CN102794847A - Method for preparing thermosetting composition - Google Patents
Method for preparing thermosetting composition Download PDFInfo
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- CN102794847A CN102794847A CN2011101375203A CN201110137520A CN102794847A CN 102794847 A CN102794847 A CN 102794847A CN 2011101375203 A CN2011101375203 A CN 2011101375203A CN 201110137520 A CN201110137520 A CN 201110137520A CN 102794847 A CN102794847 A CN 102794847A
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Abstract
The invention provides a method for preparing a thermosetting composition which prevents the possibility of generating defects along with the curing of the composition. The method comprises a filling process of filling the composition which is contracted along with thermosetting into a forming die and a curing process of heating the forming die to cure the composition after the filling process, wherein the curing process comprises a step of raising temperature: raising the temperature of the composition which is subjected to the filling process by raising the temperature of the composition or combining the temperature raising and temperature maintenance; and a step of preventing separation: stopping the temperature raising of the composition after the temperature raising process to ensure that the composition is changed between the high temperature and the low temperature in a reciprocating mode from the temperature of the composition which is subjected to the temperature raising process to the temperature which reaches a temperature zone again of the composition which is subjected to the temperature raising process, so that the phenomenon that the composition is separated from the forming die because of the contraction of the composition caused along with the curing of the composition is avoided.
Description
Technical field
The present invention relates to the manufacturing approach of thermoset composition, relate in particular to following the composition that shrinks based on the curing of heat to be filled to the manufacturing approach that mould and heating make the thermoset composition that said composition solidifies.In addition, " composition " in this specification comprises the composition that has or once had this characteristic of thermosetting.That is, represent the composition that heat cure is preceding sometimes, also represent heat cure composition afterwards sometimes.
Background technology
In recent years, in optical material, replace glass lens, popularizing rapidly of plastic lens advances.Plastic lens has advantages such as light weight, resistance to impact, workability and easy dyeing property.Therefore, plastic lens is at optical material, especially universal rapidly in the eyeglass field.
In process that this is popularized, this requirement that will reduce the thickness of eyeglass for the aesthetic property that improves eyeglass continued into the present from the glass lens epoch.Generally, the thickness that wants to reduce eyeglass then need use the material of high index of refraction.
This have plastic lens be better than glass lens aspect.For example if glass lens, the ground proportion that then is directly proportional with refractive index can significantly increase, and the weight of eyeglass can significantly increase.If so, also remarkable variation of the comfortable wearing degree of eyeglass.
On the other hand, if plastic lens, even then refractive index uprises, proportion also increases not significantly, and the weight of eyeglass can significantly not increase yet.The comfortable wearing degree variation that therefore, can suppress eyeglass.
As the high plastics of refractive index, known have diallyl carbonic ester, epoxy methacrylates, diallyl phthalate (DAP:Di Allyl Phthalate below be also referred to as " DAP ".) etc.On the other hand, plastic lens also has softer and compares its surface with glass lens and is easy to generate this character of flaw.Select the plastic lens of high index of refraction if consider this character, then DAP suits.In addition, this DAP also is known as thermoset composition.
As the technology that has adopted this thermoset composition (DAP), the manufacturing approach of plastic lens molding with mould and plastic lens for example disclosed in the patent documentation 1.Particularly, following method being disclosed: uses DAP as monomer, this monomer is filled in the mould, make its polymerization, curing through heating then, thereby obtain lens.
In addition; Manufacturing approach as the plastic lens that has adopted thermoset composition; Known have a following technology: will be as the composition injection moulding mould on the basis of plastic lens, and the hot briquetting mould, thereby with the composition heating and solidify (for example with reference to patent documentation 2～5).
In these patent documentations, all came heating combination with 20 hours, the result is until 20 hours the time of curing needs that finishes composition.
In addition; Opposite with above-mentioned requirements; In order to make high index of refraction and thicker plastic lens; Known have a following technology: carry out temperature maintenance or heating again after polymerizable composition, polymerizable composition is filled to mould, rise and carry out refrigerating work procedure (for example with reference to patent documentation 6) in order to prevent that polymerization speed is local then.
In this patent documentation, need the time of (short more also wanting more than 16 hours) more than 20 hours until the curing that finishes composition.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 6-339938 communique
Patent documentation 2: TOHKEMY 2005-107192 communique
Patent documentation 3: TOHKEMY 2005-131799 communique
Patent documentation 4: TOHKEMY 2007-261054 communique
Patent documentation 5: international publication number WO2009/017191 communique
Patent documentation 6: TOHKEMY 2009-226742 communique
Summary of the invention
The problem that invention will solve
Like the record that also has in the patent documentation 6, plastic lens is normally through solidifying the composition that is filled in the mould to form.Yet under the situation that the composition polymerization is solidified, polymerization speed can change according to temperature.Therefore, the small Temperature Distribution in the composition might cause taking place rising, the decline of local polymerization speed.
If rising, the decline of local polymerization speed take place, then for example the molecular weight of the part of polymerization speed rising increases meeting more than other parts.This part can sedimentation downwards in composition or to above float.And then, also possibly produce convection current in the inside of mould (being in the composition).And if composition solidifies under the residual state that above-mentioned vestige arranged, then plastic lens might produce optical distortion, vein.
In order to suppress the generation of this optical distortion, vein, in patent documentation 2～5, with time heating combination long like this more than 20 hours.Even at the patent documentation that is provided with refrigerating work procedure midway 6 of heating, until the short again time that also needs more than 16 hours of the curing that finishes composition.
Under this situation; On the such basis of above-mentioned " aesthetic property ", " comfortable wearing degree " from wearer one side's requirement, in order to tackle for the vigorous demand of plastic lens and to " increase production plastic lens ", in other words " shortening manufacturing time " such from one side's of plastic lens manufacturer requirement also grow.In order to satisfy this requirement, must shorten curing process to composition.
As the gimmick that shortens curing process, can consider to use catalyst to reduce the gimmick of the curable temperature of composition.Yet; Promptly enable to use catalyst to shorten curing process; When resulting plastic lens here being carried out hard conating coating (hard coat), dyeing, the compound that uses during used here catalyst also might be coated with, dye hard conating produces harmful effect.
As a result, promptly enable to shorten curing process, also might can't carry out hard conating coating, dyeing, thereby can cause the scope of applied end article to narrow down.
Even so; If but at will shorten curing process at a venture, then on the basis of above-mentioned optical distortion, vein, also might be created in composition from mould during the demoulding plastic lens surface inhomogeneous such defective (following also this defective is called " concavo-convex ") appears.
Worse, when wanting to shorten curing process, on the basis of " concavo-convex ", " vein ", also might be created in defective that plastic lens is produced before the demoulding, i.e. " malsegregation " from mould.This " malsegregation " is meant the defective of following generation: in the process that composition is solidified or after solidifying; Composition is detached into type die; Because gravity and take place contact again, (followingly also this defective is called " leaving mould " thereby produce malsegregation with the mould of downside.From the photo of mould be shown in can after Fig. 5 of describing in the project of the embodiment that states.In addition, the Fig. 6 that after the mechanism that mould produces is shown in, states).
In detail, composition 4 is detached into (Fig. 6 (c)) after the type die 1, because gravity, said composition 4 contacts (Fig. 6 (d)) to I haven't seen you for ages with the mould of downside 1 (i.e. the use face 22a of second mould 22) generation again.Thus, the surface of composition 4 even plastic lens can produce flaw, produces " from mould ".
If behind curing process, produce, though then other operations will be set, these flaws can be removed through grinding, annealing or AR coating (antireflective coating, antireflection coating).Yet,, can produce flaw in the inside of plastic lens just in case in the process of curing process, produce.
If so, these flaws can be removed through grinding to wait, and can only discard this plastic lens.As a result, only cause yield rate to reduce because want to shorten curing process, can't satisfy above-mentioned requirements, this is a present situation.
The objective of the invention is to, provide and suppress to follow composition to solidify and produce the manufacturing approach of thermoset composition of the possibility of defective.
The scheme that is used to deal with problems
The possibility that the inventor produces defective in order to suppress to follow curing process to shorten has been carried out research again for existing curing process.At this moment, the inventor especially is conceived to " from mould " this defective and comes the new variations in temperature method in the curing process is studied.
Through this research, the inventor has formed following understanding: " from mould " this defective is to follow the composition that shrinks based on the curing of heat to produce owing to using.And infer that " from mould " is following the generation: because composition shrinks in curing process, make composition be detached into the surface of type die, thereby produce from mould.And, infer also that meanwhile make the surface of composition polish owing to composition solidifies, composition becomes and is detached into type die easily also is a reason that breaks away from.
Then; Based on this supposition; The inventor has expected being provided with before the heating process with patent documentation 6 that kind the diverse following gimmick of gimmick of refrigerating work procedure: behind the heating process that composition is cured, earlier the temperature of composition is reduced, and then so that the temperature of composition returns to the degree of the humidity province before the cooling heats up.
Follow based on the curing of heat and the composition that shrinks can produce spontaneous heating usually.The heat of this spontaneous heating increases in curing process, reaches peak value, reduces then.It is basic identical that this and composition solidify the degree of carrying out.That is, gradually change equally with heat is aforesaid, composition solidifies gradually, and its speed reaches peak value, and curing rate reduces gradually then.
So the spontaneous heat that the inventor is conceived to composition reaches peak value situation afterwards.So the inventor notices that on the one hand, the reduction of the caloric value of (being composition) composition, composition are lowered the temperature in mould, and on the other hand, the design temperature of mould in the past outer (being thermoregulator) makes its intensification.As a result, mould is inside and outside can to produce temperature difference, and the composition that this temperature difference makes the surface polish just is detached into the main cause of type die, and the inventor has formed as above understanding.
Based on this understanding, the inventor infers: if in heating process the curing of composition carried out a greater part of after as the caloric value of following composition reduce as the temporary transient temperature that reduces composition, be effective suppressing on mould generation this point at least then.This is with the design of patent documentation 6, promptly the diverse design of design of refrigerating work procedure is set for the increase with polymerization speed offsets.
In addition, the inventor has formed following understanding: through the temperature of so temporary transient reduction composition, but composite inhibiting is detached into the possibility on the surface of type die.On this basis, suppress earlier to solidify and then, composition is solidified through temporary so that the temperature of composition returns to the degree of the humidity province before the cooling heats up.Through the reciprocal variation of this temperature, can be detached into type die by composite inhibiting.As a result, the inventor has formed following understanding: can suppress in the mould generation, to accomplish the curing of composition as stated, and state of cure is reached no less than degree in the past.
Based on this understanding; Then for example if use the words of the plastic lens that contains the DAP composition; Then can be cured operation with 10 hours, and made plastic lens can significantly suppress to produce the possibility of the such defective of above-mentioned " concavo-convex ", " vein ", " from mould ".Also embody to some extent in Fig. 1 (a) and (b) of the embodiment 2～3 that this fact is stated after illustrating and the experimental condition of comparative example 1～2 and result.
Therefore in addition, because these defectives can form shadow to the plastic lens irradiates light time, also these defectives are referred to as " shadow defective " below.
Embodiment of the present invention based on above understanding is made is following.
First embodiment of the present invention is a kind of manufacturing approach of thermoset composition; It is characterized in that; It has with follow the composition that shrinks based on the curing of heat be filled to mould inside filling work procedure and behind aforementioned filling work procedure through heating the curing process that aforementioned mould solidifies foregoing
Aforementioned curing process has:
Heating process is through heating up or heat up foregoing and the combination of temperature maintenance heating up the temperature of foregoing behind the aforementioned filling work procedure; With
Break away from and suppress operation; Behind aforementioned heating process, stop the foregoing that heats up; Foregoing is back and forth changed between the high and low temperature till the temperature of the humidity province of temperature after reaching aforementioned heating process once more behind aforementioned heating process, thereby suppress to break away from aforementioned mould by following foregoing to solidify the foregoing that contraction caused that causes.
According to the described embodiment of first embodiment; Second embodiment of the present invention is characterised in that, its further have the humidity province after after aforementioned disengaging suppresses operation, will reaching aforementioned heating process temperature foregoing cooling and with the stripping process of foregoing demoulding from aforementioned mould.
According to the described embodiment of first or second embodiment, the 3rd embodiment of the present invention is characterised in that foregoing contains the diallyl phthalate compound.
According to the described embodiment of the 3rd embodiment, the 4th embodiment of the present invention is characterised in that aforementioned curing process carried out with interior at 10 hours.
According to the described embodiment of the 3rd or the 4th embodiment; The 5th embodiment of the present invention is characterised in that; If from aforementioned curing process begin to the time that finishes be 100% o'clock, after beginning through at least 80% time, begin aforementioned disengaging inhibition operation from aforementioned curing process.
The effect of invention
According to the present invention, can suppress to follow composition to solidify and the possibility of generation defective.
Description of drawings
Fig. 1 illustrates embodiment 2～3 and the experimental condition of comparative example 1～2 and result's figure; (a) being that the design temperature of thermoregulator and the figure of time relation are shown, (b) is the figure that the shadow generation of defects rate in the plastic lens that the glasses made in embodiment 2～3 and the comparative example 1～2 use is shown.
Fig. 2 is design temperature and the actual temperature of time or composition and the figure of time relation that the thermoregulator among the embodiment 1 is shown.
Fig. 3 illustrates design temperature and the time of the thermoregulator among the embodiment 4, actual temperature and the actual temperature of time or composition and the figure of time relation of thermoregulator.
Fig. 4 is design temperature and the actual temperature of time or composition and the figure of time relation that the thermoregulator in the comparative example 1～2 is shown.
Fig. 5 is the photo that is illustrated in the comparative example 2 situation of shadow defective (from mould) expansion in the plastic lens that the glasses made use.
Fig. 6 is the sketch map that can be used for making the mould of the plastic lens that glasses use, and is the figure that is used to explain shadow defective (from mould) mechanism of production.
Description of reference numerals
1 mould
2 moulds (mold)
21 first moulds
21a (first mould) use face
22 second moulds
22a (second mould) use face
3 packing rings (gasket)
31 composition inlets
4 compositions
The specific embodiment
At first, the variations in temperature that in " embodiment 1 ", focuses on thermoset composition describes.
Then, in " embodiment 2 " to refinement the 1.C of " embodiment 1 ") a) heating process and 1.C) b) break away from the suitable example that suppresses operation and describe.
After this, in " embodiment 3 ", focus on be used for to the mould that portion within it is filled with thermoset composition give variations in temperature thermoregulator, be that the design temperature of thermoregulator describes.
At last, in " embodiment 4 ", various variation are described.
Followingly specify embodiment of the present invention with reference to accompanying drawing.
In this embodiment, use Fig. 6 to describe by following order.In addition, the stage of the variations in temperature of record in the table 1 of the embodiment that states after below " Phase I～V " of record is meant and the table 2.
1. the manufacturing approach of thermoset composition
A) prepare thermoset composition
B) filling work procedure
C) curing process (Phase I～V)
A) heating process (Phase I～III)
B) break away to suppress operation (Phase IV～V)
I) cooling process (Phase IV)
Ii) rewarming operation (stage V)
D) stripping process
E) other operations
2. the resulting effect of embodiment
1. the manufacturing approach of thermoset composition
A) prepare thermoset composition
In this embodiment,, the situation of making the plastic lens that glasses use is described as an example of the manufacturing approach of thermoset composition.In addition, as stated, " composition " in this specification comprises the composition that has or once had this characteristic of thermosetting.That is, represent the composition (composition before the heat cure) of the feed stage of plastic lens sometimes, also represent after the heat cure sometimes and D) the preceding composition (composition after the heat cure) of stripping process.In addition, for the ease of explanation, the plastic lens of also glasses being used abbreviates " lens " as.
In this embodiment,, describe containing the diallyl phthalate compound compositions as an example of composition.Therefore this diallyl phthalate compound suits when making the lens of high index owing to have higher refractive index.In addition, the diallyl phthalate compound forms thermosetting resin making as monomer under the situation that is used for carrying out polymerization.In addition, the diallyl phthalate compound is followed based on the curing of heat and is shunk.
Certainly, also can in composition, suitably add the compound except that the diallyl phthalate compound.And then, also can in said composition, suitably add polymerization initiator etc.Detailed content after describe in " embodiment 4 " stated.In addition, in this embodiment, the composition before the curing process uses liquid material.
B) filling work procedure
Above-mentioned composition is fully mixed, then said composition 4 is filled to the inside of the mould 1 shown in Fig. 6 (a).Below this mould 1 is described.
In addition, in this embodiment, the shape of first mould 21 is so that the front surface of made lens has the mode of convex surface sets.Otherwise the shape of second mould 22 is so that the back surface of made lens has the mode of concave surface sets.In addition, packing ring 3 both played a role as the periphery maintaining part of mould 2, was bringing into play the effect that determines lens thickness again.
In addition, as the material of mould 2 and packing ring 3, so long as can be with above-mentioned composition 4 injection moulding moulds 1, the material of composition 4 polymerizations promptly can be used.But, as mould 2, the preferred use in order to make it be not easy the damaged glass molding of carrying out chemical enhanced processing with being scratched.
C) curing process (Phase I in the table 1～V)
A) heating process (Phase I～III)
In heating process, through composition 4 being heated up or heats up and the combination of temperature maintenance making composition 4 from B) temperature behind the filling work procedure heats up.In this operation, make liquid composition 4 gelations, it is solidified gradually.In addition, " intensification " in this embodiment is to instigate temperature to rise continuously, and " temperature maintenance " is meant and do not carry out variations in temperature.Therefore; " combination of intensification and temperature maintenance " is meant interimly and heats up; Be meant the situation of " heating up in a certain stage; carry out temperature maintenance ", also refer to the situation of in contrast " carry out temperature maintenance in a certain stage, heat up " in back to back next stage in back to back next stage.Generally speaking, this operation is meant the operation of not carrying out lowering the temperature.
B) break away to suppress operation (Phase IV～V)
Under the situation of as this embodiment, using DAP as the monomer of lens, owing to solidify, composition 4 can shrink self.If so; Shown in Fig. 6 (c); Although be with composition 4 from mould 1 before the demoulding, the possibility that composition 4 is detached into type die 1 (being that composition 4 breaks away from the use face 21a of first mould 21 and the use face 22a of second mould 22) also can increase.Especially, if its molding shrinkage of the words of the monomer of lens in the past is lower than 1%, and DAP has the high shrinkage of molding shrinkage up to nearly 10% degree.Therefore, if use DAP, then can produce and compare in the past the very easy situation that composition 4 is detached into type die 1 that takes place.
After composition 4 was detached into type die 1, shown in Fig. 6 (d), said composition 4 arrives owing to gravity, and I haven't seen you for ages took place to contact with the mould of downside 1 (i.e. the use face 22a of second mould 22) again.At first, because this contacts again, composition 4 can produce flaw.
And then the curvature of face side part can be owing to the curvature (Fig. 6 (c)) of shrinking the curved surface that becomes second mould 22 that is different from mould 1 behind the lens when composition 4 forms lens.Then, if, then can under composition 4 and second mould, 22 contacted states, be cured operation (Fig. 6 (d)) this disengaging taking place and being cured operation under the state of contact again.If so, the inside of composition 4 can form the flaw (promptly being printed on the flaw of a part of shape of second mould 22) of circular die.
Incidentally, should be the more significant defective that when wanting to shorten curing process, can become from mould.This is owing to shorten this operation meaning of curing process: suppose that then necessary raising is for the rate of temperature change of composition 4 if the range of temperature of whole curing process is set for identical with in the past.If so, sharply intensification composition 4 and likewise sharply cooling.If so, be not only concavo-convex, vein, and the possibility that produces from mould can increase all.
Therefore, in this embodiment,, thereby carry out this operation for composite inhibiting 4 breaks away from mould 2 so that do not form Fig. 6 (c), (d) such state.
In this operation, at first, composition 4 stops to heat up.Then, make said composition 4 from C) a) temperature behind the heating process is until reaching C once more) a) back and forth change between the high and low temperature till the temperature of the humidity province behind the heating process.Particularly, this operation is by i) cooling process and ii) these two operations of rewarming operation form.
I) cooling process (Phase IV)
In this operation, come composite inhibiting 4 to be detached into the surface of type die 1 through the temperature of temporary transient reduction composition 4.Because a) the heating process C that carries out before this operation), composition 4 is solidifying.
As stated, if composition 4 is cured, then the caloric value of composition 4 can reach peak value, reduces then, and composition 4 self can tend to cooling.Yet in the past, even at this in a flash, the thermoregulator that is used for hot briquetting mould 1 is still so that the mode that composition 4 heats up is carried out work.Therefore, in this operation, in order to remedy the temperature difference that produced and the temperature of composition 4 is reduced this moment.That is, begin to carry out the reciprocal variation of temperature from low temperature side.
Through carrying out above-mentioned operation composition 4 is solidified, surface that thus can composite inhibiting 4 becomes too smooth, even can composite inhibiting 4 becomes and be easy to be detached into type die 1, can suppress to produce from mould.
Ii) rewarming operation (stage V)
In this embodiment, carrying out above-mentioned i) make desuperheated composition 4 return to original temperature once more after the cooling process.That is, make the temperature of composition 4 return to C once more) a) temperature (if this embodiment then also is to be about to the carry out C) b of the humidity province behind the heating process) i) temperature before the cooling process).Through carrying out this reciprocal variation between high and low temperature, composition 4 is solidified.That is, through i) the next temporary transient curing that suppresses of cooling process, it is too smooth that the surface of composite inhibiting 4 becomes, and makes to have adaptation to a certain degree between composition 4 and the mould 1.But, if, then also have the not enough possibility of state of cure like this with composition 4 cooling and the demouldings.Therefore, also for state of cure is reached no less than in the past degree and carry out this operation.
In addition, in this operation, not that composition 4 is carried out simple intensification, return to " temperature of the humidity province behind the heating process " this characteristic but have the temperature that makes composition 4.Through temperature is recovered, not only can not increase the possibility that produces from mould once more, and state of cure is reached no less than degree in the past owing to excessively heating up.
At this; " temperature of the humidity province behind the heating process " preferably with heating process after temperature be uniform temp; Can not be accurately for uniform temp, can allow with composition 4 after the demoulding in the stripping process stated, have when manufacturing lens and can stand practical state of cure and not produce temperature amplitude by the degree of the flaw that causes from mould.Under the situation of as this embodiment, using DAP as monomer, if be in a ratio of approximately with temperature behind the heating process ± 3 ℃, then can allow.
At above i) cooling process and ii) in these two operations of rewarming operation, back and forth change through the temperature that makes composition 4, can be detached into type die 1 by composite inhibiting 4.As a result, as stated, can suppress in the mould generation, to accomplish the curing of composition 4, and state of cure is reached no less than degree in the past.
In addition, under the situation of as this embodiment, using DAP, C) b) breaking away from the reciprocal variation that suppresses the temperature in the operation preferably carries out with the temperature amplitude that surpasses 3 ℃.If temperature amplitude surpasses 3 ℃, the then fully curing of composite inhibiting 4, and can effectively suppress to produce from mould.
In addition, C) b) break away from suppress operation preferably at least at C) begin after a) following in the heating process spontaneous heating that above-mentioned composition 4 solidifies the above-mentioned composition 4 that carries out to reach peak value.Thus, can be at C) a) curing of composition 4 has been carried out positively following the reduction of the caloric value of composition 4 after a greater part of in the heating process, and can effectively suppress to produce from mould.
In addition, result from composition 4 from the generation of mould and follow the contraction of solidifying and taking place.Therefore, molding shrinkage is high more, composition 4 should take place more easily be detached into type die 1.Yet, through carrying out the such C of this embodiment) and b) break away from and suppress operation, even the molding shrinkage height also can produce disengaging by composite inhibiting 4.Therefore, at the compound of being avoided because molding shrinkage is high in the past, if use this embodiment then also can make lens etc.That is, can enlarge the range of application of the high material of molding shrinkage in goods.
In addition, molding shrinkage is high more, and the value of the effect that this embodiment brought is big more.As a result, if the molding shrinkage of the composition that uses in this embodiment 4 is more than 1%, then can improves composite inhibiting 4 and be detached into type die 1 or even suppress to leave the such effect of mould generation.
And then for the thickness of lens, the difference of the thickness of lens middle body and rims of the lens part is big more, and the effect of this embodiment is big more.For example the lens middle body as thin as a wafer, under the quite thick by comparison situation of rims of the lens part, even the whole molding shrinkage of lens is identical, the lens middle body is also greatly different with rims of the lens amount of contraction partly.That is, compare with the lens middle body, the amount of contraction of rims of the lens part is very big.As a result, in the use face 21a of mould 2,22a, be equivalent to the part of rims of the lens part, composition 4 can become very big with the possibility that mould 1 breaks away from.To this, through carrying out the C of this embodiment) b) break away from and suppress operation, even the lens of shape also can be made when mould produces in inhibition like this.In addition, if the thickness of lens middle body (optical centre part or geometric center part) is thinner than the thickness of rims of the lens part, then more can bring into play this effect.
In addition, at C) b) ii) during the rewarming operation, also can form the stage of the temperature of keeping composition 4.That is, keep the temperature of composition 4 roughly certain within a certain period of time, make the temperature of composition 4 return to C then) a) temperature behind the heating process.Wherein, because C) b) break away from and suppress operation and also have the purpose that temporary transient composite inhibiting 4 solidifies, therefore should " certain hour " be preferably set to the time that does not have the length of effect for the state of cure of the lens of final manufacturing.
In addition, establishing from C) curing process begin to the time that finishes be 100% o'clock, C) b) break away from and suppress operation preferably from C) curing process begins after beginning through at least 80% time.If change a kind of saying, then establishing from C) curing process begin to the time that finishes be 100% o'clock, C) a) heating process preferably from C) curing process begins to carry out at least 80% time.
As previously mentioned, this operation meaning is to suppress by C) composition 4 shrinks use face 21a, the 22a that the composition 4 that causes is detached into type die 1 in the curing process.That is, this operation can become the stage of problem on the surface whether composition 4 is detached into type die 1, i.e. curing has been carried out the stage to a certain degree and carried out.The reduction of the design temperature that in addition, the curing of composition 4 is carried out after the more than half part in heating process, the caloric value of composition 4 reaches the thermoregulator that the mode that reduces with the temperature of following composition 4 when reducing behind the peak value carries out is also relevant with the condition enactment of above-mentioned time.
As stated, in this embodiment, preferably begin through carrying out C after at least 80% time from curing process) b) break away from and suppress operation.Thus, more effectively composite inhibiting 4 is detached into type die 1.
And then C) curing process preferably carried out with interior at 10 hours.In addition, even carrying out C with 10 hours) under this condition of curing process, also preferably guarantee C) b) i) the spent time of cooling process is more than 1 hour.And preferably carry out cooling process with the temperature amplitude above 3 ℃ this moment.This be because, through the composition 4 of can fully lowering the temperature like this, and surface that can composite inhibiting 4 becomes too smooth, can further suppress to produce from mould.
In addition; C) curing process can not carry out with interior at 10 hours; And substitutingly as after Fig. 1, the Fig. 2 and shown in Figure 3 shown in the embodiment that states, will be from whole C) rate of temperature change during curing process is set at 40 ℃ (80 ℃ of temperature maximums the variations in temperature of composition 4 are poor with 40 ℃ of temperature minimum of a values)/more than 10 hours, more than 4.0 ℃/hour.
D) stripping process
After this, carry out the stripping process of mold release compositions 4 from mould 1.At this moment, preferably with C) b) break away to suppress to reach after the operation humidity province behind the heating process temperature composition 4 coolings and from mould 1 mold release compositions 4.
E) other operations
After carrying out above-mentioned operation, then composition 4 is carried out surface treatment, annealing, cutting or washing etc. if desired.So make lens as goods.
2. the resulting effect of embodiment
According to this embodiment, can bring into play following effect.That is, when making lens, can be with significantly foreshortening to below 10 hours at the curing process that needs 20 hours compositions 4 more than (weak point is also wanted 16 hours again) in the past.And then, even significantly shortened curing process, also can suppress the possibility that lens produce shadow defective (especially from mould).
The result; Can satisfy when manufacturing has the lens of high index, reduce lens edge thickness this for the requirement of " aesthetic property " with suppress " comfortable wearing degree " this requirement that the weight of lens increases from wearer one side, and can satisfy in order to tackle this requirement of will " increasing production plastic lens " for the thriving demand of lens from lens manufacturers one side.
And then, if be this embodiment, then need not use catalyst for the curable temperature that reduces composition 4, can successfully carry out hard conating coating, dyeing to the gained lens.As a result, curing process can be shortened, and the range of application of the lens of manufacturing can be enlarged.
In this embodiment, to refinement the 1.C of " embodiment 1 ") a) heating process and 1.C) b) break away from the suitable example that suppresses operation and describe.At first, with C) a) heating process be divided at least two stages the situation of intensification composition 4 be described.After this, with C) b) break away to suppress the i of operation) cooling process is divided into the situation of at least two stage publicly price-reduction temperature compositions 4.
C) a) heating process (Phase I～III)
I) first heating process (Phase)
At first, in first heating process, rate of temperature change is set at and surpasses 2.5 ℃/hour and be lower than 5 ℃/hour.Set through carrying out this temperature, can suppress to produce concavo-convex that variations in temperature owing to the first half term of curing process produces.
Ii) second heating process (Phase I)
Behind first heating process, make rate of temperature change be higher than above-mentioned first heating process above-mentioned composition 4 that heats up.At this moment, rate of temperature change is set at is lower than 12 ℃/hour.Set through after carrying out first heating process, carrying out this temperature, can the composite inhibiting 4 interior excessive convection current that produce.As a result, the vein that produces in the variations in temperature that has suppressed further to suppress on the concavo-convex basis to produce equally owing to the first half term of curing process.
Through the heating process in above so at least two stages of setting, can suppress to produce, and can suppress shadow defective, the i.e. generation of concavo-convex, vein in addition from mould.
In addition, except first heating process with second heating process,, then can be provided with by another operation (the for example Phase I of table 1) that heats up and/or temperature maintenance constitutes so long as the temperature of composition 4 behind the filling work procedure heated up.Yet, even heat up stage by stage, also preferably at above-mentioned i) then carry out ii) second heating process behind first heating process.
In addition; With rate of temperature change is set at surpass 2.5 ℃/hour and to be lower than variations in temperature stage of 5 ℃/hour be i) first heating process; Be ii) second heating process with the heating process that after this then carries out, it is preferred setting with the mode of the condition that satisfies the said temperature rate of change.In addition, if with C) heating process that a) reaches maximum rate of temperature change in the heating process is as ii) second heating process, then can more effectively suppress generation concavo-convex, vein.
And then the viewpoint that never makes composition 4 be detached into type die 1 is considered, preferably a) is ii) then carrying out b behind second heating process) break away from and suppress operation.But, also can between these two operations, carry out can not making composition 4 to be detached into the intensification and/or the temperature maintenance operation of the degree of type die 1.
In addition, if consider, preferably in whole C from the viewpoint that fully is cured, shortens hardening time) a) persistently overheating composition 4 in the heating process.
C) b) break away from the inhibition operation
I) cooling process
1) first cooling process
At first, in first cooling process, the rate of temperature change of composition 4 is set at and surpasses 0 ℃/hour and be lower than 4 ℃/hour.Can suppress the shadow defective and produced as long as originally satisfy the condition of embodiment 1, yet consider, more preferably at C from the viewpoint of the risk that reduces to produce the shadow defective that can't expect) b) i) rapid cooling composition 4 within reason in the cooling process.Set through carrying out such temperature, can suppress to produce the shadow defective that causes by rapid variations in temperature.
2) second cooling process
Behind first cooling process, make rate of temperature change be higher than above-mentioned first cooling process above-mentioned composition 4 of lowering the temperature.At this moment, rate of temperature change is set at the degree that surpasses first cooling process.Set through carrying out this temperature, can reach original purpose, promptly suppress to produce from mould.
As above; Setting is divided into the cooling process in two stages, lowers the temperature slowly earlier at the beginning, carries out by comparison cooling faster then; The shadow defective that can suppress thus to expect produces, and can more effectively reach original purpose, i.e. inhibition from the mould generation.
In addition, except first cooling process with second cooling process, so long as from C) a) the temperature cooling above-mentioned composition 4 behind the heating process, another operation that is made up of cooling and/or temperature maintenance then can be set.Wherein, under the situation of lowering the temperature stage by stage, preferably above-mentioned 1) then carry out 2 behind first cooling process) second cooling process.
In addition; With rate of temperature change is set at surpass 0 ℃/hour and to be lower than 4 ℃ of/hour variations in temperature stages be 1) first cooling process; With the cooling process that after this then carries out is 2) second cooling process, it is preferred setting with the mode of the condition that satisfies the said temperature rate of change.
And then the viewpoint that never makes composition 4 be detached into type die 1 is considered, preferably at b) i) 2) then carry out b behind second cooling process) ii) rewarming operation.But, also can between these two operations, carry out the cooling and/or the temperature maintenance operation of the degree of unlikely generation shadow defective.
In addition, if from suppress over-cured, effectively composite inhibiting 4 viewpoint that is detached into type die 1 is considered, preferably in whole C) b) i) continue cooling composition 4 in the cooling process.Further, preferably at C) b) break away from and suppress composition 4 not to be lowered the temperature before the operation.
In this embodiment; Be not as " embodiment 1 " from the variations in temperature of composition 4, but focus on thermoregulator that mould 1 occurrence temperature that is used to make inside be filled with composition 4 changes, be that the design temperature of thermoregulator describes.
Basically, so that composition 4 reaches the temperature setting that the mode of the temperature conditions of above-mentioned embodiment is carried out thermoregulator.But, when reality is made lens, can produce difference between the temperature of the composition 4 of the design temperature of thermoregulator and reality sometimes.In this embodiment, consider the temperature setting that this difference is carried out thermoregulator.
The temperature of this thermoregulator is set especially at C) b) i) be important in the cooling process.In the above-described embodiment, explained that it is effective for composition 4 cooling process being divided into two stages.On the other hand, as shown in Figure 3 for the thermoregulator of this embodiment, it is preferred carrying out with the mode of the cooling process that carries out a stage that temperature sets.More detailed, with the rate of temperature change of the cooling process in this stage be set at be lower than 20 ℃, and with 1 hour with on the composition 4 of lowering the temperature be preferred.
As stated, can produce difference between the temperature of the composition 4 of the design temperature of thermoregulator and reality.In this case, if set the rate of temperature change of the design temperature of thermoregulator too rapid, then composition 4 can with fully the state of cooling move to next rewarming operation.If so, the curing of can can't fully suppress carrying out, the result can't suppress to produce from mould.
Therefore, in this embodiment, with the rate of temperature change of the design temperature of the thermoregulator in the cooling process be set at be lower than 20 ℃, with 1 hour with on the composition 4 of lowering the temperature.Thus, can take time and fully suppress to solidify, and then can more effectively suppress to produce from mould.
This is for wanting C) curing process be controlled at 10 hours especially effective with interior situation.Generally, if want to shorten whole C) curing process, tend to shorten C wherein usually) b) i) cooling process.Yet, positive so-called " haste brings no success ", anti-its road of this embodiment and go, the rate of temperature change of the design temperature of thermoregulator is set at be lower than 20 ℃, with 1 hour with the abundant composition 4 of lowering the temperature that comes up.
In addition, the condition of this rate of temperature change and time is not only applicable to the design temperature of thermoregulator, is applicable to composition 4 yet.That is, at C) b) i) in the cooling process, the rate of temperature change of composition 4 is set at be lower than 20 ℃, cooling composition 4 also was preferred to come up fully with 1 hour.At this moment, can as " embodiment 2 ", be divided into two stages carries out cooling process, also can be the cooling process in a stage.
In addition, technical scope of the present invention is not limited to above-mentioned embodiment, is also included within can draw through adding the embodiment that various changes, improvement obtain in the scope of the technical characterictic of invention, certain effects that its combination obtains.
Use DAP as monomer in the above-mentioned embodiment, but so long as follow the composition 4 that shrinks based on the curing of heat, then also can use material in addition.If give an example, can expect that then composition 4 is through polymerization or crosslinked situation of solidifying.
In addition; As the thermosetting resin except that DAP, can illustration going out phenolic resins, urea resin, urea formaldehyde resin, melmac, polyester-melmac, melamine formaldehyde resin, alkyd resins, epoxy resin, epoxy-melmac, unsaturated polyester resin, polyimide resin, acrylic resin, polyorganosiloxane resin, polyurethane resin, urethane methacrylate resin, methacrylate resin, diallyl carbonate resin, PMMA resin (plexiglass), thioxanthamide and be resin, polycarbonate resin, episulfide is the general bi-component curing type acrylic resin (acrylic polyol solidfied material) of resin, resin etc.
In addition; Except that these; For example also can enumerate out phenolic varnish type phenolic resins such as phenol novolac resin, cresols novolac resin, bisphenol-A phenolic varnish gum; Phenolic resins such as bakelite; Bisphenol-type epoxy resin such as bisphenol A epoxide resin, bisphenol F epoxy resin, phenolic resin varnish type epoxy resins such as phenolic resin varnish, cresols phenolic resin varnish, biphenyl type epoxy resin, 1; Epoxy resin such as 2-talan type epoxy resin, triphenol methane type epoxy resin, alkyl-modified triphenol methane type epoxy resin, the epoxy resin that contains triazine nuclear, dicyclic pentylene modified phenol type epoxy resin; Urea resin, melmac etc. contain the resin of triazine ring, and unsaturated polyester resin, bimaleimide resin, organic siliconresin, the resin that contains the benzoxazine ring, cyanate ester resin, epoxide modified siloxanes etc. can use a kind of in these or two or more combinations are used.
And then, can in the such monomer of DAP, further add ultra-violet absorber.If enumerate example, then can enumerate out being selected from least a in BTA being of benzophenone series as ultra-violet absorber.And,, can enumerate out 2 as this benzophenone series ultra-violet absorber; 4-dihydroxy benaophenonel, 2-hydroxyl-4-acetoxyethoxy benzophenone, 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,2 '-dihydroxy-4; 4 '-dimethoxy-benzophenone, UV-531,2,2 '-dihydroxy-4,4 '-dimethoxy-5; 5 '-disulfo benzophenone 2 sodium salts, 2-hydroxyl-4-octyloxy benzophenone, 2,2 ', 4; 4 '-tetrahydroxy-4-octyloxy benzophenone and 2,2 ', 4 '-trihydroxy-4-octyloxy benzophenone etc.; As BTA is ultra-violet absorber, can enumerate out 2-(2, the 4-dihydroxy phenyl)-BTA, 2-(2; 4,6-trihydroxy phenyl)-BTA, 2-(2 '-hydroxyl-5-octyl phenyl) BTA, 5-chloro-2-(2, the 4-dihydroxy phenyl)-BTA, 5-chloro-2-(2; 4,6-trihydroxy phenyl)-BTA, 5-bromo-2-(2, the 4-dihydroxy phenyl)-BTA, 5-bromo-2-(2; 4; 6-trihydroxy phenyl)-BTA, two chloro-2-(2, the 4-dihydroxy phenyl)-BTA, dibromo two chloro-2-(2, the 4-dihydroxy phenyl)-BTA etc.Wherein, be preferably and be selected from 2-hydroxyl-4-octyloxy benzophenone, 2,2 '; 4,4 '-tetrahydroxy-4-octyloxy benzophenone, 2,2 '; At least a in 4 '-trihydroxy-4-octyloxy benzophenone and 2-(2 '-hydroxyl-5-octyl phenyl) BTA; Preferred especially 2,2 ', 4 '-trihydroxy-4-octyloxy benzophenone.Certainly, even the known ultra-violet absorber except that above-mentioned also can suitably select according to the kind of thermoset composition 4.
At this moment, in order to adjust tone, can add known metallic particles or metallic compound with the function that is used to adjust tone.If give an example, then can enumerate out with composition, be CoOAl
2O
3And/or CoAl
2O
4The cobalt compound of expression, Au particulate etc.
And then, also can in the such monomer of DAP, add polymerization initiator.As polymerization initiator, monomer polymerization is then not special to be limited as long as can make, and can use known material, is preferably to be selected from least a in organic peroxide and the organic azo-compound.As this organic peroxide, can enumerate out benzoyl peroxide, peroxidating Methylethyl, methyl ethyl ketone peroxide, di-t-butyl peroxide, lauroyl peroxide, acetyl peroxide, di-isopropyl peroxydicarbonate, two (the 4-tert-butyl group hexamethylene) esters of peroxy dicarbonate, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, uncle's hexyl peroxidating-2 ethyl hexanoic acid ester etc.; As organic azo-compound, can enumerate out 2, the two bis-isobutyronitriles, 2 of 2 '-azo; 2 '-azo two (2 Methylpropionic acid methyl), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2; The 4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acids) etc.In the middle of these, be preferably and be selected from least a in benzoyl peroxide, di-isopropyl peroxydicarbonate and tert-butyl hydroperoxide-2 ethyl hexanoic acid ester.
In addition, making C in the above-described embodiment) composition 4 before the curing process is for liquid, and also can use liquid or solid-state composition 4.So long as in mould 1, make liquid composition 4 to solidify, after this do not make mould 1 and the situation that composition 4 breaks away from, can use the present invention.That is, even at B) for example be solid-state in the filling work procedure, also can be at B) carry out C after melting the processing of composition 4 behind the filling work procedure) curing process.
In addition, for above-mentioned embodiment, at C) b) break away from and suppress to have carried out a variations in temperature back and forth in the operation, and also can carry out two above back and forth variations in temperature.Yet, in this case, after with composition 4 cooling once, need make it restore to C) and a) temperature of the humidity province behind the heating process.And need lower the temperature to composition 4 once more from this temperature, and make it restore to C equally) a) temperature of the humidity province behind the heating process.
In addition, in the above-described embodiment so that the front surface of made lens has the shape that the mode of convex surface is set first mould 21, and also can be in contrast, so that the front surface of made lens has the shape that the mode of concave surface is set first mould 21.Equally, for second mould 22, also can set the shape opposite for above-mentioned embodiment.In addition, first mould 21 and second mould 22 all can be so that the two sides of made lens have the mode of convex surface sets, also can be so that the two sides of made lens has the mode of concave surface sets.
In addition; In order to give photochromism to the lens of making in the above-mentioned embodiment; Can use following method: the method that the coating (photochromic films) that comprises photochromic pigment is set on lens substrate; The be covered method of photochromic films of scioptics base material, the method for configuration photochromic films etc. between two lens substrates.
In addition, in the above-mentioned embodiment glasses have been carried out illustration with plastic lens, but so long as followed based on the curing of heat and the composition that shrinks can be used the present invention.For example if enumerate applicable example; Then can be except that glasses with the plastic optics the plastic lens; Also can be the lens that read of the middle equimultiple type that uses such as duplicator, facsimile machine, LED printer, also can be achromatic lens, the variable focal length lens of camera, the such distributed refractive index plastic lens of the lens of finding a view (finder lens).
Embodiment
Then provide embodiment and specify the present invention.Certainly, the present invention is not limited to following examples.
A) prepare thermoset composition
In diallyl phthalate, add IPP-27 (Japanese grease manufacturing) as polymerization initiator; And adding is as the UV-5411 (SUN CHEMICAL COMPANT LTD. manufacturing) of ultra-violet absorber; Stir at normal temperatures, and under reduced pressure outgas while stirring.After this, the liquid that stirred is filtered, make the composition that uses in the present embodiment.
B) filling work procedure
In the mould 1 shown in Fig. 6 (a), fill filtered liquid.Particularly, inject above-mentioned composition so that it is filled in the mould 1 from composition inlet 31.In addition, make it during injection under air atmosphere, the design temperature of thermoregulator that will be used to be adjusted to the temperature of type die 1 is set at 42 ℃.
C) curing process
In addition, for each stage, required time of design temperature, each stage, the rate of temperature change (℃/hour) that is drawn by design temperature and time are different in each stage.In addition, for the temperature and the rate of temperature change in following each stage, the numerical value in the setting of thermoregulator is shown.For the temperature and the rate of temperature change of the composition 4 of reality, each special record.
Table 1
| Stage | The setting of arrival temperature (℃) | The time in stage (hour) | Rate of temperature change (℃/hour) |
| Before the curing process | 42 | - | - |
| I | 53 | 5 | 2.2 |
| II | 60 | 1.5 | 4.7 |
| |
80 | 2 | 10 |
| |
70 | 0.5 | -20 |
| V | 85 | 1 | 15 |
A) heating process
In the present embodiment, as heating process, set Phase I～III.In addition, in the present embodiment, the Phase in the table 1 (4.7 ℃/hour of rate of temperature changes) is equivalent to i) first heating process.In addition, Phase I (10 ℃/hour of rate of temperature changes) is equivalent to ii) second heating process.
B) break away from the inhibition operation
In the present embodiment, suppress operation, set Phase IV～V as breaking away from.In addition, in the present embodiment, the Phase IV in the table 1 (rate of temperature change-20 ℃/hour) is i) cooling process, stage V (15 ℃/hour of rate of temperature changes) is ii) rewarming operation.
D) stripping process
Finishing above-mentioned C) after the curing process, will reach composition 4 coolings of the temperature of the humidity province behind the heating process.Then, pull down mould 2 and packing ring 3, with composition 4 demouldings.
E) other operations
Table 2
| Stage | The setting of arrival temperature (℃) | The time in stage (hour) | Rate of temperature change (℃/hour) |
| Before the curing process | 42 | - | - |
| I | 53 | 5 | 2.2 |
| II | 60 | 1.5 | 4.7 |
| III | 77 | 1.5 | 11.3 |
| |
70 | 1 | -7 |
| V | 85 | 1 | 15 |
In addition, in embodiment 4, for composition 4, at b) i) carry out 1 in the cooling process) first cooling process and 2) second cooling process.On the other hand, in thermoregulator, set the cooling process in a stage, rate of temperature change is set at has been lower than 20 ℃, and temperature fall time was set at more than 1 hour.
Comparative example 1～2
Comparative example 1 is at C) carry out the variations in temperature shown in below table 3 in each stage in the curing process.And then comparative example 2 carries out the variations in temperature shown in below table 4 in each stage.In addition, for the variations in temperature of table 3 and table 4, the design temperature that thermoregulator is shown and the actual temperature of time or composition 4 and the figure of time relation are shown in Fig. 4.In addition carry out the operation same with embodiment 1.
Table 3
| Stage | The setting of arrival temperature (℃) | The time in stage (hour) | Rate of temperature change (℃/hour) |
| Before the curing process | 40 | - | - |
| I | 40 | 1.5 | 0 |
| II | 50 | 4.5 | 2.2 |
| III | 55 | 1 | 5 |
| IV | 75 | 1.5 | 13.3 |
| V | 85 | 0.5 | 20 |
| VI | 85 | 1 | 0 |
Table 4
| Stage | The setting of arrival temperature (℃) | The time in stage (hour) | Rate of temperature change (℃/hour) |
| Before the curing process | 40 | - | - |
| I | 40 | 1.5 | 0 |
| II | 50 | 3 | 3.3 |
| III | 55 | 1 | 5 |
| IV | 75 | 2.5 | 8 |
| V | 85 | 1 | 10 |
| VI | 85 | 1 | 0 |
Estimate
Glasses for making in embodiment 1～4 and the comparative example 1～2 are used plastic lens, situation or shadow defective generation rate that check shadow defective produces.In addition, for the shadow defective, use high-pressure sodium lamp to check.Particularly, will by the light of above-mentioned high-pressure sodium lamp projection throw glasses with plastic lens on and be projected on the curtain.With this transmission picture of visualization.In addition,, calculate: check the glasses made with the same hand method how through above-mentioned visualization, thereby calculate with the quantity of the lens of generation shadow defective in the plastic lens through following method for shadow defective generation rate.
At first, for embodiment 1, unconfirmed to the generation of shadow defective.Equally, for embodiment 4, also unconfirmed to the generation of shadow defective.
And then to embodiment 2～3 check shadow defective generation rates, shown in Fig. 1 (b), shadow defective generation rate is about below 1%, and the shadow defective has obtained very effectively suppressing.
On the other hand, in comparative example 1～2, shown in Fig. 1 (b), shadow defective generation rate is about 10% or higher.Fig. 5 shows the reason that this shadow defective generation rate increases.Fig. 5 illustrates the figure of the glasses of making in the comparative example 2 with situation about producing from mould in the plastic lens.Can know situation about expanding gradually from mould to (e) successively by Fig. 5 (a).
As stated, for embodiment,, also can effectively suppress the shadow defective though have the time in the past required the curing process of (20 hours, shorter also want 16 hours) reduced in comparison to about 1/2～5/8 (10 hours) with curing process.Can know on the other hand, in not using the comparative example of present embodiment, only simply curing process foreshortened to 10 hours and can't suppress the generation of shadow defective.
Following remarks other preferred embodiment.
A kind of manufacturing approach of thermoset composition is characterized in that, aforementioned disengaging suppresses the reciprocal variation of the temperature in the operation and carries out with the temperature amplitude above 3 ℃.
A kind of manufacturing approach of thermoset composition is characterized in that, aforementioned disengaging suppresses to begin after operation follows the spontaneous heating of the foregoing of foregoing curing to reach peak value at least in aforementioned heating process.
A kind of manufacturing approach of thermoset composition is characterized in that, the molding shrinkage of foregoing is more than 1%.
A kind of manufacturing approach of thermoset composition is characterized in that, persistently overheating foregoing in aforementioned heating process.
A kind of manufacturing approach of thermoset composition is characterized in that, aforementioned disengaging suppresses operation to have to the cooling process of foregoing with in the rewarming operation that makes the temperature after foregoing returns to aforementioned heating process behind the aforementioned cooling process,
Aforementioned cooling process further has first cooling process of cooling foregoing and behind aforementioned first cooling process, makes rate of temperature change be higher than lower the temperature second cooling process of foregoing of aforementioned first cooling process.
A kind of manufacturing approach of thermoset composition; It is characterized in that; Aforementioned heating process has first heating process of intensification foregoing and behind aforementioned first heating process, makes rate of temperature change be higher than heat up second heating process of foregoing of aforementioned first heating process
The rate of temperature change of aforementioned first heating process is above 2.5 ℃/hour and be lower than 5 ℃/hour, and the rate of temperature change of aforementioned second heating process is lower than 12 ℃/hour,
Wherein, with the operation that reaches the maximum temperature rate of change in the aforementioned heating process as second heating process.
A kind of glasses is characterized in that with the manufacturing approach of plastic lens, behind aforementioned first heating process, then carry out aforementioned second heating process.
A kind of manufacturing approach of thermoset composition is characterized in that, carries out the aforementioned cooling process more than 1 hour, with the cooling of the temperature amplitude above 3 ℃ foregoing.
Remarks 9(following design temperature) about thermoregulator
A kind of manufacturing approach of thermoset composition is characterized in that, the temperature conditions that aforementioned curing process is set regulation for through the thermoregulator that will be used to aforementioned mould occurrence temperature is changed carries out,
Aforementioned disengaging suppresses that operation has the cooling process of cooling aforementioned temperature adjuster and in the rewarming operation that makes the temperature after the aforementioned temperature adjuster returns to aforementioned heating process behind the aforementioned cooling process,
Aforementioned cooling process is set at the rate of temperature change of the design temperature of aforementioned temperature adjuster and is lower than 20 ℃/hour, with 1 hour with on carry out.
A kind of manufacturing approach of thermoset composition is characterized in that, the temperature conditions that aforementioned curing process is set regulation for through the thermoregulator that will be used to aforementioned mould occurrence temperature is changed carries out,
Persistently overheating aforementioned temperature adjuster in aforementioned heating process.
Remarks 11
A kind of manufacturing approach of thermoset composition is characterized in that, the temperature conditions that aforementioned curing process is set regulation for through the thermoregulator that will be used to aforementioned mould occurrence temperature is changed carries out,
Aforementioned heating process has first heating process of intensification aforementioned temperature adjuster and behind aforementioned first heating process, makes rate of temperature change be higher than heat up second heating process of aforementioned temperature adjuster of aforementioned first heating process,
The rate of temperature change of aforementioned first heating process is lower than 5 ℃/hour, and the rate of temperature change of aforementioned second heating process is lower than 12 ℃/hour.
Remarks 12(following) for summing up
A kind of manufacturing approach of thermoset composition; It is characterized in that; It has with follow the composition that shrinks based on the curing of heat be filled to mould inside filling work procedure and behind aforementioned filling work procedure through heating the curing process that aforementioned mould solidifies foregoing
Aforementioned curing process has following operation:
Heating process is through heating up or heat up foregoing and the combination of temperature maintenance heating up the temperature of foregoing behind the aforementioned filling work procedure; With
Break away from and suppress operation; Behind aforementioned heating process, stop the foregoing that heats up; Foregoing is back and forth changed between the high and low temperature till the temperature of the humidity province of temperature after reaching aforementioned heating process once more behind aforementioned heating process; Thereby suppress to break away from aforementioned mould by following foregoing to solidify the foregoing that contraction caused that causes
Foregoing contains the diallyl phthalate compound,
Aforementioned curing process carried out with interior at 10 hours,
Aforementioned disengaging suppresses the reciprocal variation of the temperature in the operation and carries out with the temperature amplitude above 3 ℃; And then; If from aforementioned curing process begin to the time that finishes be 100% o'clock, carry out aforementioned disengaging inhibition operation when surpassing for 80% time having begun to pass through from aforementioned heating process.
Claims (5)
1. the manufacturing approach of a thermoset composition; It is characterized in that; It has with follow the composition that shrinks based on the curing of heat be filled to mould inside filling work procedure and behind said filling work procedure through heating the curing process that said mould solidifies said composition
Said curing process has following operation:
Heating process is through heating up or heat up said composition and the combination of temperature maintenance heating up the temperature of said composition behind the said filling work procedure; With
Break away from and suppress operation; Behind said heating process, stop the intensification of said composition; Said composition is back and forth changed between the high and low temperature till the temperature of the humidity province of temperature after reaching said heating process once more behind said heating process, thereby suppress to break away from said mould by following said composition to solidify the said composition that contraction caused that causes.
2. the manufacturing approach of thermoset composition according to claim 1; It is characterized in that, its further have the humidity province after after said disengaging suppresses operation, will reaching said heating process temperature said composition cooling and with the stripping process of said composition demoulding from said mould.
3. the manufacturing approach of thermoset composition according to claim 1 and 2 is characterized in that, said composition contains the diallyl phthalate compound.
4. the manufacturing approach of thermoset composition according to claim 3 is characterized in that, said curing process carried out with interior at 10 hours.
5. according to the manufacturing approach of claim 3 or 4 described thermoset compositions; It is characterized in that; If from said curing process begin to the time that finishes be 100% o'clock, after beginning through at least 80% time, begin said disengaging inhibition operation from said curing process.
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| US20210079151A1 (en) | 2018-03-27 | 2021-03-18 | Mitsui Chemicals, Inc. | Method for setting polymerization condition and method for manufacturing optical material |
| US20210372984A1 (en) | 2018-07-24 | 2021-12-02 | Mitsui Chemicals, Inc. | Method for setting polymerization condition and method for manufacturing optical material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427767A (en) * | 2000-03-30 | 2003-07-02 | Q2100有限公司 | Apparatus and system for production of plastic lenses |
| CN1489706A (en) * | 2001-11-09 | 2004-04-14 | 大日本印刷株式会社 | Optical element |
| JP2004209968A (en) * | 2002-12-18 | 2004-07-29 | Seiko Epson Corp | Method for producing plastic lens and raw material storage/supply apparatus |
| US20060192306A1 (en) * | 2005-02-25 | 2006-08-31 | The Microoptical Corporation | Manufacturing methods for embedded optical system |
| CN101321616A (en) * | 2005-12-21 | 2008-12-10 | 埃西勒国际通用光学公司 | Method for coating an ophthalmic lens within an injection molding machine |
| CN101339301A (en) * | 2008-08-06 | 2009-01-07 | 上海康耐特光学股份有限公司 | Shock resistance optical resin lens and method of manufacture |
| JP2009226742A (en) * | 2008-03-24 | 2009-10-08 | Seiko Epson Corp | Manufacturing method of plastic lens |
| CN101765494A (en) * | 2007-07-25 | 2010-06-30 | Hoya株式会社 | Method for producing plastic lens |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069133A (en) * | 2000-06-16 | 2002-03-08 | Showa Denko Kk | Plastic lens material, method for producing the material, composition for plastic lens, plastic lens obtained by curing the composition and method for producing the plastic lens |
| JP2006239977A (en) * | 2005-03-02 | 2006-09-14 | Seiko Epson Corp | Manufacturing method of plastic lens |
-
2011
- 2011-05-24 CN CN201110137520.3A patent/CN102794847B/en active Active
-
2012
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427767A (en) * | 2000-03-30 | 2003-07-02 | Q2100有限公司 | Apparatus and system for production of plastic lenses |
| CN1489706A (en) * | 2001-11-09 | 2004-04-14 | 大日本印刷株式会社 | Optical element |
| JP2004209968A (en) * | 2002-12-18 | 2004-07-29 | Seiko Epson Corp | Method for producing plastic lens and raw material storage/supply apparatus |
| US20060192306A1 (en) * | 2005-02-25 | 2006-08-31 | The Microoptical Corporation | Manufacturing methods for embedded optical system |
| CN101321616A (en) * | 2005-12-21 | 2008-12-10 | 埃西勒国际通用光学公司 | Method for coating an ophthalmic lens within an injection molding machine |
| CN101765494A (en) * | 2007-07-25 | 2010-06-30 | Hoya株式会社 | Method for producing plastic lens |
| JP2009226742A (en) * | 2008-03-24 | 2009-10-08 | Seiko Epson Corp | Manufacturing method of plastic lens |
| CN101339301A (en) * | 2008-08-06 | 2009-01-07 | 上海康耐特光学股份有限公司 | Shock resistance optical resin lens and method of manufacture |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112612175A (en) * | 2020-12-16 | 2021-04-06 | 深圳市光科数字科技有限公司 | Miniature projection curtain and preparation process thereof |
| CN112612175B (en) * | 2020-12-16 | 2022-08-09 | 深圳市光科数字科技有限公司 | Miniature projection curtain and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102794847B (en) | 2017-08-29 |
| JP5926561B2 (en) | 2016-05-25 |
| JP2012240414A (en) | 2012-12-10 |
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