CN1223724A - Stabilized matrix for photochromic articles - Google Patents
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- CN1223724A CN1223724A CN 97195955 CN97195955A CN1223724A CN 1223724 A CN1223724 A CN 1223724A CN 97195955 CN97195955 CN 97195955 CN 97195955 A CN97195955 A CN 97195955A CN 1223724 A CN1223724 A CN 1223724A
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Abstract
A stabilizing matrix for photochromic compounds is disclosed in which a functionalized hindered amine light stabilizer capable of reacting with an isocyanate group is linked to the polymer backbone by a covalent bond to form a grafted structure. The resulting matrix is characterized by having a stabilizing effect on the photochromic dye, in particular, spirooxazines. Preferred specific articles of the invention are photochromic organic lenses.
Description
Background of invention
The present invention relates to photochromic article, it is that polymeric matrix by novel stabilization is applied on the transparent ground and forms, and described matrix comprises photochromic dyes and is grafted on being used on the matrix stablizes the reagent of this dyestuff with anti-illumination.
Organic photochromic material is that people are known.They comprise the polymeric matrix that contains photochromic dyes.A shortcoming of these materials of great majority is that its photochromic properties is degenerated too soon, so that they can not make commercial available goods, because the life-span of these goods falls short of.The degeneration of this photochromic properties is because light has caused the fatigue of photochromic dyes.Therefore, need stable organic photochromic material for many years always.
People have proposed several different methods and have made this product.For example, the someone proposes photochromic dyes sneaked into and gives resulting polymers in the polymerisable composition with photochromic properties.The where the shoe pinches of this method is that photochromic dyes is destroyed in polymerization process sometimes.In recent years, people have proposed several new suggestions and have alleviated these problems.The example of these methods has jointly the U.S. Provisional Patent Application that awaits the reply, transfer the possession of jointly number 60/000,829,60/001,677,60/004,492 and 60/011,429.
Disclosed among EP A 0195898 and its equating patent USA 4,720,356 hindered amine has been sneaked in the composition of polymerizable matrix as light stabilizer (this hindered amine as light stabilizer is commonly called HALS).(be obstructed, be meant the meaning of steric hindrance herein.Though) HALS added the anti-fatigue ability that quite can improve photochromic dyes in the composition of polymerizable matrix, still need more durable photochromic material.
Purpose of the present invention satisfies this demand exactly.
The general introduction of invention
In brief, the present invention is based on following thought: hindered amine is combined with the macromolecular compound of polymeric matrix with chemical bond, rather than as above-mentioned patent hindered amine is sneaked in the matrix simply.
The present invention relates to a kind of photochromic article, its feature is to comprise transparent ground, at least scribble the coating that one deck is made by polymeric matrix on this ground, described polymeric matrix comprises photochromic dyes and hindered amine, this hindered amine is a kind of as stablizing described dyestuff to resist the reagent of illumination, and it combines with the macromolecular compound of polymeric matrix with chemical bond.
The present invention is specifically related to a kind of stabilized matrix that is used for photochromic compound, described matrix comprises functionalized hindered amine as light stabilizer, described stabilizing agent can react with isocyanate group (isocyanate group), and be connected on the main polymer chain by covalent bond, form the structure of stable functionalized (being grafting).
According to preferable embodiment, polymeric matrix is a polyurethane.In this embodiment, the present invention relates to photochromic organic material, it comprises plastic bottom material, formed the coating of one deck matrix composition on ground, described composition is the polyurethane formulation (polyurethane formulation) that comprises isocyanates, polyvalent alcohol, hindered amine as light stabilizer and photochromic dyes.
The invention still further relates to a kind of polymerisable coating composition, it can form photochromic stable polyurethane, be used to make photochromic article of the present invention, described composition comprises: at least a polyisocyanates and at least a polyvalent alcohol, will select polyisocyanates-polyvalent alcohol in such a way for use, promptly a kind of in them can provide a functional group than another kind more; Photochromic dyes is preferably Luo oxazine (spiroxazines) class; The light stabilizer of hindered amine type, described amine comprise the reactive functional with the isocyanate group reaction; And optional catalyzer.
The term polyisocyanates should be understood that to represent to contain the compound of two or more isocyanate groups.Similarly, the term polyvalent alcohol should be understood that to represent to contain the compound of two or more hydroxyls, and condition is that used polyisocyanates and polyvalent alcohol comprises at least 5 isocyanate groups and hydroxyl altogether.That is to say that polyisocyanates must contain at least 3 isocyanate groups when polyvalent alcohol is dibasic alcohol, polyvalent alcohol must contain at least three hydroxyls when polyisocyanates is diisocyanate.
Be used for term polyvalent alcohol of the present invention and comprise polythiol.
Be preferably, hindered amine comprises reactive hydroxyl, and polyisocyanates contains 3 isocyanate groups, and polyvalent alcohol is a dibasic alcohol.
Another aspect of the present invention relates to a kind of method of photochromic organic articles produced according to the present invention, following carrying out:
(a) provide transparent plastic bottom material;
(b) on the one side at least of ground, apply the polymerisable composition of one deck polyurethane matrix of the present invention, and
(c) described composition layer polymerization is become photochromic polyurethane coating.
Matrix be preferably comprise polyisocyanates, polyvalent alcohol, hindered amine as light stabilizer (it have an energy and isocyanate reaction form the urethanes official can group), spiral shell oxazine, catalyzer and solvent.
The thickness of coating can be preferably the 10-100 micron in the scope of 5-150 micron.
Detailed description of the invention
Photochromic material needs good anti-photodegradative stability in particular for eye with the photochromic material of occasion (as lens).Therefore, these materials must be in whole serviceable life of lens process antifatigue significantly.Being used for photochromic ophthalmic is spiral shell oxazine (spirooxazines) with the useful photochromic dyes of a class of occasion.As previously mentioned, a where the shoe pinches of preparation photochromic article is that photochromic dyes loses photochromic activity easily in time in polymeric matrix.Some stabilizing agents that are used for this purposes that have been suggested are hindered amine as light stabilizer, i.e. HALS.Concrete for eye with occasion for, need on lens, apply than the photochromic coating that approaches.
Known, for the surface coverage that obtains the good shallow layer ， Luo oxazine of photochromic response must reach about 0.35 milligram/centimetre
2See the application photochromic polymer system (Applied Photochromic Polymer Systems) of C.B.McArdle chief editor's J.C.Crano etc., (Chapman and Hall, NY:1992) the 68th page.Also known, for effectively, obtain near about twice of the required coverage of concentration Wei Luo oxazine of the required HALS of good photochromic response.See Nory Y.C.Chu, the optical material technology VII (Optical Materials Technology for Energy Efficiency and SolarEnergy Conversion VII) that is used for energy efficiency and conversion of solar energy, Spie.Vol.1016 (1988), the 152nd page.As seen, for the coating of minimal thickness, the concentration of good required De Luo oxazine of photochromic response and HALS is unrealisticly high.These high concentrations are impracticable, because Luo oxazine and the HALS solubleness in matrix is lower.In addition, physics and the chemical property at high like this concentration lower substrate can change significantly.
I have found that a class hindered amine as light stabilizer can alleviate the problems referred to above.Concrete is that I have found to be used for the hindered amine as light stabilizer with reactive functionalities of the present invention's practice.The useful especially example of the HALS that these are functionalized is tetramethylpiperidinol (tetramethyl piperidinol is available from ALDRICH), and it contains an OH group, and this group can obtain urethanes official energy with isocyanate reaction.Particularly ,-functionalized the HALS of OH is blended in the polyurethane formulation of the potpourri that comprises polyisocyanates and polyvalent alcohol.Tentatively without being limited by theory, I believe that HALS and isocyanate group react, and am connected to by covalent bond in this process and form Grafting Structure on the main polymer chain.
The gained matrix that contains Grafting Structure is high stability, and HALS and matrix become an integral body.This matrix is stable, because grafting has prevented any gathering or the crystallization of HALS.And the concentration ratio of the HALS of the grafting concentration during with the HALS (as the TINUVIN 770 of CIBA-GEIGY) of conventional free molecule wants high.
Coating formulation composed as follows: (unit is weight %)
30-55% (weight) polyisocyanates, 20-35% (weight) polyvalent alcohol, 2-10% (weight) have reactive stabilizing agent, 0.1-2% (weight) photochromic dyes, 0-2% (weight) catalyzer and 5-30% (weight) solvent that adds functional group.The photochromic dyes of 0.1-1% (weight) ratio is preferably.Solidify back (after being polyreaction), the composition of coating (is unit with weight %) is preferably: 30-60 polyisocyanates, 20-35 polyvalent alcohol, the pure and mild 0.1-1.0 photochromic dyes of 2-10 tetramethyl piperidine.
The example that can be used for polyisocyanates of the present invention has: two isocyanic acid m-xylene esters and two isocyanic acid P-xylene esters, 1, hexamethylene-diisocyanate, isophorone diisocyanate, two isocyanic acids 4,4 ＇-biphenyl ester, two isocyanic acids 4,4 ＇-diphenyl-methane ester (4,4 ＇-diphenylmethane diisocyanate), two isocyanic acids 4,4 ＇-dicyclohexyl methyl hydride ester and trimethyl-1,6-two isocyanate group hexanes, but be not limited to these.
Dibasic alcohol and polyvalent alcohol be for example: ethylene glycol, propylene glycol, 1, the little tiller of 4-is because of glycol (1,4-berbinediol), 1,6-hexanediol, 1,8-ethohexadiol and similar compound, cyclohexanedimethanol, molecular weight are less than 10,000 dibasic alcohol gathers alkoxy ethers (for example polyglycol, polypropylene glycol etc.), polyester binary alcohols (for example polycaprolactone glycol), aromatic diol, PCDL, glycerine, trimethylolpropane, hexanetriol, pentaerythrite, polythiol etc., but is not limited to these.
Spirooxazine all photochromic dyeses all be fit to.Open source literature about this theme is very abundant.For example can referring to, US A 3,562,172,4,634,767,4,637,698,4,720,547,4,756,973,4,785,097,4,792,224,4,816,584,4,831,142,4,909,963,4,931,219,4,936,995,4,986,934,5,114,621,5,139,707,5,233,038,4,215,010,4,342,668,4,699,473,4,851,530,4,913,544,5,171,636,5,180,524,5,166,345 and EP A 0,508,219,0,232,295 and 0,171,909, and books:
Photochromism (Photochromism), G.Brown, Editor, chemical technology (Techniques ofChemistry), Wiley Interscience, volume III (1971), chapter III, 45-294 page or leaf, R.C.Bertelson.
Photochromism-molecule and system (Photochromism-Molecules ﹠amp; Systems), H.DurrH.Bouas-Laurent, Editor, Elsevier (1990), chapter 8: spiro-pyrans (Spiropyrans), 314-455 page or leaf, R.Guglielmetti.
Optional catalyzer comprises all catalyzer that are usually used in the polyurethane formulation.The most normally used is dibutyl tin laurate and stannous octoate.
Following examples are used to illustrate the present invention, but are not limit by it.
Embodiment
1. coating composition (matrix): embodiment 1 expression the present invention, and embodiment 2 and 3 is compositions of usefulness relatively, expression is used the preparation of non-functionalized HALS and without the preparation of stabilizing agent respectively.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| --------------weight (gram)------------ | |||
| Polyisocyanates 1 | ????9.42 | ????9.42 | ????9.42 |
| Polyvalent alcohol 2 | ????5.30 | ????5.30 | ????5.30 |
| Stabilizing agent 3 | ?????-- | ????1.75 | ????-- |
| Reactive stabilizing agent 4 | ????1.15 | ????-- | ????-- |
| Photochromic dyes 5 | ????0.15 | ????0.15 | ????0.15 |
| Catalyzer 6 | ????0.02 | ????0.02 | ????0.02 |
| Solvent 7 | ????4.00 | ????4.00 | ????4.00 |
1CYTHANE 3160 (aliphatic polyisocyanate resin of AMERICAN CYANAMID COMPANY)
2The molecular weight of ALDRICH is 530 polycaprolactone glycol
3TINUVIN 770 DF (HALS) of CIBA-GEIGY
4The tetramethylpiperidinol of ALDRICH
5VARICROL BLUE D (a kind of Luo oxazine photochromic dyes of ENICHEM)
6The dibutyl tin laurate of ALDRICH
7The tetrahydrofuran of ALDRICH
2. each of above-mentioned three kinds of photochromic preparations is applied in by CR39
ROn the planar lens surface that (available from poly-two (allyl carbonates) of a kind of diglycol of PPG Industries) make, the thickness of every kind of coating is 100 microns.Solidified 1 hour at 50 ℃, and solidified again 1 hour in 130 ℃.
After the curing, measure the penetrability of every kind of sample through applying.Three kinds of samples have all shown very high penetrability (＞90%).And every kind of sample all has acceptable optical quality.
3. in following experiment, three kinds of each in the samples of coating are exposed to xenon source (E=150,000, Lx/I=850W/m in about 40 ℃
2) following 240 hours.After 72,120 and 240 hours, measure the penetrability of every kind of sample again.The result is as follows:
| Sample 1 | Sample 2 | Sample 3 | ||||
| --------------------penetrability (%)-------------------------------- | ||||||
| Time (hour) | ????T o | ????T x | ????T o | ????T x | ????T o | ????T x |
| ????0 | ????90 | ????2.5 | ????90 | ????2.5 | ????90 | ????2.5 |
| ????72 | ????90 | ????2.5 | ????90 | ????10 | ????10 | ????-- |
| ????120 | ????90 | ????10 | ????90 | ????30 | ????10 | ????-- |
| ????240 | ????90 | ????50 | ????90 | ????90 | ????10 | ????-- |
T
oThe penetrability % that (promptly is not exposed under the light) under the active state not
T
xPenetrability % under the active state (be exposed to ultraviolet mercury lamp following time obtain maximum blackness required time)
As above shown in the table,, just lost photochromic effect under the light after 72 hours being exposed to the coated sample 3 of preparation (not containing stabilizing agent) of the relatively usefulness of embodiment 3.With the coated sample 2 of preparation (having used TINUVIN 770) of the relatively usefulness of embodiment 2, owing to the crystallization of stabilizing agent shows opacifiation.Through observing, the stabilizing agent of non-grafting (TINUVIN 770) is being exposed to the surface and the crystallization from the teeth outwards of moving to sample under the light after 72 hours.Measure with differential thermal analysis (DTA), the fusing point of crystal is about 85 ℃, and this is the fusing point of stabilizing agent.
More than experiment has shown, use the stabilizing agent of grafting of the present invention (functionalized) to improve to be exposed to the photochromic properties after the light, and can also allow a large amount of stabilizing agents sneak in the matrix and can not produce any tangible adverse effect, because the stabilizing agent of these grafting is nonmigratory to photochromic properties.
Claims (19)
1. photochromic organic material, it comprises plastic bottom material, on described ground, formed the coating composition of polymeric matrix and hindered amine as light stabilizer, described matrix has macromolecular compound and contains photochromic dyes, and described hindered amine as light stabilizer combines with the macromolecular compound of described polymeric matrix with chemical bond.
2. photochromic material as claimed in claim 1, wherein said polymeric matrix comprises polyurethane.
3. photochromic material as claimed in claim 1, wherein said composition also comprises catalyzer and solvent.
4. photochromic material as claimed in claim 1, wherein said photochromic dyes Shi Luo oxazine.
5. photochromic material as claimed in claim 1, the thickness of wherein said coating is in the scope of 5-150 micron.
6. photochromic material as claimed in claim 5, wherein said coating is in the scope of 10-50 micron.
7. photochromic material as claimed in claim 1, wherein said plastic bottom material are the lens that two (allyl carbonates) make that gather by diglycol.
8. polymerisable coating composition, it can form stable photochromic polyurethane, be used to make photochromic article of the present invention, described composition comprises: at least a polyisocyanates, at least a polyvalent alcohol, will select polyisocyanates-polyvalent alcohol by this way for use, promptly a kind of in them can provide a functional group than another kind more; The photochromic dyes of spirooxazine; The light stabilizer of hindered amine type; And optional catalyzer.
9. composition as claimed in claim 8, it is characterized in that described hindered amine as light stabilizer is carried out with a group functionalized, described group can with isocyanate reaction to obtain the functionality of polyurethane.
10. composition as claimed in claim 9 is characterized in that described hindered amine contains a reactive hydroxyl.
11. composition as claimed in claim 10 is characterized in that described hindered amine is a tetramethylpiperidinol.
12. as claim 10 or 11 described compositions, it is characterized in that polyisocyanates contains three isocyanate groups, polyvalent alcohol is a dibasic alcohol.
13., it is characterized in that described composition contains the 30-55% that unit is weight % (weight) polyisocyanates, 20-35% (weight) polyvalent alcohol, 2-10% (weight) reactive stabilizing agent, 0.1-2% (weight) photochromic dyes, 0-2% (weight) catalyzer and 5-30% (weight) solvent that adds functional group arranged as each described composition among the claim 8-11.
14. a method for preparing photochromic article as claimed in claim 2 is characterized in that comprising the steps:
(a) select the ground that makes by transparent polymeric material;
(b) on the one side at least of ground, apply the polymerisable composition of each described polyurethane matrix among one deck such as the claim 6-10, and
(c) described composition layer polymerization is become photochromic polyurethane coating.
15. photochromic organic material, it comprises transparent plastic bottom material, on described ground, formed the coating of the photochromic matrix of one deck, described coating basically by following be that the material of unit is formed with weight %: 30-60 polyisocyanates, 20-35 polyvalent alcohol, the reactive light stabilizer of 2-10 and 0.1-1.0 photochromic dyes.
16. a method for preparing photochromic organic material is characterized in that being undertaken by following steps:
(a) provide plastic bottom material;
(b) polyisocyanates, polyvalent alcohol, hindered amine as light stabilizer, spiral shell oxazine, catalyzer and solvent are formed solution, wherein hindered amine as light stabilizer contain an energy and isocyanate reaction form the urethanes official can group; And
(c) on the one side at least of described ground, apply the coating of the described solution of one deck.
17. method as claimed in claim 16 is characterized in that it also comprises the step of solidifying described ground.
18. method as claimed in claim 16, the thickness that it is characterized in that described coating is in the scope of 10-50 micron.
19. method as claimed in claim 16, wherein said solution are made up of the following material of representing with weight % basically: 30-55 polyisocyanates, 20-35 polyvalent alcohol, 2-10 functionalized or reactive stabilizing agent, 0.1-2.0 photochromic dyes, 0-2 catalyzer and 5-30 solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97195955 CN1223724A (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR96/09236 | 1996-07-23 | ||
| CN 97195955 CN1223724A (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
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| CN1223724A true CN1223724A (en) | 1999-07-21 |
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| CN 97195955 Pending CN1223724A (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104335083A (en) * | 2012-06-26 | 2015-02-04 | 三井化学株式会社 | Polymerizable composition for optical material, optical material and plastic lens obtained from said composition |
| CN106589296A (en) * | 2015-10-16 | 2017-04-26 | 奕益实业有限公司 | Hindered amine system light stabilizer and composite |
| CN106589574A (en) * | 2015-10-16 | 2017-04-26 | 奕益实业有限公司 | Method for preparing composite wood and composite wood |
| CN106832213A (en) * | 2017-02-21 | 2017-06-13 | 东莞市雄林新材料科技股份有限公司 | A kind of Photosensitive TPU film and preparation method thereof |
| CN107207851A (en) * | 2015-03-10 | 2017-09-26 | 株式会社德山 | The manufacture method of photochromic solidfied material |
| CN113788923A (en) * | 2015-08-17 | 2021-12-14 | 光学转变公司 | Curable photochromic compositions |
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- 1997-06-26 CN CN 97195955 patent/CN1223724A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104335083A (en) * | 2012-06-26 | 2015-02-04 | 三井化学株式会社 | Polymerizable composition for optical material, optical material and plastic lens obtained from said composition |
| CN107207851A (en) * | 2015-03-10 | 2017-09-26 | 株式会社德山 | The manufacture method of photochromic solidfied material |
| CN107207851B (en) * | 2015-03-10 | 2020-07-17 | 株式会社德山 | Method for producing photochromic cured product |
| CN113788923A (en) * | 2015-08-17 | 2021-12-14 | 光学转变公司 | Curable photochromic compositions |
| CN113788923B (en) * | 2015-08-17 | 2023-07-28 | 光学转变公司 | Curable photochromic compositions |
| US11795331B2 (en) | 2015-08-17 | 2023-10-24 | Transitions Optical, Inc. | Curable photochromic compositions |
| CN106589296A (en) * | 2015-10-16 | 2017-04-26 | 奕益实业有限公司 | Hindered amine system light stabilizer and composite |
| CN106589574A (en) * | 2015-10-16 | 2017-04-26 | 奕益实业有限公司 | Method for preparing composite wood and composite wood |
| CN106832213A (en) * | 2017-02-21 | 2017-06-13 | 东莞市雄林新材料科技股份有限公司 | A kind of Photosensitive TPU film and preparation method thereof |
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