CN1354188A - Production method of photochromic resin lens and its lens - Google Patents

Abstract

The method of making photochromic resin lens is characterized by that the dried anhydrous allochromatic powder material is mixed into the unconverted liquid monomer resin, fully stirred uniformly; and the initiating agent is added, and fully stirred and mixed; then the obtianed liuqid mixture is poured into lens mould and formed so as to obtain the invented product.

Description

The manufacture method of photochromic resin lens and eyeglass thereof

This invention relates to the production of the resin lens of variable color.

Glasses are at the initial stage of development, and the specific refractory power of the glass of its use is 1.5230, for example: gram department, Ke Sai, UV sheet etc.Along with the continuous development of opticglass, the making that the material of high refractive index is applied to glasses also morely comes up to alleviate its weight, and resembling the multiple ultra-thin eyeglass that occurs in recent years is exactly the strong evidence of this application.Many new requirements are arranged in the use of glasses, such as, in order to adapt to eyes are felt comfortably cool in order to avoid the stimulation of high light.The photochromic glass that develops over nearly 40 years is exactly the new product that occurs in order to solve this contradiction, the principle of photochromic glass is that the silver salt and the copper peroxide of adding haloid element on the basis of silicate glass is Red copper oxide, after glass smelting is finished, exist a boron-rich phase in the glass, silicate glass with boron-rich phase is after suitable heat-treated, just formed the crystallite of silver halide in glass, boron-rich phase provides the nest that exists for this crystallite.This glass after heat treatment is under action of ultraviolet ray, positive ion and the haloid element negative ion that generates silver takes place to decompose in silver halide, silver ions obtains an electronics from Red copper oxide become simple substance silver, just occur light is risen the metallic silver particles of shielding effect like this in the glass, hindered passing through of light.Though this phenomenon occurs on the atomic level of structure,, from macroscopic view and on the whole, the glass of monoblock is blackening equably all.This ultraviolet ray is the excitation energy of silver halide, and when ultraviolet ray did not exist, the state when glass can reset into exposure not naturally promptly returned to colourless state.So this variation is repeatedly electrodeless, can exist forever.From microcosmic, this variation is separated attitude (its size occurs on the atomic level) in spatial distribution, still, and they same every also still relatively uniformly.Because glass structure is long-range orderly, the unordered pattern of short range, if the spatial distribution of this silver halide function F (x, y z) represents, that petty independent variable(s) X, Y, Z almost changes with arithmetic series, and the order of magnitude of its variation is on atomic level, so generally speaking the distribution of variable color particle is uniform, being small at interval, also is discontinuous really.Therefore say that this variation is incomplete, even that is to say above-mentioned variation has taken place, still have the phenomenon of light leak yet, only this light leakage phenomena is not discovered by human eye.Because the space between the simple substance silver is far smaller than people's the visual discrimination limit, so just on the whole, all variable colors of the glass of monoblock.

Here we must say a servant resolving limit problem.People's the explanation limit is that minimum explanation angle is 1 minute normally, is approximately 0.05 millimeter.The size of silver ions is the explanation ultimate that is far smaller than the people, and therefore, human eye is the existence that can't aware it.Also there is a visual problem in the people but simultaneously.So-called vision is the stimulation that light is given human eye, and it is two different notions with minimum explanation angle, and it is irrelevant with the size of the object that is observed, and is only relevant with the intensity of light stimulus.

In addition, glasses can be regulated the luminous energy except people require it, wish that also weight progressively alleviates, and particularly to the wearer of high myopia, this requirement are seemed particularly urgent, and simultaneously, unorganic glass is a kind of hard brittle material, and are broken easily.So, resin lens has appearred recently decades in succession, and its great advantage is exactly in light weight, difficult broken.Make it in traditional eyewear market, occupy a tiny space just because of these characteristics.But it also has and occurs surface scratch easily and make surface quality can not get guaranteeing, work-ing life is short.

Resin lens has been arranged, and people just wish that it also can produce variable color naturally.In order to realize the resin lens variable color, this has many people to do a large amount of research and test in this respect in decades.But make till the present, do not find yet can variable color the organic synthesis material, so a lot of people with the starting point be placed on inorganic photo chromic glass and organic resin in conjunction with on adopt and address this problem.Present solution is broadly divided into following four classes:

One, photo chromic glass and resin are done film forming layer or the single or multiple lift of rete is glued on the synthetic glass matrix, also have and separate gummed, that is: the single face contact contacts two kinds of situations with multiaspect.

Two, the powder of inorganic photo chromic glass directly is pressed into forms photochromic layer in the resinous substrates.

Three, with the surface formation surface discolouration layer of inorganic photo chromic glass spraying plating to organic resin.

Four, inorganic variable color powder is participated in the resin lens matrix to realize whole variable color.

The obvious problem of first three methods is a lot.At first, inorganic variable color powder is easy to destroy color changing structure with contacting of air, just makes it lose the ability that obtains and discharge electronics as the oxidized variation of Red copper oxide, and this just makes variable color and restores and can't carry out the variable color end of life.Because the coefficient of expansion of variation of temperature photochromic layer and organic resin is incomplete same, causes photochromic layer and matrix resin layer to come off easily.In addition, the effect of damp atmosphere also can impel the termination of variable color and coming off of interlayer.Here want the have a talk shortcoming of the 4th kind of scheme (as United States Patent (USP) 4581288) of emphasis, promptly the molten scheme in resin of inorganic variable color particle.This scheme has two kinds of technologies, and a kind of is with polymeric resin (solidifying) fusion at high temperature, then inorganic variable color particle is participated in wherein, becomes one through pressure again.Another kind is inorganic variable color particle not to be added to go to make it that metachrosis is arranged in the polymeric resin fully.Because the practical problems of first kind of scheme is very many, key is that it can't solve all even transparent problem, does not do too much analysis at this.Do following analysis with regard to second kind of specific embodiments below:

One, taking high temperature after resin monomer is aggregated is worthless with the scheme that the variable color particulate is added in the resin.Such method will make attached to the discharge of the air of particle surface very difficult.If between particle and resin, air gap is arranged, will form the plane of reflection of two sealings, because the existence of air gap, the refractive index difference of these two plane of reflection will be very big, the intensity of reflection and scattering will be very big.This serious situation will cause whole goods muddiness, be exactly usually said " mist ", even may devitrification.

Under high-temperature situation, carry out in the middle of on the technology variable color particle being added to resin, also can make whole eyeglass exist the internal stress of pressure character and the partial polarization phenomenon occurs, cause the reduction of transmission performance.

Two, the size range of inorganic variable color particle is too big.The theory that has thinks that size range should be at the 0.5-150 micron, and thinking of also having should be in the scope of 0.5-100 micron, is the scope of 10-50 micron and think best.The particle range of 10-50 micron also is bigger than normal in fact, and particularly 50 microns of the upper limits are near people's the explanation limit.The product that the particle of this scope is made at first just is enough to now be examined by naked eyes at the initial stage of variable color macroparticle, in the product existence of foreign matter is arranged because its reflection and scattering strength can make the people feel, and influences very big to overall transparency.So as if from general overall feeling, variable color is not synchronous.

Three, the coupling of specific refractory power is accurate inadequately.The scope of differing that United States Patent (USP) 4581288 proposes the specific refractory power of the specific refractory power of inorganic variable color particle and organic resin is ± 0.002.This precision obviously is not enough.At first, the dispersion equation of two kinds of materials is not the same, this interface that just makes particle and matrix is to the selective reflection of different wave length, and strengthened the loss of scattering and reflection, the intensity of this scattering and reflection can cause viewer's vision response, particularly when the size of particle was big, classical scattering (Rayleigh scattering) intensity can not be ignored.In addition, because the temperature refraction rate of two kinds of materials of variation of temperature is also different, their change direction even might be opposite makes the difference of its specific refractory power become big, and above-mentioned phenomenon by reflection and scattering generation is more aggravated.Even more serious is, because the compensation of specific refractory power is inaccurate, at the glass granules, particularly big particulate wherein that take place just might observe under the situation of variable color in resin.

Four, inorganic variable color particulate weight adding per-cent is very responsive.If the per-cent that adds is excessive, not only can lose the lightweight advantage of resin lens, be not equal to zero, the fluctuating of density particularly can occur at gravity direction but also density gradient can occur, this also is an important physical phenomena that produces scattering, can make the goods muddiness too.

Five, the distribution of each regional inorganic metachromatic granule quantum count can have serious consequences as not controlling also in the resin.If inorganic variable color particle participates in the resin, the distribution of quantity do not controlled, along with the thickness difference, and transmissivity just can not be even after the variable color.Thick transmissivity is low, thin transmissivity height.To the high myopia glasses, look that in appearance the center of glasses is white, but very black all around, the eyelet of similar panda.Come law according to Korea Spro: τ=e ^-klWherein, τ represents transmissivity, and k represents material photoabsorption constant, and L represents that light passes through thickness, and e is the end of natural logarithm.Obviously, the thickness degree of material is huge to the influence of final transmissivity.In technology, must address this problem.

The object of the present invention is to provide a kind of manufacture method and eyeglass thereof of photochromic resin lens.

The manufacture method of photochromic resin lens, the material that will have discoloration is fused in the resin, it is characterized in that the anhydrous variable color powder of drying is mixed in the unpolymerized liquid monomer resin, stir, add initiator again and stir and make it thorough mixing, mix from monomer, participate in the polymerization whole process, pour three's mixed solution in lens mold moulding.

The manufacture method of aforesaid photochromic resin lens is characterized in that be that the photo chromic glass powder of 0.0001-0.001 mixes with the monomer (polymerization single polymerization monomer) of resin with accounting for total amount 5-30%, size less than 15 microns, specific refractory power and the refractive index difference scope of resin.

The manufacture method of aforesaid photochromic resin lens is characterized in that the consumption of photo chromic glass powder is 10-15%, is of a size of the 7-9 micron, and initiator is the 2.5-3.0% of gross weight.

The manufacture method of aforesaid photochromic resin lens is characterized in that the mould convex surface down.

Photochromic resin lens, it is formed by powder material with discoloration and resin fusion, it is characterized in that the anhydrous variable color powder of drying is mixed in the unpolymerized liquid monomer resin, stir, add initiator again and stir and make it thorough mixing, mix from monomer, participation polymerization whole process is poured three's mixed solution into that moulding forms in the lens mold.

Aforesaid photochromic resin lens is characterized in that be that the photo chromic glass powder of 0.0001-0.0001 mixes with the monomer (polymerization single polymerization monomer) of resin with accounting for total amount 5-30%, size less than 15 microns, specific refractory power and the refractive index difference scope of resin.

Aforesaid photochromic resin lens is characterized in that the consumption of photo chromic glass powder is 10-15%, is of a size of the 7-9 micron, and initiator is the 2.5-3.0% of gross weight.

The process implementing scheme of the embodiment of the invention is as follows: one, first machine photo chromic glass chooses

The best specific refractory power with a certain single polymers of the selection of inorganic photo chromic glass specific refractory power is identical, in order to avoid make refractive index match.The production of inorganic photo chromic glass can be accomplished this point.In certain scope, adjust the element silicon in the glass, can make inorganic photo chromic glass obtain any identical specific refractory power.If do not possess the condition of making the photo chromic glass technology, can select currently available products.The specific refractory power of the resin lens of selecting is preferably between two monomeric specific refractory poweres of vicinity, also can select the specific refractory power of photo chromic glass according to the requirement of own mould refractive index.Two, the acquisition 1 of glass granules, with the photo chromic glass fragmentation, select suitable ball mill that the photo chromic glass crushing piece is carried out ball milling, obtain like this

The photo chromic glass powder, its size range is bigger, the size of chien shih particle is attached to 8 microns when adjusting ball milling

Closely draw close, or the size of most particles is about 8 microns.If the granularity model of inorganic photo chromic glass

Enclose and be no more than 10 microns, the quantity of so inorganic variable color particle will be double-digit multiple to be increased, dispersity

Will increase widely, its homogeneity can greatly improve, and meanwhile, the loss of reflection and scattering just

Can sharply descend, transparency can obtain very big improvement.2, glass particle sieves, and allows the particle below 8 microns pass through, and then unsanctioned continuation is carried out again

Ball milling, screening, circulation so several times.It is every that what can pass through promptly is utilizable.If sieve

Divide difficulty, can utilize flotation.Can suspend in liquid, this liquid preferably selects to be about to ginseng

A kind of with in the polymeric monomer drafts certain hour, then suspended substance shifted out, and its throw out is not

Close the particle of requirement.3, the suspended substance that will shift out liquid filters out, and carries out high bake, and storing temperature is at 350-450 degree centigrade,

And constantly stir glass powder in the hope of thoroughly removing the moisture that adheres to.4, the powder that will thoroughly dry moves in the exsiccant container, under situation with good conditionsi, container is evacuated,

To get rid of the air in slit between glass particle.Sometimes even can be attached to the air of particle surface also portion

Take away with dividing.5, the weight of choosing glass particle is about 10% of goods gross weight, if the discoloration of glass is good, and can

With few what 10%.Three, monomer ratio is calculated and the specific refractory power of mixing 1. successful candidates is not a monomer when possessing, and will choose two kinds of monomers like this and arrange in pairs or groups.

Wherein, one of two monomeric specific refractory power that are selected should be a little more than selected specific refractory power, and another should

A little less than selected specific refractory power.Calculate two kinds of per-cents that monomer is shared with adding, that is: with theorem

N1*x+N2* (1-x)=N (N is the specific refractory power of selected goods, that is to say the specific refractory power of glass particle, N1,

N2 is respectively two monomeric specific refractory poweres, and x is N1 monomer shared ratio in mixture, and N2 is shared

Per-cent be 1-x).2. determine the gross weight of goods, go out two kinds of monomeric weight separately, taking out according to above-mentioned percentage calculation

Before getting monomer, monomer must be earlier sieve by one 2 microns to filter out foreign material and bubble.To extract

Two monomeric liquid pour into lentamente in two different containers and to determine its weight.Pouring container into

Process in, avoid being involved in of air and produce bubble.To seal for volatile monomer.3. two kinds of monomers are moved in the same container and mix, also should be careful especially in operating process, to keep away

Exempt from being involved in of air and produce bubble.4. mixed two monomers are fully stirred, make it even, can stir with helical-ribbon type and leaf oar formula

Device.Should be specifically noted that during stirring liquid is seethed, in order to avoid air is involved in, the leaf paddle stirrer also

Can only be that liquid is stirred, and can not seethe, in order to avoid air is involved in.In a word, should make liquid agitation

Evenly, air is involved in.5. the specific refractory power of mixed solution is measured with Abbe refractometer.Choose two mutually vertically on the surface of solution

Four end points and an intersection point of diameter are measured the specific refractory power at the position of selected point.If spiral shell

Ribbon agitator also should be measured at half five points in place of container depth.Reflect for Abbe

The reading of the each point under the instrument on behind the radix point four with the specific refractory power indifference of the finished product.Also be and glass

Glass particle specific refractory power indifference on four figures behind the radix point.If the specific refractory power deviation of each point is too big,

Should continue to stir, until the specific refractory power basically identical of each point.If the take off data of specific refractory power is nonconforming,

To suitably increase the monomeric weight of height (or low) specific refractory power to reach desired specific refractory power.Can use

A glass stick of being made by same photo chromic glass lot number material of making is in advance done tracking, with this root

After the glass stick wiped clean, insert in the mixed solution and stir.By mixed solution sight glass rod, if

Can not find the trace of glass stick in container, this optical interface that just shows glass stick and liquid level disappears

Lose.This meets the demands with regard to the coupling that proves two kinds of monomeric specific refractory poweres.But this is at Abbe refractometer

Carry out under the prerequisite that reading meets the demands.Four, mixed solution and glass particle mixes

The glass particle of handling well slowly and is carefully added (phenomenon that does not pour) in the mixed solution, and the limit edged stirs lentamente, and till with both mixings, the precaution in the stirring still as described above.Five, the selection that mixes 1. initiators of mixed solution and initiator.Initiator should be selected the low melting point type, and its fusing point should be more or less the same with normal temperature, like this

Easily with mixed solution in two monomers go up mutually compatible.2. the weight of initiator should be looked its theoretical active oxygen amount, activation energy and molecular weight and decided.In practice can

Adopt IPP (peroxy dicarbonate diisopropyl fat), can add 2.5 of gross weight as initiator

-3.0％。3. load weighted initiator is poured in the mixed solution lentamente, and stirring makes it enter liquid fully lentamente,

Look the room temperature situation and the temperature of solution is reached or slightly surpass its fusing point and constantly stir, examine and have or not

Suspended substance.If no suspended substance shows that initiator has become liquid state, constantly stir simultaneously and make it fully mixed

Close.Stir precaution as previously mentioned.4. after mixing container is not exclusively sealed, stay next gas-pervious place, reduce volatilization on the one hand, in addition

On the one hand, making the air above the liquid is a normal atmosphere.Quiet putting for some time, time length is looked container

The degree of depth and decide.Quiet purpose of putting is to make particle and initiator add the fashionable air of bringing into to float gradually, row

Remove liquid.Examine the situation of come-up gas, until first bubble come-up.Six, any one extracts liquid to the mensuration 1. of final specific refractory power in last mixed solution, adopts Abbe refractometer to measure.If refraction

Rate consistent with the specific refractory power of photo chromic glass on behind the radix point the 3rd just meets the demands.2. should stir again in case produce because of density is different in the process of pouring into a mould with the leaf paddle stirrer this moment

Precipitation is prepared cast then.Seven, cast 1. is the same with common resin lens casting, and what pay special attention to is to pour into a mould while stirring, to guarantee together

The variable color situation unanimity of a collection of resin eyeglass.2. when cast, must fill with mould and not produce bubble.Eight, polymerization

Polymeric technology is similar substantially with resin lens.Should notice that mould should guarantee convex surface down, like this, the vertex that mixes liquid level is exactly the edge of eyeglass.In the process that heats up, if the glass particle surface also is attached with the air of minute quantity, rising along with temperature, volume of air enlarges (because the coefficient of expansion of air is 1/273) rapidly, buoyancy also increases thereupon, bubble can rise to the vertex of liquid level very soon and at the edge of eyeglass, product can not produce muddiness like this.If plano lens because thickness relative difference middle and all around is little, can begins polymeric at once and heat up, like this, can impel monomeric polymerization to improve the viscosity of liquid as early as possible, make the mobile difficulty of glass granules, make the distribution of glass granules in eyeglass more even at last.If concave lens (thick around the intermediate thin), should be down with the mould convex surface filled with, the quiet certain hour of putting allows the photo chromic glass particulate sink and gathers to the centre, thereby improves because the different caused variable color differences of thickness are avoided " panda eyelet ".Nine, other

Technology subsequently, as: heating curve, the demoulding, cleaning or the like, identical with the production technique of resin lens.

Also the resin color-changing lens can be made product in addition with different background colors.One of method is the inorganic photo chromic glass particulate of introducing with different background colors, and only granularity should be littler and incorporation should be done suitable increase.The approach that other band background color is also arranged.

Claims (7)

1, the manufacture method of photochromic resin lens, the material that will have discoloration is fused in the resin, it is characterized in that the anhydrous variable color powder of drying is mixed in the unpolymerized liquid monomer resin, stir, add initiator again and stir and make it thorough mixing, mix from monomer, participate in the polymerization whole process, pour three's mixed solution in lens mold moulding.

2, the manufacture method of photochromic resin lens as claimed in claim 1 is characterized in that be that the photo chromic glass powder of 0.0001-0.001 mixes with the monomer (polymerization single polymerization monomer) of resin with accounting for total amount 5-30%, size less than 15 microns, specific refractory power and the refractive index difference scope of resin.

3, the manufacture method of photochromic resin lens as claimed in claim 2 is characterized in that the consumption of photo chromic glass powder is 10-15%, is of a size of the 7-9 micron, and initiator is the 2.5-3.0% of gross weight.

4, as the manufacture method of claim 1,2,3 described photochromic resin lens, it is characterized in that the mould convex surface down.

5, photochromic resin lens, it is formed by powder material with discoloration and resin fusion, it is characterized in that the anhydrous variable color powder of drying is mixed in the unpolymerized liquid monomer resin, stir, add initiator again and stir and make it thorough mixing, mix from monomer, participation polymerization whole process is poured three's mixed solution into that moulding forms in the lens mold.

6, photochromic resin lens as claimed in claim 5 is characterized in that be that the photo chromic glass powder of 0.0001-0.001 mixes with the monomer (polymerization single polymerization monomer) of resin with accounting for total amount 5-30%, size less than 15 microns, specific refractory power and the refractive index difference scope of resin.

7, photochromic resin lens as claimed in claim 6 is characterized in that the consumption of photo chromic glass powder is 10-15%, is of a size of the 7-9 micron, and initiator is the 2.5-3.0% of gross weight.