroxyl group.

(In the formula, X ₁ , X ₂ and X ₃ each represent a substituent selected from a hydrogen atom, a halogen and an organic residue.)
Specific examples of the compound represented by the general formula (1) include 4- (1-methyl-1-phenylethyl) phenol, 4- (1,1-dimethyl-ethyl) phenol, 4-dodecylphenol, 3, 5-dimethylphenol, 3-methyl-4- (1-methylethyl) phenol, 1,1'-biphenyl-4-ol, 4-cyclohexylphenol, 4'-octyloxy [(1,1'-biphenyl) -4 -Ol], 4'-tetradecyloxy [1,1'-biphenyl-4-ol], 4,4'-methylenebisphenol, 2,2-bis (4-hydroxyphenyl) propane, 4-hydroxyacetophenone, p -Hydroxybenzoic acid, p-hydroxybenzoic acid ester, 5-hydroxyisophthalic acid, 5-hydroxyisophthalic acid ester, Roxy-1-tetralone, 6-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid ester, 4-hydroxybiphenyl-4'-carboxylic acid, 4-hydroxybiphenyl-4'-carboxylic acid ester, p- Hydroxyphenylacetamide, p-hydroxyphenylacetic acid, p-hydroxyphenylacetic acid methyl ester, p-hydroxyphenylpropionic acid, p-hydroxyphenethyl alcohol, 4-hydroxypropiophenone, m-phenylphenol, p-phenylphenol, 4- Phenoxyphenol, pt-butylphenol, p-methoxymethylphenol, 4-methoxyphenol, 4,4'-ethylidene bisphenol, 4,4'-propylidene bisphenol, 4,4 '-(2-methyl-propylidene ) Bisphenol, 4,4 '-(3-methylbutylidene) bisphenol, 4,4'-(2-ethylhexylidene) bisphenol, 4,4'-decylidene bisphenol, 4,4'-dodecylidene bisphenol 4,4 '-(1,3-dimethylbutylidene) bisphenol, 4,4'-(1-methyl-propylidene) bisphenol, 4,4 '-(1-methyl-heptylidene) bisphenol, 4,4'- (1-methyl-octylidene) bisphenol, 4,4 '-(1-methyl-nonylidene) bisphenol, 4,4'-(1-methyl-dodecylidene) bisphenol, 4,4 '-(1-methyl-tetradecylidene) bisphenol 4,4 '-(1,5,9,13-tetramethyl-tetradecylidene) bisphenol, 4,4'-( -Ethylpropylidene) bisphenol, 4,4 '-(phenylmethylene) bisphenol, 4,4'-(1-phenylethylidene) bisphenol, 4,4 '-(diphenylmethylidene) bisphenol, 4,4'-cyclopent Redene bisphenol, 4,4'-cyclohexylidene bisphenol, 4,4 '-(4-methyl-cyclohexylidene) bisphenol, 4,4'-(4-ethylcyclohexylidene) bisphenol, 4,4 '-( 4-propylcyclohexylidene) bisphenol, 4,4 '-[4- (1-methylethyl) cyclohexylidene] bisphenol, 4,4'-(9H-fluorene-9-ylidene) bisphenol, 4,4'- Oxybisphenol, 4,4 '-(dimethylsilylene) bisphenol, bi (4-hydroxyphenyl) methanone, [1,1′-biphenyl] -4,4′-diol, 4,4 ′-(1,2-ethanediyl) bisphenol, 2,2-bis (4-hydroxyphenyl) propion Acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, 2,2-bis (4-hydroxyphenyl) propionic acid methyl ester, 2,2-bis (4-hydroxyphenyl) propionic acid ethyl ester, 4, 4-bis (4-hydroxyphenyl) pentanoic acid butyl ester, 4,4 '-[(4-fluorophenyl) methylene] bisphenol, 4,4'-[2,2,2-trifluoro-1- (trifluoro) Methyl) ethylidene] bisphenol, 4,4 ′-[(4-chlorophenyl) methylene] bisphenol, 4,4 ′, 4 "-methylidenetrisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 2,4 ', 4 "-Methylidenetrisphenol, 4,4 '-[(2-hydroxyphenyl) methylene] bis (3-methylphenol), 4,4', 4" -ethylidenetrisphenol, 2,6-bis (4-hydroxy) Phenylmethyl) -4-ethylphenol, 2,4-bis [(4-hydroxyphenyl) methyl] -6-cyclohexylphenol, 4,4 ', 4 "-(3-methyl-1-propanyl-3-ylidene) Trisphenol, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisph Enol, 4,4 ′, 4 ″, 4 ′ ″-(1,2-ethanediylidene) tetrakisphenol, 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol, 4, Examples thereof include 4 ′, 4 ″, 4 ′ ″-tetrakis [(1-methylethylidene) bis (1,4-cyclohexylidene)] phenol.

Of the photochromic compounds, spirooxazine derivatives are shown below, but the present invention is not limited thereto.
As indoline spirobenzoxazine compounds,
1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
6'-chloro-5-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
3,3-dimethyl-1-ethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5,7-difluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-cyano-3,3-dimethyl-1- (methoxycarbonyl) methylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1′-methyl dispiro [cyclohexane-1,3 ′-[3H] indole-2 ′ (1′H), 3 ″-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1'-methyl-5'-nitrodispiro [cyclopentane-1,3 '-[3H] -indole-2'(1'H), 3 "-[3H] pyrido [4,3-f] [1,4 Benzoxazine],
1,3,3,5′-tetramethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
6'-fluoro-1'-methyl dispiro [cyclohexane-1,3 '-[3H] indole-2'(1'H), 3 "-[3H] pyrido [4,3-f] [1,4] benzo Oxazine],
1-benzyl-6'-chloro-3,3-dimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
6'-methoxy-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-chloro-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-bromo-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-iodo-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-trifluoromethyl-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
3,3-diethyl-1-methylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1,3,3,6′-tetramethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
6-chloro-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5'-fluoro-1'-methyl dispiro [cyclohexane-1,3 '-[3H] indole-2'(1'H), 3 "-[3H] pyrido [4,3-f] [1,4] benzo Oxazine],
5-cyano-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-ethoxycarbonyl-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
4 ', 6'-difluoro-1'-methyldispiro [cyclohexane-1,3'-[3H] indole-2 '(1'H), 3 "-[3H] pyrido [4,3-f] [1, 4] benzoxazine],
3,3-dimethyl-1- (methoxycarbonyl) methylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
3,3-dimethyl-1-phenylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
5-methoxy-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1,3,3,5-tetramethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
7'-chloro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1,3,3,7′-tetramethylspiro [2H-indole-2,3 ′-[3H] pyrido [4,3-f] [1,4] benzoxazine],
7'-methoxy-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine],
1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
6'-chloro-5-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
5-chloro-1,3-dimethyl-3-ethyl-5'-methoxyspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
3,3-diethyl-1-methyl-5-nitrospiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1 ', 6'-dimethylspiro [cyclohexane-1,3'-[3H] indole-2 '(1'H), 3 "-[3H] pyrido [2,3-f] [1,4] benzoxazine ],
9 "-Bromo-1'-methoxycarbonylmethyl-5'-trifluoromethyl dispiro [cyclopentane-1,3 '-[3H] -indole-2'[1'H],3"-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1-Benzyl-3,3-di-nbutyl-7'-ethyl-5-methoxyspiro [2H-indole-1,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine ],
1'-n-butyl-6'-iododispiro [cycloheptane-1,3 '-[3H] -indole-2'(1'H), 3 "-[3H] pyrido [2,3-f] [1 , 4] benzoxazine],
3,3-dimethyl-9'-iodo-1-naphthylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
4'-cyano-1 '-(2- (methoxycarbonyl) ethyl) dispiro [cyclohexane-1,3'-[3H] indole-2 '(1'H), 3 "-[3H] pyrido [2,3 -F] [1,4] benzoxazine],
7-methoxycarbonyl-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
4-bromo-3,3-diethyl-9'-ethoxy-1- (2-phenyl) ethylspiro [2H-indole-2,3 '-[2,3-f] [1,4] benzoxazine],
1′-methyl dispiro [cyclohexane-1,3 ′-[3H] -indole-2 ′ (1′H), 3 ″-[3H] pyrido [2,3-f] [1,4] benzoxazine],
6-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
5-ethyl-9-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1'-benzyl-6 "-iododispiro [cyclopentane-1,3 '-[3H] -indole-2'(1'H),3"-[3H] pyrido [2,3-f] [1,4 Benzoxazine],
5-ethoxy-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1'-methyl-5'-trichloromethyl dispiro [cyclohexane-1,3 '-[3H] -indole-2'(1'H), 3 "-[3H] pyrido [2,3-f] [1 , 4] benzoxazine],
1,3-diethyl-3-methylspiro [2H-indole-2,3 ′-[3H] pyrido [2,3-f] [1,4] benzoxazine],
1'-methoxycarbonylmethyl dispiro [cyclohexane-1,3 '-[3H] -indole-2'(1'H)-[3H] pyrido [2,3-f] [1,4] benzoxazine], etc. Examples of the substituents such as halogen, methyl, ethyl, methylene, ethylene, and hydroxyl groups of the indole ring and benzene ring of indolinospirobenzoxazine can be given.

As indoline spiro naphthoxazine compounds,
1,3,3-trimethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-chloro-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-bromo-spiroindoline naphthoxazine,
1,3,3,5-tetramethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-n-propyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-iso-butyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-methoxy-spiroindoline naphthoxazine,
1,3,3-trimethyl-5-n-propoxy-spironaphthoxazine,
1,3,3-trimethyl-5-cyano-spiroindoline naphthoxazine,
1-n-ethyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-n-propyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-iso-butyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-n-octyl-3,3-dimethyl-spiroindoline naphthoxazine,
1-n-octadecyl-3,3-dimethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-8'-sulfonic acid sodium-spiroindoline naphthoxazine,
1,3,3-trimethyl-9'-methoxyspiroindoline naphthoxazine,
1,3,3-trimethyl-5-trifluoro-spiroindoline naphthoxazine,
1-benzyl-3,3-dimethyl-spironaphthoxazine,
1- (4′-methylphenyl) -3,3-dimethyl-spironaphthoxazine,
1,3,3-trimethyl-6 '-(2,3-dihydro-1-indolino) -spiroindoline naphthoxazine,
1,3,3-trimethyl-6 '-(1-piperidinyl) -spiroindoline naphthoxazine,
1,3,3-trimethyl-6-trifluoromethyl-6 '-(1-piperidinyl) -spiroindoline naphthoxazine,
1-benzyl-3,3-dimethyl-spiroindoline naphthoxazine,
1- (4-methoxybenzyl) -3,3-dimethyl-spiroindoline naphthoxazine,
1- (4-chlorobenzyl) -3,3-dimethyl-spiroindoline naphthoxazine,
1-ethyl-3,3-dimethyl-spiroindoline naphthoxazine, 1-isopropyl-3,3-dimethyl-spiroindoline naphthoxazine,
1- (2-phenoxyethyl) -3,3-dimethyl-spiroindoline naphthoxazine,
1,3-dimethyl-3-ethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-9'-hydroxy-spiroindoline naphthoxazine,
1,3-dimethyl-3-ethyl-8'-hydroxy-spiroindoline naphthoxazine, 1,3,3,5-tetramethyl-9'-methoxy-spiroindoline naphthoxazine,
1,3,3,5,6-pentamethyl-9'-methoxy-spiroindoline naphthoxazine,
1,3,3-trimethyl-4-trifluoromethyl-5'-methoxy-spiroindoline naphthoxazine,
1,3,3-trimethyl-5'-methoxy-6'-trifluoromethyl-spiroindoline naphthoxazine,
1,3,3-trimethyl-4-trifluoromethyl-9'-methoxy-spiroindoline naphthoxazine,
1,3,5,6-tetramethyl-3-ethyl-spiroindoline naphthoxazine,
1,3,3,5,6-pentamethyl-spiroindoline naphthoxazine,
1-methyl-3,3-diphenyl-spiroindoline naphthoxazine,
1- (4-methoxybenzyl) -3,3-dimethyl-spiroindoline naphthoxazine,
1- (3,5-dimethylbenzyl) -3,3-dimethyl-spiroindoline naphthoxazine,
1- (2-fluorobenzyl) -3,3-dimethyl-spiroindoline naphthoxazine, etc., each indole ring of indolinospironaphthoxazine and benzene ring halogen, methyl, ethyl, methylene, ethylene, hydroxyl group, etc. It can be illustrated.

  Examples of indoline spirophenanthrooxazine compounds include 1,3,3-trimethyl-spiroindoline phenanthrooxazine, 1,3,3-trimethyl-5-chloro-spiroindoline phenanthrooxazine, India Examples of the substituents such as halogen, methyl, ethyl, methylene, ethylene, and hydroxyl groups of the indole ring and the benzene ring of linospirophenanthrooxazine can be given.

  Examples of indolinospiroquinolinoxazine compounds include 1,3,3-trimethyl-spiroindoline quinolinoxazine, indole ring of indolinospiroquinolinoxazine and benzene ring halogen such as methyl, ethyl, methylene, ethylene, hydroxyl group, etc. Each substituent can be illustrated.

Among the photochromic compounds, spiropyran derivatives are shown below, but the present invention is not limited thereto.
1,3,3-trimethylindolinobenzopyrospirane, 1,3,3-trimethylindolino-6'-bromobenzopyrrirospirane, 1,3,3-trimethylindolino-8'-methoxybenzopyrriros Examples include pyran, 1,3,3-trimethylindolino-β-naphthopyrilospirane, 1,3,3-trimethylindolino-6′-nitrobenzopyrospirane and the like.

The weight ratio of the photochromic compound to the styrene oligomer is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 500.
By satisfying the weight ratio, the effect of improving the light resistance is excellent, and the photochromic compound can exhibit a sufficient color density.
The weight ratio of the photochromic compound to the compound having a phenolic hydroxyl group is preferably 0.5: 1 to 10000: 1, and more preferably 0.8: 1 to 100: 1. By satisfying the weight ratio, there is an effect that the light deterioration promotion phenomenon does not appear and the color tone at the time of color development can be arbitrarily changed according to the addition amount of phenol.

（式中、Ｒ_１は炭素数１乃至３０のアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５はそれぞれ炭素数１乃至５のアルキル基を示し、ｎは１以上の整数を示し、Ｒ_６はｎ価の有機残基を示す。） Furthermore, a hindered amine light stabilizer can be added to the photochromic granular material of the present invention to further improve the light resistance.
Although a hindered amine type compound is illustrated below, this invention is not limited to these compounds.
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,
2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl),
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate,
1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4 , 8,10-tetraoxaspiro [5.5] undecane mixed esterified product,
Mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,
1,2,2,6,6-pentamethyl-4-piperidyl-methacrylate,
N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine- 2-yl) -4,7-diazadecane-1,10-diamine,
Examples thereof include N-methyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperezinyl) pyrrolidine-2,5-dione.
As the hindered amine light stabilizer, a compound represented by the following general formula (2) is preferably used.

(In the formula, R ₁ represents an alkyl group having 1 to 30 carbon atoms, R ₂ , R ₃ , R ₄ and R ₅ each represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 or more. , R ₆ represents an n-valent organic residue.)

The photochromic material is encapsulated in a capsule wall film to form a photochromic microcapsule.
The microcapsules satisfy practicality in the range of an average particle size of 0.5 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 30 μm.
When the average particle size of the microcapsules exceeds 100 μm, the dispersion stability and processability are poor when blended into ink, paint or resin.
On the other hand, when the average particle diameter is less than 0.5 μm, it is difficult to exhibit high density color development.
Microencapsulation includes conventionally known isocyanate-based interfacial polymerization methods, in-situ polymerization methods such as melamine-formalin system, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion There are a cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to the application. Further, a secondary resin film may be provided on the surface of the capsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

The photochromic microcapsule is conventionally blended in a vehicle containing a fixing agent selected from general-purpose binder resins, for example, various synthetic resin emulsions, water-soluble or oil-soluble synthetic resins, and other pastes, printing inks, Clayons can be prepared by preparing paints, stamping inks and writing instrument inks or dispersing them in wax.
Using the printing ink, printed matter can be produced by forming a photo-discoloring layer on a support such as paper, synthetic paper, glass, plastic, metal, wood, stone, leather, etc. It is also possible to form a coating by forming a photochromic layer on the surface.
Furthermore, it is possible to produce a sheet, filament, or arbitrarily shaped molded body blended and molded in a thermoplastic resin or a thermosetting resin.
The photochromic microcapsules of the present invention can also exhibit a color change of color (1) ← → color (2) by appropriately adding general dyes and pigments.

Example 1
Preparation of Photochromic Microcapsule 2 parts by weight of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) -spironaphthoxazine was added to low molecular weight polystyrene [manufactured by Sanyo Chemical Industries, Ltd., trade name: HAIMER SB- 75, weight average molecular weight 2000] 50 parts by weight, 4,4 '-(2-methylpropylidene) bisphenol 2 parts by weight, aromatic isocyanate prepolymer 20 parts by weight as a membrane material, ethyl acetate 20 parts by weight After mixing, this was put into 100 parts by weight of a 15% gelatin aqueous solution, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Example 2
Preparation of photochromic microcapsule 4 parts by weight of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) -spironaphthoxazine was added to a styrene-α-methylstyrene copolymer [Rika Hercules Co., Ltd., Product name: Picola stick A75, weight average molecular weight 917] 40 parts by weight, 4,4 '-(2-ethylhexylidene) bisphenol 0.5 parts by weight, aromatic isocyanate prepolymer 20 parts by weight as membrane material, ethyl acetate After mixing in a mixed solution consisting of 20 parts by weight, this was put in 100 parts by weight of a 15% aqueous gelatin solution, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Example 3
Preparation of photochromic microcapsule 4 parts by weight of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) -spironaphthoxazine was added to a styrene-α-methylstyrene copolymer [Rika Hercules Co., Ltd., Product name: Picola stick A75, weight average molecular weight 917] 40 parts by weight, 2,4 '-(2-ethylhexylidene) bisphenol 2 parts, aromatic isocyanate prepolymer 20 parts by weight as membrane material, ethyl acetate 20 parts by weight After mixing in a mixed solution consisting of parts, it was placed in 100 parts by weight of a 15% gelatin aqueous solution, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Example 4
Preparation of photochromic microcapsule 4 parts by weight of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) -spironaphthoxazine was added to a styrene-α-methylstyrene copolymer [Rika Hercules Co., Ltd., Product name: Picola stick A75, weight average molecular weight 917] 40 parts by weight, 4,4 '-(2-ethylhexylidene) bisphenol 5 parts by weight, 20 parts by weight of aromatic isocyanate prepolymer as membrane material, 20 parts by weight of ethyl acetate After mixing in a mixed solution consisting of parts, it was placed in 100 parts by weight of a 15% gelatin aqueous solution, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Example 5
Preparation of photochromic microcapsule 1 part by weight of 1,3,3-trimethyl-6-trifluoromethyl-6 '-(1-piperidinyl) -spiroindoline naphthoxazine was added to a styrene-α-methylstyrene copolymer [Rika Hercules Product name: Picolastic A5, weight average molecular weight 317] 50 parts by weight, 1,4 parts of 4,4 '-(1-phenylethylidene) bisphenol, 20 parts by weight of aromatic isocyanate prepolymer as membrane material, acetic acid After mixing in a mixed solution consisting of 20 parts by weight of ethyl, this was put in 100 parts by weight of a 15% aqueous gelatin solution, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Example 6
Preparation of photochromic microcapsule 2 parts by weight of 1,3,3-trimethyl-6-trifluoromethyl-6 ′-(1-piperidinyl) -spiroindoline naphthoxazine was added to a styrene-α-methylstyrene copolymer [Rika Hercules Manufactured by Co., Ltd., trade name: pico-stick A75, weight average molecular weight 917] 30 parts by weight, 4,4 '-(1-phenylethylidene) bisphenol 0.5 parts by weight, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) Sebacate 8 parts by weight, mixed with a mixed solution consisting of 20 parts by weight of an aromatic isocyanate prepolymer and 20 parts by weight of ethyl acetate as a film material, and then placed in 100 parts by weight of a 15% gelatin aqueous solution The mixture was stirred to form fine droplets and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Comparative Example 1
Preparation of photochromic microcapsule 2 parts by weight of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) -spironaphthoxazine was added to low molecular weight polystyrene [manufactured by Sanyo Chemical Industries, Ltd., trade name: HAIMER SB- 75, weight average molecular weight 2000] 50 parts by weight, mixed with a mixed solution consisting of 20 parts by weight of an aromatic isocyanate prepolymer and 20 parts by weight of ethyl acetate as a film material, and put this in 100 parts by weight of a 15% gelatin aqueous solution. The mixture was stirred to form fine droplets and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Comparative Example 2
Preparation of photochromic microcapsule 4 parts by weight of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) -spironaphthoxazine was added to a styrene-α-methylstyrene copolymer [Rika Hercules Co., Ltd., Product name: Picola stick A75, weight average molecular weight 917] 40 parts by weight, mixed with a mixed solution consisting of 20 parts by weight of an aromatic isocyanate prepolymer and 20 parts by weight of ethyl acetate as a film material, and then mixed with 100% by weight of 15% aqueous gelatin solution The mixture was placed in a part, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Comparative Example 3
Preparation of photochromic microcapsule 1 part by weight of 1,3,3-trimethyl-6-trifluoromethyl-6 '-(1-piperidinyl) -spiroindoline naphthoxazine was added to a styrene-α-methylstyrene copolymer [Rika Hercules Co., Ltd., trade name: pico-stick A5, weight average molecular weight 317] mixed with a mixed solution consisting of 50 parts by weight, 20 parts by weight of an aromatic isocyanate prepolymer and 20 parts by weight of ethyl acetate as a film material. The solution was placed in 100 parts by weight of an aqueous gelatin solution, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Comparative Example 4
Preparation of photochromic microcapsule 2 parts by weight of 1,3,3-trimethyl-6-trifluoromethyl-6 ′-(1-piperidinyl) -spiroindoline naphthoxazine was added to a styrene-α-methylstyrene copolymer [Rika Hercules Product name: Picolastic A75, weight average molecular weight 917] 30 parts by weight, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 8 parts by weight, aromatic isocyanate as membrane material After mixing in a mixed solution consisting of 20 parts by weight of prepolymer and 20 parts by weight of ethyl acetate, this was put into 100 parts by weight of a 15% gelatin aqueous solution, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour. .
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Comparative Example 5
Preparation of photochromic microcapsules 1 part by weight of 1,3,3-trimethyl-6-trifluoromethyl-indolino-6 '-(1-piperidinyl) -spironaphthoxazine was added to 4,4'-(2-ethylhexylidene ) After mixing in a mixed solution consisting of 50 parts by weight of bisphenol, 20 parts by weight of an aromatic isocyanate prepolymer as a film material, and 20 parts by weight of ethyl acetate, this was put into 100 parts by weight of a 15% gelatin aqueous solution so as to form fine droplets. The mixture was stirred and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and then photochromic microcapsules were obtained by a centrifugal separation method.

Preparation of Test Sample 4 parts by weight of the photochromic microcapsules of Examples 1 to 6 and Comparative Examples 1 to 5 are dispersed in 10 parts by weight of an ethylene vinyl acetate copolymer resin emulsion, and the wet film is 90 μm thick on a white synthetic paper with a bar coater. After coating, a test sample was obtained by drying.

Color tone test Each test sample was irradiated with light from a light source (manufactured by Toshiba Lighting & Technology Co., Ltd., bulb-type fluorescent lamp, trade name: Neoball 5 Black Light EFD15BLB) for 1 minute, and then the color tone was confirmed.
Light resistance test Each test sample was irradiated for 1 hour, 2 hours, 3 hours, 4 hours, 5 hours at an illuminance of 140000 lux using a desktop light resistance tester (manufactured by Heraeus, SUNTEST CPS), and then a color difference meter. The brightness value was measured at.

  The following table shows the color tone test and light resistance test results of each test sample.

The symbols related to the evaluation of the light resistance test in the table are as follows.
(Double-circle): The color density of 100 to 80% is hold | maintained compared with the initial stage.
A: The color density of 80 to 60% is maintained compared to the initial value.
(Triangle | delta): 60-40% of color density is hold | maintained compared with the initial stage.
(Triangle | delta): 40-20% of color density is hold | maintained compared with the initial stage.
X: The color density of 20 to 0% is maintained as compared with the initial value.

Example 7
Preparation of photochromic microcapsules 1,3,3-trimethyl-6-trifluoromethyl-indolino-6 '-(1-piperidinyl) -spironaphthoxazine 4 parts by weight, styrene-α-methylstyrene copolymer [Rika Hercules Co., Ltd., trade name: pico-stick A75, weight average molecular weight 917] capsule inclusion in which 10 parts by weight and 0.5 part by weight of 4,4 '-(2-ethylhexylidene) bisphenol are uniformly dissolved Then, the inclusion was covered with an epoxy resin to obtain a photochromic microcapsule.

Preparation of photochromic printed matter A mixture of 1 part by weight of the microcapsules and 20 parts by weight of a 50% acrylic resin toluene solution was coated on white synthetic paper with a wire coater with a wet film thickness of 50 μm and dried to obtain a photochromic printed matter. Obtained.
The printed matter had a reddish purple color when irradiated with ultraviolet rays and became white in the dark.

Comparative Example 6
Preparation of photochromic composition 1,3,3-trimethyl-6-trifluoromethyl-indolino-6 '-(1-piperidinyl) -spironaphthoxazine 4 parts by weight, styrene-α-methylstyrene copolymer [Rika Hercules Co., Ltd., trade name: pico-stick A75, weight average molecular weight 917] 10 parts by weight and 0.5 part by weight of 4,4 '-(2-ethylhexylidene) bisphenol were uniformly dissolved to prepare a photochromic composition. Obtained.

Preparation of photochromic printed matter A mixture of 1 part by weight of the photochromic composition and 20 parts by weight of a 50% acrylic resin toluene solution was coated on white synthetic paper with a wire coater with a wet film thickness of 50 μm and dried to obtain a photochromic printed matter. Got.
The printed matter had a bluish purple color when irradiated with ultraviolet rays and turned white in the dark.

Application example 1
Preparation of Photochromic Liquid Composition 40 parts by weight of the photochromic microcapsules obtained in Example 3 were 58 parts by weight of an ethylene vinyl acetate copolymer resin emulsion, 3 parts by weight of an antifoaming agent, 1 part by weight of a thickener (sodium alginate), A photochromic liquid composition (screen ink) was obtained by uniformly mixing in a vehicle comprising 3 parts by weight of a leveling agent and 1 part by weight of a preservative.

Production of Photochromic Laminate A photochromic laminate (photochromic printed matter) was obtained by forming a photochromic layer of a grape pattern by screen printing on the white synthetic paper (support) using the screen ink.
The printed matter was white before being exposed to sunlight, but when exposed to sunlight, a blue-purple grape pattern appeared. After that, when left for a while, the pattern of the grape disappeared and became the original white color.
This color change could be repeated.

Application example 2
Preparation of photochromic pellets 75 parts by weight of the dried product obtained by dehydrating the photochromic microcapsules obtained in Example 6 and 750 parts by weight of low-pressure polyethylene were mixed, and molded at 160 to 170 ° C. using an extruder. Extruded at a temperature and pelletized with a pelletizer to obtain a pellet.

Production of Photochromic Molded Article Using the pellets, a 1 mm thick photochromic molded article was obtained using an injection molding machine at a set temperature of 160 to 170 ° C.
The molded product was white before being exposed to sunlight, but when it was exposed to sunlight, it turned reddish purple. After that, when it was left indoors for a while, the reddish purple color disappeared and became the original white color.
This color change could be repeated.

Claims (6)

  A photochromic microcapsule in which a photochromic compound selected from a spirooxazine derivative or a spiropyran derivative, a styrene-based oligomer having a weight average molecular weight of 200 to 6000, and a compound having a phenolic hydroxyl group are encapsulated in a capsule wall film.   The photochromic microcapsule according to claim 1, wherein a weight ratio of the photochromic compound to the styrene oligomer is 1: 1 to 1: 10000.   The photochromic microcapsule according to claim 1 or 2, wherein a weight ratio of the photochromic compound to the compound having a phenolic hydroxyl group is 0.5: 1 to 10,000: 1. The photochromic microcapsule according to any one of claims 1 to 3, wherein the compound having a phenolic hydroxyl group is a compound represented by the following general formula (1).

(In the formula, X ₁ , X ₂ and X ₃ each represent a substituent selected from a hydrogen atom, a halogen and an organic residue.)   The photochromic microcapsule according to any one of claims 1 to 4, comprising a hindered amine light stabilizer. The photochromic microcapsule according to claim 5, wherein the hindered amine light stabilizer is a compound represented by the following general formula (2).

(In the formula, R ₁ represents an alkyl group having 1 to 30 carbon atoms, R ₂ , R ₃ , R ₄ and R ₅ each represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 or more. , R ₆ represents an n-valent organic residue.)