CN101233196A - Process for producing melanin, melanin produced by the process, functional film containing the melanin, and process for producing the same - Google Patents
Process for producing melanin, melanin produced by the process, functional film containing the melanin, and process for producing the same Download PDFInfo
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Abstract
To provide: a melanin which has the excellent property of dyeing a functional film and is excellent in reproducibility and storage stability; a process for producing the melanin; a functional film which contains the melanin, is reduced in melanin fluctuation, and has the excellent ability to protect the eyes from ultraviolet; and a process for producing the film. The process for melanin production comprises: an oxidation reaction step in which a melanin precursor is continuously oxidized with an oxidizing agent in an aqueous alkali solution while the molar ratio of the melanin precursor to the oxidizing agent is kept constant; and a precipitation step in which the liquid reaction mixture after the oxidation step is acidified to precipitate a melanin. The process for producing the melanin-containing functional film comprises: a step in which a film is treated with an aqueous alkali solution containing at least the melanin; and a step in which the film treated with the aqueous alkali solution is treated with an aqueous solution containing an inorganic salt.
Description
Technical field
The present invention relates to melanochrome and manufacture method thereof, particularly be meant dyeability good and reproducibility and good melanochrome and the manufacture method thereof of storage stability on functional film.In addition; the invention still further relates to and contain melanic functional film and manufacture method thereof, particularly be meant improved that contained melanic change in the functional film, protection eyes avoid the uv damage superior performance contain melanic functional film of the present invention and manufacture method thereof.
Background technology
Our known melanochrome is present in animals and plants circle widely, can prevent eyes and skin oxidation by absorbing ultraviolet ray.Therefore, utilize this melanic character, be expected to develop and protect eyes to avoid melanic functional film of containing of uv damage.
Be to generate melanochrome (following patent documentation 1,2) by melanin precursors such as pyrocatechol are carried out oxidation in the aqueous solution in the past.In addition, the melanochrome of known generation is three-dimensional polymer noncrystal and that nonuniformity is higher, can't specific its structure, and the nonuniformity of this resultant is by the active site quantity decision (following non-patent literature 1) of melanin precursor and reaction intermediate.
Patent documentation 1: the flat 8-500371 communique of special table
Patent documentation 2: special table 2002-533516 communique
Non-patent literature 1:S.Mobelli etc., " the 12nd international pigment cell meeting ", nineteen eighty-three, 66-77 page or leaf.
Summary of the invention
The problem that invention will solve:
But the resultant of the melanochrome that is obtained in the above-mentioned patent documentation for not having reproducibility.Therefore, promptly use its manufacturing to contain melanic functional film and also can't obtain reproducibility, its dyeability is relatively poor.In addition, because melanochrome also takes place to go bad in the preservation process, cause its reproducibility further to reduce.And then use the melanochrome manufacturing to have reproducibility and functional and contain very difficulty of melanic functional film.
Therefore, be manufactured on the good and good homogeneous melanochrome of reproducibility of dyeability on the functional film and become the invention problem.In addition, it is good and contain the problem that melanic functional film also becomes invention to make reproducibility.
The present invention is mirror with above-mentioned; good melanochrome and the manufacture method thereof of dyeability on the functional film will be provided at; particularly, on light polarizing film, also have the good melanochrome of good dyeability and reproducibility and storage stability and manufacture method thereof to what the melanochrome that can protect eyes to avoid uv damage is provided, contains the bitintability pigment as problem by what polyvinyl alcohol resin formed.
In addition; the present invention will contain melanic functional film and manufacture method thereof, particularly be meant with improved contained melanic change in the functional film, protection eyes avoid uv damage superior performance contain melanic functional film and manufacture method thereof as problem.
Solve the method for problem:
Though one of heterogeneous reason of melanochrome is that the nonuniformity of reaction conditions also is a major cause because the active site quantity of melanin precursor and intermediate thereof is too much.Therefore, participate in personnel of the present invention for solving above-mentioned problem, in processes such as the melanic reaction conditions of concentrating on studies, recognize for eliminating the reaction conditions that melanic nonuniformity must obtain homogeneous as much as possible in essence, found in view of the above to obtain the melanic reaction conditions of homogeneous in essence.Particularly, when finding to use oxygenant oxidation melanin precursor under controlled conditions, by keeping the mol ratio of certain melanin precursor and oxygenant, can the melanic change of revisal, finished the present invention finally according to this opinion.
In addition, participate in personnel of the present invention for solving above-mentioned problem, when melanochrome treatment condition of concentrating on studies etc. to film, find by regulation and control melanochrome treatment condition film, and in the later stage that melanochrome is handled the water treatment operation that contains inorganic salt is set, can the melanic change of revisal.
That is, melanic manufacture method of the present invention is as follows:
Make melanic manufacture method under controlled conditions, the oxidizing reaction operation of when being included in certain melanin precursor of maintenance in the alkaline aqueous solution and oxygenant mol ratio at least above-mentioned melanin precursor being carried out oxidation continuously, thus and separate out the melanic operation of separating out by the reaction solution behind this oxidation operation being become acidity.
Above-mentioned melanin precursor is selected a kind of for good in eumelanin precursor, class melanin precursor and different melanin precursor at least, and above-mentioned oxygenant is selected a kind of for good in containing oxygen class, superoxide and peroxy acid, peracid salt at least.
In addition, melanin precursor and oxygenant mol ratio were good between 1: 0.1～1: 10 in the above-mentioned oxidizing reaction, the residual content that above-mentioned oxidizing reaction proceeds to oxygenant by the supply oxidant content below 1% for good.In addition, the pH value of above-mentioned oxidizing reaction is good between 7～13, and the temperature of reaction of above-mentioned oxidizing reaction is good between 10～60 ℃.
And then separate out in the operation above-mentioned, it is good separating out melanochrome in the pH value is 0.5～4 acid-reaction liquid.In addition, separate out after the melanochrome of separating out in the operation separates from reaction solution above-mentioned, being provided with above-mentioned melanochrome is good with the refining step that the neutral aqueous solution that contains inorganic salt cleans; Inorganic salt concentration contained in the above-mentioned neutral aqueous solution is good at 1～20 weight %; When cleaning with above-mentioned neutral aqueous solution, cleaning to the pH value of cleaning rear solution reaches more than the pH5 for good; It is good carrying out the exsiccant operation below 80 ℃ that the melanochrome that will obtain in the above-mentioned operation is set.
Melanochrome among the present invention is the melanochrome of making by above-mentioned melanochrome manufacture method.Melanochrome store method among the present invention is that this melanochrome is preserved under shading and air tight condition.
Promptly, the manufacture method of the functional film among the present invention, it is the manufacture method that contains melanic functional film among the present invention, at least comprise with containing melanic alkaline aqueous solution and handle the operation of film, and with the film after the above-mentioned alkaline aqueous solution processing, the further operation of handling with the aqueous solution that contains inorganic salt.
The melanin concentration of above-mentioned alkaline aqueous solution is good between 0.1～6g/L; The pH value of above-mentioned alkaline aqueous solution is good between 7～10; Above-mentioned alkaline aqueous solution is good with ammonia alkali; In addition, the temperature of above-mentioned alkaline aqueous solution is good between 10～60 ℃.In addition, the concentration of above-mentioned inorganic salt solution is good between 1～20g/L
Above-mentioned inorganic salt are good with an alkali metal salt or alkali earth metal salt.Above-mentioned an alkali metal salt is selected a kind of for good in sodium sulfate, vitriolate of tartar, sodium-chlor, Repone K, SODIUMNITRATE, saltpetre, sodium phosphate and potassiumphosphate at least; Above-mentioned alkali earth metal salt is selected a kind of for good in calcium sulfate, sal epsom, calcium chloride, magnesium chloride, nitrocalcite, magnesium nitrate, calcium phosphate and trimagnesium phosphate at least.
Above-mentioned film is formed good by polyvinyl alcohol resin.
It is good containing the bitintability pigment in the above-mentioned alkaline aqueous solution.In addition, the operation that makes above-mentioned film contain the bitintability pigment can also be set.It is good that the operation that above-mentioned film is further handled with metallic compound and boric acid is set.
Functional film among the present invention is the functional film of making by the manufacture method of above-mentioned functions film, and the optical articles among the present invention contains the above-mentioned functions film.This class optical articles is used to produce polarizer, Polarizer, sun glasses, eye-protection glasses, vehicle glass, window-glass, sun visor etc. for good.
In addition, in a kind of example, the feature of the functional film among the present invention is as follows: be that to contain melanic functional film among the present invention, film thickness be that 10～100 μ m, melanic content are that 0.1～1.5 weight %, UVA shielding rate are, the UVB shielding rate is more than 80% more than 70%.
The above-mentioned functions film has polarity, and above-mentioned UVA shielding rate is more than 80%, the UVB shielding rate is more than 85%, and degree of polarization is more than 90%, the visible light transmitance is for good below 35%.
The effect of invention:
By the present invention, improved melanic nonuniformity, the dyeability on functional film is good, and reproducibility and storage stability are good, and the melanochrome of homogeneous can be provided.In addition, the functional film that the present invention relates to, the optical articles that the barrier propterty that can provide eyes not to be subjected to uv damage is good is provided in its contained melanic change.
Embodiment
Example of the present invention below is described.
The present invention is for being suitable for making the melanic melanochrome manufacture method of homogeneous, make melanochrome under controlled conditions, the oxidizing reaction operation of carrying out oxidation continuously when being included in the mol ratio of keeping certain melanin precursor and oxygenant in the alkaline aqueous solution at least, with above-mentioned melanin precursor, thus and separate out the melanic operation of separating out by the reaction solution behind this oxidation operation being become acidity.The melanochrome that the present invention relates to, by keeping the mol ratio of certain melanin precursor and oxygenant, can eliminate melanic nonuniformity in essence, for functional film, preferably contain the bitintability pigment the light polarizing film that forms by polyvinyl alcohol resin, to have good dyeability and reproducibility and storage stability good.
Here be meant under the said control condition: be creating conditions that the melanochrome among acquisition the present invention is controlled.Specifically comprise melanin precursor and oxygenant mol ratio, pH value, temperature, the reaction times in when reaction, separate out controlled creating conditions such as condition, cleaning condition, drying conditions.
In above-mentioned melanic manufacture method, by keeping the mol ratio of certain melanin precursor and oxygenant, active site to numerous melanin precursors and intermediate thereof reacts with the oxygenant of identical mole number continuously, can obtain the uniformity reaction, thereby eliminate melanic nonuniformity in essence.
Melanin precursor used among the present invention is not particularly limited, can use various melanin precursors, wherein to select 3 kinds of melanochrome groups, promptly select at least a in eumelanin, class melanochrome and the different melanic precursor to be good (publishing) with reference to R.A.Nicolaus, " Melanins ", 1968, Hermann by the R.A.Nicolaus definition.
More specifically enumerate above-mentioned melanin precursor: tyrosine, halfcystine, pyrocatechol, 1,8-dihydroxy naphthalene, Dopamine HCL, DOPA, 5,6-dihydroxy indole, 5,6-dihydroxy indole-2-carboxylic acid, procrypsis dopachrome (leucodopachrome), tryptophane, thrombotonin, suprarenin, norepinephrine, adrenochrome etc.
These precursors can react for good under the state of uniform dissolution according to its characteristic separately.
Oxygenant used among the present invention is not particularly limited, so long as the side reaction outside the non-oxidation reaction and the oxygenant of coordination reaction all can use, to select to contain at least a for good in oxygen class, superoxide and peroxy acid, the peracid salt.More specifically enumerate: air, oxygen, ozone, hydrogen peroxide, sodium peroxide, benzoyl peroxide, peroxyacetic acid, peroxybenzoic acid, Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc.
The present invention requires to guarantee as far as possible equal qualitative response, the major portion melanin precursor of reaction and the mol ratio of oxygenant is kept a certain proportion of while for this reason, and carrying out successive reaction is its feature.Therefore, the present invention when keeping certain above-mentioned mol ratio, continuous oxidation melanin precursor.In view of the above, carry out the oxygenizement of the identical mole number of successive, thereby obtain equal qualitative response at the active site of numerous melanin precursor and intermediate thereof.
The reaction mol ratio of melanin precursor in the successive reaction and oxygenant was good between 1: 0.1～1: 10.From the angle of controls reaction speed was good between 1: 0.5～1: 5, for the uniformity of controlling reaction was good at 1: 0.5～1: 2 then.If the reaction mol ratio less than 1: 0.1 of melanin precursor and oxygenant then reaction slow down, when mol ratio surpasses 1: 10 then from the very difficult control reaction temperature of the angle of reactor cooling ability.
In order under homogeneous control condition, to finish reaction, react always, in the reaction solution that overflows the oxygenant residual volume be lower than supply with oxidant content 1% for good.For this reason, need reaction conditionss such as regulation temperature of reaction, ph value of reaction, residence time.As required, react, the oxygenant residual volume in the end reaction liquid can be reduced to and supply with below 1% of oxidant content by compact cascade type.Control the mol ratio of melanin precursor and oxygenant, control reaction temperature and pH value in reaction finish to keep actual homogeneous reaction conditions until reaction simultaneously in addition.
Be meant the mode that the continuous multistage reacts at this said compact cascade type.For example, at first in first reactive tank, supply with melanin precursor and the oxygenant of having stipulated mol ratio continuously.Because of overflowing, feed to second reactive tank at this reacted resultant of reaction by continuous blow-down.Melanin precursor and oxygenant remaining in second reactive tank further react, because of overflowing by continuous blow-down.If remaining oxygenant is higher than 1% of initial supply oxidant content in the reaction solution that overflows in second reactive tank, then the reaction solution of discharging is proceeded reaction for toward the 3rd reactive tank.After this repeat above-mentioned reaction, in the reaction solution of discharging remaining oxygenant be lower than the initial stage supply with oxygenant 1% till.
The pH value of above-mentioned oxidizing reaction is good between 7～13.Be preferably between 7.5～11.If reaction pH value less than 7, then the melanochrome of Sheng Chenging exists the danger of separating out, thereby destroys the uniformity of reaction.Otherwise,, cause the uniformity of restive reaction if the pH value is higher than 13 then reaction is too fast.The span of control limit of control of pH value is good with ± 0.5.Be preferably ± 0.2.
The temperature of reaction of above-mentioned oxidizing reaction is good with 10～60 ℃, is preferably between 20～40 ℃.If 10 ℃ of temperature of reaction less thaies then speed of response are slowed down,, be difficult to the uniformity of control reaction if surpass 60 ℃ then speed of response is too fast.The temperature span of control limit of control is good with ± 0.5 ℃, is preferably ± 0.2 ℃.
Become acidity by the reaction solution that will finish substantive reaction, can separate out melanochrome.
Separate out in the operation above-mentioned, separating out melanic pH value is good with 0.5～4.Be preferably 1～3.If pH value less than 0.5 then unsafty impurity are separated out and increased, be difficult to determine the material of reactor simultaneously.In addition, if the pH value is higher than 4 then can not separate out melanochrome fully.
Above-mentionedly separate out acid used in the operation and can use various acid, but from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, choose any one kind of them at least to good.
The above-mentioned melanochrome of separating out in the operation of separating out can separate with the reaction solution that contains impurity by for example common separation methods such as filtration under diminished pressure, supercharging filtration, centrifugation.
Isolated melanochrome can clean by the neutral aqueous solution that use contains inorganic salt and makes with extra care.The inorganic salt concentration of the above-mentioned neutral aqueous solution that is used for cleaning is good with 1～20 weight %.Be preferably 3～12 weight %.If the concentration of inorganic salt is lower than 1 weight % then there is dissolved danger in part melanochrome, if the concentration of inorganic salt is higher than 20 weight % then cleaning performance has the tendency that weakens.
The above-mentioned inorganic salt that are used to clean are good with an alkali metal salt and alkaline earth salt.Particularly in the group that sodium sulfate, vitriolate of tartar, sodium-chlor, Repone K, SODIUMNITRATE, saltpetre, sodium phosphate, potassiumphosphate, calcium sulfate, sal epsom, calcium chloride, magnesium chloride, nitrocalcite, magnesium nitrate, calcium phosphate and trimagnesium phosphate constitute, choose any one kind of them at least to good.
Carry out neutral aqueous solution that above-mentioned usefulness contains inorganic salt when cleaning, be higher than 5 for good with the scavenging solution pH value that proceeds to after the cleaning.Preferably proceed to the pH value and be higher than 6.In view of the above, can be with separation such as low-molecular-weight impurities, can make functional film to homogeneous in essence, especially to containing the light polarizing film that forms by polyvinyl alcohol resin of bitintability pigment, have the good melanochrome of good dyeability and reproducibility and storage stability.
Rotten when carrying out drying for the melanochrome that prevents to obtain, can carry out drying below 80 ℃, be good below 70 ℃.In addition, preferably under reduced pressure carry out drying, can reduce and to reduce heat history again time of drying.
Dried melanochrome is preserved with the aqueous solution state that uses condition usually.But when preserving with aqueous solution state, through behind the some months, the viscosity that the aqueous solution can occur rises, separates out the insolubles iso-metamorphism.This may be because the melanic active site in reaction back does not lose activity fully, and lingering section active site still is subjected to molten in the sunlight and the aqueous solution to deposit the influence of oxygen and bacterium etc. and go bad.Therefore, for prolonged preservation melanochrome, under shading and air-tight state, save as good with solid.
Melanochrome among the present invention can be incorporated in the functional film.Here said functional film is meant the film that especially has with the light characteristic correlation function, and it is multiple to list polarized light property, dimming characteristic, shading characteristic etc. as light characteristic.Light polarizing film is exactly a kind of functional film for instance.
The thickness of functional film is not particularly limited, for example 10～100 μ m.
In addition, in the above-mentioned functions film melanin content of the present invention is not particularly limited, for example 0.1～1.5wt%.
And the melanochrome among the present invention can be used for comprising in the optical articles of functional film.Can list polarizer, Polarizer, sun glasses, eye-protection glasses, vehicle glass, window-glass, sun visor etc. as optical articles.
Relate to characteristics of the present invention, as to contain the manufacture method of melanic functional film among the present invention and be meant and comprise at least with containing melanic alkaline aqueous solution and handle the operation of film, and the operation further handled with the aqueous solution that contains inorganic salt of the film after above-mentioned alkaline aqueous solution handled.
By handling with the aqueous solution that contains inorganic salt, relate to functional film of the present invention and improved melanic change, the protection eyes are subjected to the superior performance of uv damage.
In the manufacture method of above-mentioned functions film,, can improve contained melanic change in the functional film by containing the stain of aqueous solution processing to prevent that melanochrome from causing of above-mentioned inorganic salt.Promptly handle the back and handle, can suppress the stain that heterogeneous body melanochrome causes and the generation of the thread color spot that forms by the aqueous solution that contains inorganic salt with melanochrome.
The film that the present invention is used, thickness size no matter, be meant have film, the material of shape such as thin slice and substrate.Above-mentioned film can the various resins of unrestricted use so long as resin transparent and the possess hydrophilic property group.For example can use polyvinyl alcohol resin, cellulosic resin, acrylic resin etc.Wherein, from the dyeability equal angles, it is good selecting polyvinyl alcohol resin for use.
As above-mentioned polyvinyl alcohol resin, can list polyvinyl alcohol, polyvinyl formal, polyvinylacetal, ethylene-vinyl acetate copolymer etc.Wherein, from good dyeability and have the angle of high light characteristic, it is good selecting polyvinyl alcohol for use.
Used film among the present invention also can use films such as untreated polyvinyl alcohol resin, even can use the films such as polyvinyl alcohol resin that contain the bitintability pigment, handle through metallic compound and boric acid.The manufacture method of these films has the example explanation in special public No. 2663440 communique.These are handled and use the aqueous solution, are convenient to carry out the water treatment that inorganic salt were handled and contained to follow-up melanochrome.
Handle in the operation of film at above-mentioned alkaline aqueous solution, from the angle of film degree of polarization and ultraviolet radiation absorption energy, the melanin concentration of melanochrome treatment trough is good with 0.1 to 6g/L.Be preferably 0.5 to 2g/L.If the not enough 0.1g/L of melanin concentration, then its ultraviolet radiation absorption effect is abundant inadequately, if surpass 6g/L, then the degree of polarization of the functional film that is obtained reduces.
In above-mentioned operation with alkaline aqueous solution processing film, the pH value of melanochrome treatment trough is good with 7 to 10.Be preferably 7.5 to 9.If pH value less than 7 then melanochrome may be separated out, if the pH value surpasses 10 then the light polarizing film sclerosis.
In above-mentioned operation with alkaline aqueous solution processing film, from preventing functional film hardened angle, the pH value of controlling the melanochrome tank with ammonium hydroxide is good.
In above-mentioned operation with alkaline aqueous solution processing film, the temperature of melanochrome treatment trough is good at 10 to 60 ℃.Be preferably in 25 to 45 ℃.If 10 ℃ of temperature less thaies then melanic processing speed reduce, reduce if surpass 60 ℃ then polarisation film strength.
Contain in the operation that the aqueous solution of inorganic salt handles in above-mentioned usefulness, the inorganic salt content that melanochrome is handled in the tank of back is good with 1 to 20g/L.Be preferably 3 to 12g/L.If the concentration of above-mentioned inorganic salt surpasses 20g/L, then prevent the remaining thread color spot of effect reduction meeting of stain.If not enough 1g/L, then the ultraviolet radiation absorption that melanochrome had can reduce, and UVA shielding rate and UVB shielding rate reduce.
Inorganic salt concentration increases and decreases to good according to melanic characteristic.Melanic characteristic is according to the transmitance of 280 to 315nm (UVB scope) wavelength of its diluent, and in the transmitance evaluation of 315 to 400nm (UVA scope) wavelength.When the melanochrome characteristic is strong, make the concentration of inorganic salt be lower than standard value, when the melanochrome characteristic was more weak, it was good making the concentration of inorganic salt be higher than standard value.Since melanochrome this can't specific its structure as heterogeneous body, therefore according to the inorganic salt concentration of the corresponding adjusting of the melanic characteristic very difficulty that quantizes.In a small amount of test, confirm in advance and be adjusted into good.
Above-mentioned inorganic salt are good with an alkali metal salt and alkali earth metal salt.Can list sodium sulfate, vitriolate of tartar, sodium-chlor, Repone K, SODIUMNITRATE, saltpetre, sodium phosphate and potassiumphosphate as an alkali metal salt.In addition, alkali earth metal salt can list calcium sulfate, sal epsom, calcium chloride, magnesium chloride, nitrocalcite, magnesium nitrate, calcium phosphate and trimagnesium phosphate etc.
Contain in the operation that the aqueous solution of inorganic salt handles in above-mentioned usefulness, temperature of reaction is good with 10～60 ℃, is preferably between 25～45 ℃.If 10 ℃ of temperature less thaies then handle the speed carry out with the aqueous solution that contains inorganic salt and reduce reduce if surpass 60 ℃ then the intensity of functional film.
From the angle of further raising ultraviolet radiation absorption effect, can contain in the melanic light polarizing film at these as required, add UV light absorber.
Functional film among the present invention is the functional film made from the manufacture method of above-mentioned functional film, and the optical articles among the present invention contains the above-mentioned functions film.This class optical articles is used for producing polarizer, Polarizer, sun glasses, eye-protection glasses, vehicle glass, window-glass, sun visor etc. for good.
In addition, functional film among the present invention is for containing the melanic functional film of the present invention, and its feature is as follows: the thickness of film is that 10～100 μ m, melanic containing ratio are that the shielding rate of 0.1～1.5 weight %, UVA is, the shielding rate of UVB is more than 80% more than 70%.
The shielding rate that the above-mentioned functions film has polarity, an above-mentioned UVA is more than 80%, the shielding rate of UVB is more than 85%, and then degree of polarization is more than 90%, the visible light transmitance is that characteristic below 35% is good.
Functional film according to the manufacture method of functional film of the present invention is made has above characteristic, has improved contained melanic change, can be used to produce the good optical articles of defencive function that eyes exempt from uv damage.
Exemplifying embodiment
Below describe the present invention in detail by exemplifying embodiment and comparative example, but the present invention is not subjected to any restriction of following exemplifying embodiment.
Evaluation method below is described.
(A) outward appearance: by the visual observations evaluation.
(B) transmitance: measure with spectrophotometer V-550 (Japanese beam split Co., Ltd. system).
(C) degree of polarization (P:%) calculates according to following formula.
[several 1]
In above-mentioned formula, parallel transmitance (H
0) be meant the transmitance after the parallel polaroids stack of two extinction axles, orthogonal transmitance (H
90) be meant the transmitance after the polaroid stack of two extinction axle orthogonals.
＜embodiment 1 〉
In 1 liter of reactor of band stirrer and spillway, supply with the pyrocatechol of 200g/L and the Sodium Persulfate of 500g/L with the speed of 2.7mL/min respectively.With the sodium hydroxide of 100g/L with the pH value be adjusted to 9.5 ± 0.2, temperature of reaction is controlled at 35 ℃ ± 0.1 ℃.The reaction solution that will overflow with hydrochloric acid transfers to pH1.The melanochrome that filtration is separated out uses the aqueous solution of the contains sodium sulfate of 50g/L to clean, and the pH value after cleaning reaches till 6.Melanochrome after the cleaning under 70 ℃ environment dry 1 day.In the pH value being adjusted to 8.3 the aqueous solution with ammoniacal liquor, the melanochrome that dissolving is obtained, making its concentration is 1.2g/L.Light polarizing film is tensioned state is immersed in this melanochrome aqueous solution that is adjusted to 30 ℃ 3 minutes.Keep tensioned state taking-up light polarizing film and carry out drying.
Above-mentioned light polarizing film is to make according to the method for No. 2663440 record of special permission.Particularly be with polyvinyl alcohol (KURARAY Co., Ltd. system, name of product: KURARAY vinylon #750) soak 3 minutes 35 ℃ contain in the metabisulfite solution that chrysophenine (C.I.24895) that the chlorantine fast red that concentration is 0.25g/L (C.I.28160), concentration are 0.18g/L, the luxuriant and rich with fragrance Nile blue 4GL (C.I.34200) of salad that concentration is 1.0g/L and concentration is 10g/L after, in solution, stretched 4 times.The film that will dye subsequently is immersed in 35 ℃ contain in the boric acid solution that nickel acetate that concentration is 2.5g/L and concentration is 6.6g/L and soaked 3 minutes.The tensioned state that keeps this film carries out 3 minutes heat treated at 70 ℃ and makes light polarizing film after at room temperature dry 3 minutes.But do not carry out being used for this experiment with the lamination of polycarbonate.
The light polarizing film outward appearance that obtains is good, degree of polarization is 96.3%, the transmitance of visible light scope, UVA scope and the UVB scope of monolithic is respectively 20.3%, 9.7% and 7.4%.
＜embodiment 2 and 3 〉
Under the condition identical with exemplifying embodiment 1,2 secondary one-tenth melanochrome involved in the present invention has been made light polarizing film (embodiment 2 and 3) with this melanochrome.List table 1 in previous result, its reproducibility is good.
[table 1]
Table 1
| Embodiment | Outward appearance | Degree of polarization (%) | Visible light scope (%) | UVA(％) | UVB(％) |
| 1 | Well | 96.3 | 20.3 | 9.7 | 7.4 |
| 2 | Well | 96.0 | 20.6 | 9.4 | 7.3 |
| 2 | Well | 96.1 | 20.4 | 9.5 | 7.3 |
＜embodiment 4 〉
In the reaction of embodiment 1, except being that the pyrocatechol of 200g/L changes into the Dopamine HCL that concentration is 1 39g/L (4-(2-aminoethyl)-pyrocatechol) with concentration, carry out same reaction with exemplifying embodiment 1, carry out the light polarizing film identical with the melanochrome that obtains and handle with exemplifying embodiment 1.
＜embodiment 5 〉
In the reaction of embodiment 1, except being that the pyrocatechol of 200g/L changes the DOPA that concentration is 179g/L into (3-(3 with concentration, the 4-dihydroxybiphenyl)-the a-L-Ala) outside, carry out same reaction with exemplifying embodiment 1, carry out the light polarizing film identical with the melanochrome that obtains and handle with exemplifying embodiment 1.
[table 2]
Table 2
| Embodiment | Outward appearance | Degree of polarization (%) | Visible light scope (%) | UVA(％) | UVB(％) |
| Embodiment 4 | Well | 95.8 | 21.2 | 10.1 | 7.6 |
| Embodiment 5 | Well | 95.7 | 21.4 | 9.9 | 7.6 |
＜comparative example 1 〉
In the reactor of the 1L that is with stirrer, supplying with concentration is the 500ml pyrocatechol of 200g/L.The sodium hydroxide that with concentration is 100g/L is adjusted to the pH value after 10.0, and supplying with concentration with the speed of 2.7mL/min is the Sodium Persulfate 500ml of 500g/L.The pH value of supplying with afterreaction liquid is 4, has separated out melanochrome.Obtain the melanochrome of black after filtration and the drying.Handle with the light polarizing film that the melanochrome that obtains carries out similarly to Example 1.When the light polarizing film that obtains is carried out visual inspection, find some thread color spots.
Degree of polarization is 94.1%, the transmitance of visible light scope, UVA scope and UVB scope during monolithic is respectively 23.5%, 8.7% and 6.8%.
＜comparative example 2 and 3 〉
Under the condition identical, generate the related melanochrome of this comparative example, and made light polarizing film (comparative example 2 and 3) for 2 times with this melanochrome with comparative example 1.List table 3 in previous result, fail to obtain reproducibility.
[table 3]
Table 3
| Comparative example | Outward appearance | Degree of polarization (%) | Visible light scope (%) | UVA (％) | UVB (％) |
| 1 | Some thread color spots | 94.1 | 23.5 | 8.7 | 6.8 |
| 2 | Thread color spot | 92.8 | 28.7 | 6.7 | 6.1 |
| 3 | Some thread color spots | 93.0 | 27.5 | 8.0 | 6.5 |
＜comparative example 4 〉
In the reaction of comparative example 1, except being that the 500ml pyrocatechol of 200g/L changes into the 500ml Dopamine HCL that concentration is 139g/L (4-(2-aminoethyl)-pyrocatechol) with concentration, carry out same reaction with comparative example 1, carry out the light polarizing film identical with the melanochrome that obtains and handle with exemplifying embodiment 1.
＜comparative example 5 〉
In the reaction of comparative example 1, except being that to change concentration into be that (3-(3 for the 500ml DOPA of 179g/L for the 500ml pyrocatechol of 200g/L with concentration, the 4-dihydroxybiphenyl)-the a-L-Ala) outside, carry out same reaction with comparative example 1, carry out the light polarizing film identical with the melanochrome that obtains and handle with exemplifying embodiment 1.
[table 4]
Table 4
| Comparative example | Outward appearance | Degree of polarization (%) | Visible light scope (%) | UVA (％) | UVB (％) |
| Comparative example 4 | Some thread color spots | 93.7 | 24.5 | 8.7 | 6.7 |
| Comparative example 5 | Thread color spot | 91.8 | 31.3 | 6.7 | 6.0 |
＜embodiment 6 and 7 〉
The melanochrome that will obtain according to the method for embodiment 1 behind 70 ℃ of following drying under reduced pressure, shading and airtight preservation.With the melanochrome of preserving after 3 months and 6 months, be that 1.2g/L, pH value are to dissolve in 8.3 the aqueous solution in the concentration of allocating respectively with ammoniacal liquor.The melanochrome solution appearance that obtains does not have difference, carries out the light polarizing film processing identical with embodiment 1 with these two kinds of solution, and its result is indifference also.
[table 5]
Table 5
| Embodiment | Outward appearance | Degree of polarization (%) | Visible light scope (%) | UVA (％) | UVB (％) |
| 6 (after 3 months) | Well | 96.1 | 20.5 | 9.5 | 7.3 |
| 7 (after 6 months) | Well | 96.2 | 20.4 | 9.6 | 7.3 |
＜comparative example 6 and 7 〉
After the melanochrome drying that will obtain, be that 1.2g/L, pH value are to dissolve in 8.3 the aqueous solution in concentration with ammoniacal liquor allotment according to the method for comparative example 1.The melanochrome aqueous solution that obtains was preserved respectively 3 months and 6 months.The aqueous solution (solution-air) the interface discovery black of preserving after 3 months is separated out, and the solution container inwall of preserving after 6 months is found a large amount of black precipitates.Carry out the light polarizing film identical with embodiment 1 with these two kinds of solution and handle, the result is as follows.
[table 6]
Table 6
| Comparative example | Outward appearance | Degree of polarization (%) | Visible light scope (%) | UVA (％) | UVB (％) |
| 6 (after 3 months) | Thread color spot | 92.3 | 30.5 | 7.0 | 6.2 |
| 7 (after 6 months) | Tangible thread color spot | 89.6 | 32.8 | 6.0 | 5.5 |
＜embodiment 8 〉
With the melanochrome aqueous solution of the same allotment of exemplifying embodiment 1 in, the light polarizing film of tensioned state was soaked 3 minutes in 30 ℃ solution.Take out light polarizing film under tensioned state, continuing then in concentration is to soak 3 minutes in the metabisulfite solution of 8g/L.Keep tensioned state taking-up light polarizing film and carry out drying.
Above-mentioned light polarizing film is the light polarizing film of making down with embodiment 1 the same terms.
The functional film outward appearance involved in the present invention that obtains is good, and degree of polarization is 97.3%, and the transmitance in visible light scope, UVA scope and UVB scope during monolithic is respectively 19.4%, 10.3% and 8.0%.
＜embodiment 9 and 10 〉
Under the condition identical with embodiment 8, the functional film (embodiment 9 and 10) that 2 secondary one-tenth are involved in the present invention.List table 7 in previous result, all obtain good reproducibility.
[table 7]
Table 7
| Embodiment | Outward appearance | Degree of polarization (%) | Visible light scope (%) | UVA(％) | UVB(％) |
| 8 | Well | 97.3 | 19.4 | 10.3 | 8.0 |
| 9 | Well | 97.3 | 19.3 | 10.2 | 8.0 |
| 10 | Well | 97.1 | 19.7 | 10.0 | 7.8 |
＜comparative example 8 〉
According to United States Patent (USP) the 4th, 698, the embodiment 3 in No. 374 communiques reacts for raw material substitution DOPA with pyrocatechol.Is that 1.2g/L, pH value are to dissolve in 8.3 the aqueous solution with the enriched material of the plain aqueous solution of water-soluble black that obtains in the concentration with the ammoniacal liquor allotment.Light polarizing film is tightened the back soaked 3 minutes in being adjusted to this melanochrome solution of 30 ℃.Keep tensioned state taking-up light polarizing film and carry out drying.When the light polarizing film that obtains is carried out visual inspection, find some thread color spots.Its degree of polarization is 94.2%, and the transmitance in visible light scope, UVA scope and UVB scope during monolithic is respectively 23.1%, 8.8% and 7.0%.
＜comparative example 9 and 10 〉
Under the condition identical, regenerate 2 light polarizing film (comparative example 9 and 10) with comparative example 8.List table 8 in previous result, fail to obtain reproducibility.
[table 8]
Table 8
| Comparative example | Outward appearance | Degree of polarization (%) | Visible light scope (%) | UVA (％) | UVB (％) |
| 8 | Some thread color spots | 94.2 | 23.1 | 8.8 | 7.0 |
| 9 | Thread color spot | 92.8 | 27.3 | 8.0 | 6.4 |
| 10 | Well | 95.1 | 21.5 | 9.5 | 7.5 |
Industrial utilizability
As mentioned above, melanin involved in the present invention has improved melanic anisotropism, and its repeatability and storage stability are good, can provide dyeability good melanin for functional film. In addition, functional film involved in the present invention, its contained melanic mobility is improved, and is particularly suited for producing the optical articles that the protection eyes exempt from the function admirable of uv damage.
Claims (47)
1. melanic manufacture method, make melanic manufacture method under controlled conditions, the oxidizing reaction operation of when being included in the mol ratio of certain melanin precursor of maintenance in the alkaline aqueous solution and oxygenant at least above-mentioned melanin precursor being carried out oxidation continuously, and separate out the melanic operation of separating out by the reaction solution after this oxidizing reaction operation is become acidity.
2. melanic manufacture method according to claim 1 is characterized in that: above-mentioned melanin precursor is selected a kind of in eumelanin precursor, class melanin precursor and the different melanin precursor at least.
3. melanic manufacture method according to claim 1 and 2 is characterized in that: above-mentioned oxygenant selects to contain a kind of in oxygen class, superoxide and peroxy acid, the peracid salt at least.
4. melanic manufacture method according to claim 1 and 2 is characterized in that: the mol ratio of melanin precursor and oxygenant is 1: 0.1～1: 10 in the above-mentioned oxidizing reaction.
5. melanic manufacture method according to claim 1 and 2 is characterized in that: the residual content that above-mentioned oxidizing reaction proceeds to above-mentioned oxygenant by below 1% of supply oxidant content.
6. melanic manufacture method according to claim 1 and 2 is characterized in that: the pH value of above-mentioned oxidizing reaction is 7～13.
7. melanic manufacture method according to claim 1 and 2 is characterized in that: the temperature of reaction of above-mentioned oxidizing reaction is 10～60 ℃.
8. melanic manufacture method according to claim 1 and 2 is characterized in that: above-mentioned separating out in the operation, and in being 0.5～4 acid-reaction liquid, the pH value separates out melanochrome.
9. melanic manufacture method according to claim 1 and 2 is characterized in that: above-mentioned separating out after the melanochrome of separating out in the operation separates from reaction solution also comprises the refining step that above-mentioned melanochrome is cleaned with the neutral aqueous solution that contains inorganic salt.
10. melanic manufacture method according to claim 9 is characterized in that: contained inorganic salt concentration is 1～20 weight % in the above-mentioned neutral aqueous solution.
11. melanic manufacture method according to claim 9 is characterized in that: in the above-mentioned refining step, when cleaning, proceed to the pH value of cleaning rear solution and reach more than 5 with above-mentioned neutral aqueous solution.
12. melanic manufacture method according to claim 9 is characterized in that: also comprise the melanochrome that above-mentioned refining step is obtained, at the drying process that carries out below 80 ℃.
13. a melanochrome is characterized in that: according to the melanochrome of the described melanic manufacture method manufacturing of arbitrary claim in the claim 1 to 12.
14. a melanic store method is characterized in that: to melanochrome according to the described melanic manufacture method manufacturing of arbitrary claim in the claim 1 to 12, shading and airtight preservation.
15. a functional film is characterized in that: contain the described melanochrome of claim 13.
16. functional film according to claim 15 is characterized in that: film thickness is 10～100 μ m, and melanic content described in this film is 0.1～1.5 weight %.
17. an optical articles is characterized in that containing the described functional film of claim 15.
18. optical articles according to claim 17 belongs to one of polarizer, Polarizer, sun glasses, eye-protection glasses, vehicle glass, window-glass, sun visor formation group.
19. the manufacture method of a functional film, the oxidizing reaction operation of when comprising the mol ratio of keeping certain melanin precursor and oxygenant in the alkaline aqueous solution under controlled conditions at least above-mentioned melanin precursor being carried out oxidation continuously, and the reaction solution after this oxidizing reaction operation become acidity and separate out melanic separate out the melanochrome manufacture method of operation and make contain melanic functional film manufacture method;
It is characterized in that: comprise at least and contain the operation that above-mentioned melanic alkaline aqueous solution is handled film, and the operation handled with the aqueous solution that contains inorganic salt of the film after above-mentioned alkaline aqueous solution handled.
20. the manufacture method of functional film according to claim 19 is characterized in that: above-mentioned melanin precursor is selected a kind of in eumelanin precursor, class melanin precursor and the different melanin precursor at least.
21. the manufacture method according to claim 19 or 20 described functional films is characterized in that: above-mentioned oxygenant selects to contain a kind of in oxygen class, superoxide and peroxy acid, the peracid salt at least.
22. the manufacture method according to claim 19 or 20 described functional films is characterized in that: the mol ratio of melanin precursor and oxygenant is 1: 0.1～1: 10 in the above-mentioned oxidizing reaction.
23. the manufacture method according to claim 19 or 20 described functional films is characterized in that: the residual content that above-mentioned oxidizing reaction proceeds to above-mentioned oxygenant by below 1% of supply oxidant content.
24. the manufacture method according to claim 19 or 20 described functional films is characterized in that: the pH value of above-mentioned oxidizing reaction is 7～13.
25. the manufacture method according to claim 19 or 20 described functional films is characterized in that: the temperature of reaction of above-mentioned oxidizing reaction is 10～60 ℃.
26. the manufacture method according to claim 19 or 20 described functional films is characterized in that: above-mentioned separating out in the operation, in being 0.5～4 acid-reaction liquid, the pH value separates out melanochrome.
27. manufacture method according to claim 19 or 20 described functional films, it is characterized in that: comprise above-mentioned separating out after the melanochrome of separating out in the operation separates from reaction solution, the refining step that above-mentioned melanochrome is cleaned with the neutral aqueous solution that contains inorganic salt.
28. the manufacture method of functional film according to claim 27 is characterized in that: contained inorganic salt concentration is 1～20 weight % in the above-mentioned neutral aqueous solution.
29. the manufacture method of functional film according to claim 27 is characterized in that: in the above-mentioned refining step, clean with above-mentioned neutral aqueous solution, cleaning to the pH value of cleaning rear solution reaches more than 5.
30. the manufacture method of functional film according to claim 27 is characterized in that: also comprise the melanochrome that above-mentioned refining step is obtained, carrying out the exsiccant operation below 80 ℃.
31. the manufacture method of functional film according to claim 19 is characterized in that: the melanin concentration of above-mentioned alkaline aqueous solution is 0.1～6g/L.
32. the manufacture method according to claim 19 or 31 described functional films is characterized in that: the pH value of above-mentioned alkaline aqueous solution is 7～10.
33. the manufacture method according to claim 19 or 31 described functional films is characterized in that: above-mentioned alkaline aqueous solution is an ammonia alkali.
34. the manufacture method according to claim 19 or 31 described functional films is characterized in that: the temperature of above-mentioned alkaline aqueous solution is 10～60 ℃.
35. the manufacture method of functional film according to claim 19 is characterized in that: the concentration of above-mentioned inorganic salt in the aqueous solution is 1～20g/L.
36. the manufacture method according to claim 19 or 35 described functional films is characterized in that: above-mentioned inorganic salt are an alkali metal salt or alkali earth metal salt.
37. the manufacture method of functional film according to claim 36 is characterized in that: above-mentioned an alkali metal salt is selected a kind of in sodium sulfate, vitriolate of tartar, sodium-chlor, Repone K, SODIUMNITRATE, saltpetre, sodium phosphate and potassiumphosphate at least.
38. the manufacture method of functional film according to claim 36 is characterized in that: above-mentioned alkali earth metal salt is selected a kind of in calcium sulfate, sal epsom, calcium chloride, magnesium chloride, nitrocalcite, magnesium nitrate, calcium phosphate and trimagnesium phosphate at least.
39. the manufacture method according to claim 19 or 31 described functional films is characterized in that: above-mentioned film is formed by polyvinyl alcohol resin.
40. the manufacture method according to claim 19 or 31 described functional films is characterized in that: also contain the bitintability pigment in the above-mentioned alkaline aqueous solution.
41. the manufacture method according to claim 19 or 31 described functional films is characterized in that: also comprise the operation that makes above-mentioned film contain the bitintability pigment.
42. the manufacture method according to claim 19 or 31 described functional films is characterized in that: comprise the operation that above-mentioned film is handled with metallic compound and boric acid.
43. a functional film is according to the manufacture method manufacturing of claim 19 or 31 described functional films.
44. an optical articles contains the described functional film of claim 43.
45. according to the described optical articles of claim 44, belong to by polarizer, Polarizer, sun glasses, eye-protection glasses, vehicle glass, window-glass, sun visor constitute group one of.
46. functional film, when comprising the mol ratio of keeping melanin precursor certain in the alkaline aqueous solution and oxygenant under controlled conditions at least above-mentioned melanin precursor is carried out continuously the oxidizing reaction operation of oxidation, and the reaction solution after this oxidizing reaction operation become acidity and separate out the melanic functional film that contains that the melanic melanochrome manufacture method of separating out operation makes; It is characterized in that: film thickness is that above-mentioned melanic amount is that 0.1～1.5 weight %, UVA shielding rate are, the UVB shielding rate is more than 80% more than 70% in 10～100 μ m, this film.
47. according to the described functional film of claim 46, it is characterized in that: the above-mentioned functions film has polarity, above-mentioned UVA shielding rate is more than 80%, the UVB shielding rate is more than 85%, and degree of polarization is more than 90%, the visible light transmitance is below 35%.
Applications Claiming Priority (5)
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| JP207002/2005 | 2005-07-15 | ||
| JP2005207002A JP5403568B2 (en) | 2005-07-15 | 2005-07-15 | Method for producing melanin and melanin produced by the method |
| JP207001/2005 | 2005-07-15 | ||
| JP2005207001A JP4664139B2 (en) | 2005-07-15 | 2005-07-15 | Functional film containing melanin and method for producing the same |
| PCT/JP2006/314077 WO2007010861A1 (en) | 2005-07-15 | 2006-07-14 | Process for producing melanin, melanin produced by the process, functional film containing the melanin, and process for producing the same |
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| CN101233196B CN101233196B (en) | 2012-04-11 |
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| CN102604293A (en) * | 2012-02-27 | 2012-07-25 | 江南大学 | Thermoplastically processable polyvinyl alcohol composite and preparation method thereof |
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| JP5403568B2 (en) * | 2005-07-15 | 2014-01-29 | Ｍｇｃフィルシート株式会社 | Method for producing melanin and melanin produced by the method |
| WO2013154139A1 (en) * | 2012-04-13 | 2013-10-17 | 日本化薬株式会社 | Polarizing element, and polarizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| IT1255146B (en) * | 1992-05-08 | 1995-10-20 | Intercast Europ | SYNTHETIC PURIFIED MELANIN PARTICULARLY FOR OPTICAL DEVICES LOW DIFFUSION |
| JPH11291617A (en) * | 1998-04-09 | 1999-10-26 | Seiko Epson Corp | Recording medium |
| US6103777A (en) * | 1998-12-18 | 2000-08-15 | Bayer Corporation | Thermoplastic composition suitable for optical applications having low haze values |
| JP4698421B2 (en) * | 2003-10-22 | 2011-06-08 | 大塚化学株式会社 | Process for producing 2,3,6,7,10,11-hexahydroxytriphenylene |
| JP5403568B2 (en) * | 2005-07-15 | 2014-01-29 | Ｍｇｃフィルシート株式会社 | Method for producing melanin and melanin produced by the method |
-
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| CN104017202B (en) * | 2009-10-23 | 2016-09-28 | 首尔大学校产学协力团 | Melanin granule of nano-scale and preparation method thereof |
| CN102666671A (en) * | 2009-10-23 | 2012-09-12 | 首尔大学校产学协力团 | Nano-sized melanin particles and method of producing same |
| CN102666671B (en) * | 2009-10-23 | 2014-06-11 | 首尔大学校产学协力团 | Nano-sized melanin particles and method of producing same |
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| JP2007025234A (en) | 2007-02-01 |
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