CN102091705B - Cleaning method of glass mold forming plastic lens forming mold - Google Patents
Cleaning method of glass mold forming plastic lens forming mold Download PDFInfo
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- CN102091705B CN102091705B CN2009101704542A CN200910170454A CN102091705B CN 102091705 B CN102091705 B CN 102091705B CN 2009101704542 A CN2009101704542 A CN 2009101704542A CN 200910170454 A CN200910170454 A CN 200910170454A CN 102091705 B CN102091705 B CN 102091705B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
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Abstract
The invention provides a cleaning method of glass mold forming a plastic lens forming mold, which comprises a washing process of using a plastic lens forming die washing agent composition to wash the glass die. The plastic lens forming die washing agent composition comprises at least one of phenyl ethers shown in the following formula (1) and the following formula (2). The phenyl ether comprises, by weight, 2% - 20%.
Description
Technical field
The present invention relates to constituting the method that plastic lens cleans with the glass mold of shaping dies and the manufacture method of having used the plastic lens of this clean method.
Background technology
Plastic lens is compared with inorganic lenses, and quality is light, be difficult to break and dyeing easily.And the raising by the hard conating correlation technique and have the more exploitation of the resin material of high index of refraction can be made thinner, lighter plastic lens.Along with these development of technology, be in a plurality of fields of representative with the eyeglass lens field, plastic lens begins to substitute inorganic lenses and popularizes.
In the past, using maximum as the resin that constitutes plastic lens is by making the diethylene glycol diene propyl carbonate carry out the resin that radical polymerization obtains.But, developed the higher resin material of this resin of refractive index ratio recently.Its typical example is thioretinites such as sulfur-containing polyurethane resin, sulfur-bearing epoxy resin, poly-sulfo-(methyl) acrylate, poly-(methyl) acrylate of sulfur-bearing, episulfide resin.The refractive index of the plastic lens substrate that the shaping of use thioretinite obtains is up to more than 1.55.
As the shaping dies of plastic lens substrate, generally use 1 pair of glass mold.This 1 pair of shaping dies seals with encapsulants such as adhesive tape or gasket seals by utilizing to fix, thereby forms sealed material and 1 pair of cavity that the glass mold encirclement forms.In this cavity, inject polymerizable monomer etc., carry out polymerizing curable by making polymerizable monomer, thereby obtain plastic lens substrate.The gained plastic lens substrate uses the composition of detergent of regulation to wash (for example with reference to TOHKEMY 2001-129500 communique).On the other hand, for glass mold, after the demoulding, wash, use for several times repeatedly in order to be shaped a plurality of plastic lens.Before the re-using of glass mold, be with owing to the soil release of adhering to as the use of shaping dies.As the dirt that is attached on the glass mold, for example can enumerate the resin that constitutes plastic lens substrate and not polymer, the plasticizer that from gasket seal, oozes out, fixing adhesive, operator's fingerprint and the dust in the environment etc. with adhesive tape.
Wherein, because above-mentioned resin height ground is crosslinked, be securely fixed in very much on the glass mold, therefore extremely difficulty is removed.
As the washing agent that is used for the cleaning glass mould, use the alkalis that contains alkaline agents such as KOH all the time.But, the resin that is attached on the glass mold when forming the resin that is attached to when refractive index is sulfur-bearing plastic lens substrate more than 1.55 on the glass mold with the plastic lens substrate that formed than low-refraction is in the past compared, and is attached on the glass mold more securely.Therefore, the resin that is attached on the glass mold more is difficult to peel off, and the adhesion amount on glass mold is also many.Under this background, in TOHKEMY 2006-124696 communique and the TOHKEMY 2003-81660 communique composition of detergent that above-mentioned resin dirt is demonstrated higher washing performance is disclosed.
But, in the washing of having used TOHKEMY 2006-124696 communique or the disclosed composition of detergent of TOHKEMY 2003-81660 communique, can't fully remove above-mentioned resin dirt.
Summary of the invention
The invention provides the method that the glass mold to constituting the plastic lens shaping dies that can remove the resin dirt that is attached on the plastic lens shaping dies well cleans and the manufacture method of having used the plastic lens of this clean method.
The method that the glass mold that constitutes the plastic lens shaping dies is cleaned of the present invention contains the washing procedure that uses the plastic lens shaping dies to wash above-mentioned glass mold with composition of detergent, described plastic lens shaping dies contains at least a kind of phenyl ether that is selected from the phenyl ether shown in the phenyl ether shown in the following general formula (1) and the general formula (2) with composition of detergent, and the content of described phenyl ether is 2 weight %～20 weight %.
Above-mentioned general formula (1), (2) in, k is 1 or 2, EO is oxyethylene group, AO is that carbon number is 3 and/or 4 oxyalkylene group, n1 and n2 are average addition molal quantity, n1 and n2 can be different mutually, m1 and m2 are that 3 oxyalkylene group (PO) is the average addition molal quantity of PO when constituting at AO by carbon number, are that 4 oxyalkylene group (BO) is the average addition molal quantity of BO when constituting at AO by carbon number, are the sum of the average addition molal quantity of the average addition molal quantity of PO and BO when AO comprises PO and BO, m1 and m2 can be different mutually, n1 is 3～100 number, and n2 is 3～100 number, and m1 is the number of 0～0.2 * n1, m2 is the number of 0～0.2 * n2, (EO)
N1(AO)
M1(EO)
N2(AO)
M2EO separately and the arrangement of AO can be block also can be random, when AO comprises PO and BO, the arrangement of PO and BO can be block also can be random, EO can insert in the arrangement that is made of PO and/or BO with block or random mode.
The manufacture method of plastic lens of the present invention contains following operation: use the be shaped forming process of plastic lens substrate of the shaping dies of 1 pair of glass mold that the interval contain to stipulate disposes opposite to each other; Stripping process with the demoulding from the above-mentioned plastic lens substrate of above-mentioned glass mold; Behind above-mentioned stripping process, the cleaning process that uses the method that the glass mold that constitutes the plastic lens shaping dies is cleaned of the present invention that above-mentioned glass mold is cleaned, wherein, for a plurality of plastic lens substrates that are shaped, above-mentioned 1 pair of glass mold reuses through behind the above-mentioned cleaning process.
Description of drawings
Fig. 1 is the flow chart of an example of the manufacture method of explanation plastic lens of the present invention.
The specific embodiment
(embodiment 1)
Employed plastic lens shaping dies by containing the specific phenyl ether of ormal weight, can be removed the resin dirt (solidfied material of plastic lens material) of firm attachment on the glass mold of formation plastic lens shaping dies with composition of detergent (following also abbreviate as sometimes " composition of detergent ") well in the method that the glass mold that constitutes the plastic lens shaping dies is cleaned of the present invention.
(specific phenyl ether)
Specific phenyl ether contained in the said detergent composition is by following general formula (1) or following general formula (2) expression.
Wherein, k is 1 or 2, EO is oxyethylene group, AO is that carbon number is 3 and/or 4 oxyalkylene group, n1 and n2 are average addition molal quantity, n1 and n2 can be different mutually, m1 and m2 are that 3 oxyalkylene group (PO) is the average addition molal quantity of PO when constituting at AO by carbon number, are that 4 oxyalkylene group (BO) is the average addition molal quantity of BO when constituting at AO by carbon number, are the sum of the average addition molal quantity of the average addition molal quantity of PO and BO when AO comprises PO and BO, m1 and m2 can be different mutually, n1 is 3～100 number, and n2 is 3～100 number, and m1 is the number of 0～0.2 * n1, m2 is the number of 0～0.2 * n2, (EO)
N1(AO)
M1(EO)
N2(AO)
M2EO separately and the arrangement of AO can be block also can be random, when AO comprises PO and BO, the arrangement of PO and BO can be block also can be random, EO can insert in the arrangement that is made of PO and/or BO with block or random mode.Average addition molal quantity can utilize
1H-NMR measures.
EO and AO be arranged as block the time, the block number of EO and the block number of AO as long as each average addition molal quantity in above-mentioned scope, can be respectively 1, also can be respectively more than 2.In addition, be 2 when above at the block number that is constituted by EO, in each block the repeat number of EO can be identical mutually also can be different.The block number of AO is 2 when above, in each block the repeat number of AO also be can be identical mutually also can be different.Too, the block number of EO can be 1 when EO inserted in the arrangement that is made of PO and/or BO in the mode of block, also can be for more than 2, the block number that is made of EO is 2 when above, in each block the repeat number of EO can be identical mutually also can be different.
When AO comprises PO and BO, PO and BO be arranged as block the time, the block number of PO and the block number of BO need only average addition molal quantity in above-mentioned scope, can be respectively more than 1, also can be for more than 2.In addition, the block number that is made of PO is 2 when above, in each block the repeat number of PO can be identical mutually also can be different.The block number of BO is 2 when above, in each block the repeat number of BO also be can be identical mutually also can be different.
In addition, from guaranteeing suitable water miscible viewpoint, going up preferred bonding at the oxygen atom (O) that constitutes ehter bond has EO.
Be attached to the fissility of the resin dirt on the surface of glass die and the deliquescent viewpoint in the aqueous medium of the specific phenyl ether of raising composition of detergent from raising, number, the n2 that preferred n1 is 3～70 number, m1 is 0～0.1 * n1 is that 3～70 number, m2 are the number of 0～0.1 * n2, and more preferably n1 is that 3～50 number, m1 are 0, n2 is that 3～50 number, m2 are 0.
Wherein, the polyoxyethylene-3 of preferred n1=5～50, m1=0, polyoxyethylene talan phenyl ethers such as two (1-phenylethyl) phenyl ethers of 5-, the polyoxyethylene of n2=5～50, m2=0-2,4, polyoxyethylene tribenzyl phenyl ethers such as 6-three (1-phenyl methyl) phenyl ether, the more preferably polyoxyethylene of n1=5～50, m1=0-3, two (1-phenylethyl) phenyl ethers of 5-etc.
From the viewpoint of the productivity ratio that improves plastic lens, said detergent composition with will above-mentioned specific phenyl ether as the washing for glass mold of the form of the solution of principal component.At this moment, be attached to the viewpoint of the fissility of the resin dirt on the surface of glass die from raising, the content of the above-mentioned specific phenyl ether in the composition of detergent be preferably 2 weight % above, more preferably more than the 4 weight %.In addition, from improving the viewpoint of rinsing, the content of the above-mentioned specific phenyl ether in the composition of detergent is preferably below the 20 weight %, more preferably below the 15 weight %.Therefore, the content of the specific phenyl ether in the composition of detergent is preferably 2～20 weight %, more preferably 2～15 weight %, 4～15 weight % more preferably.
(solvent)
As long as contained solvent can play the effect as solvent in the said detergent composition, be not particularly limited, for example can enumerate ultra-pure water, pure water, ion exchange water or distilled water etc., preferred ultra-pure water, pure water or ion exchange water, more preferably pure water.In addition, pure water and ultra-pure water for example can followingly obtain: running water is fed carry out ion-exchange treatment in the active carbon, further distill, shine the ultraviolet sterilizing lamp of regulation as required or make it pass through filter, thereby obtain.For example the conductance under 25 ℃ as a rule, pure water is that 1 μ S/cm is following, ultra-pure water is below the 0.1 μ S/cm.
From stability and the property handled that improves composition of detergent and the viewpoint that improves liquid waste processing, protection environment, the content of the solvent in the composition of detergent is preferably 80～98 weight %, more preferably 85～98 weight %, 85～96 weight % more preferably.
(composition arbitrarily)
In addition, also other contained in common composition of detergent compositions be can in the scope of not damaging effect of the present invention, contain as required in the said detergent composition, chelating agent, pH conditioning agent, anticorrisive agent, antirust agent etc. such as water-miscible organic solvent beyond the above-mentioned solvent contained in the defoamer that suppresses to foam in the washing procedure, the said detergent composition, EDTA for example can be contained.
As defoamer, for example can enumerate siloxanes, higher alcohol, higher fatty acids or its salt, Pluronic type copolymer, Tetranic type copolymer, polyethylene glycol, polypropylene glycol etc.Can in said detergent composition, cooperate these materials.From the viewpoint that suppresses foaming, do not hinder rinsing, the content of defoamer is preferably 0.01～3.0 weight % in the composition of detergent total amount, more preferably 0.05～2.0 weight %, 0.1～1.0 weight % more preferably.
When containing water-miscible organic solvent in the composition of detergent, specific phenyl ether improves the compatibility of resin dirt.Therefore, composition of detergent improves the wetability of resin dirt, and the performance of removing of the resin dirt that composition of detergent produces further improves.
As water-miscible organic solvent, can enumerate polyalcohols or water-soluble glycol ethers etc.As polyalcohols, for example can enumerate gamma butyrolactone, dimethyl formamide, dimethyl sulfoxide (DMSO), ethylene glycol or propane diols etc.As water-soluble glycol ethers etc., can enumerate ethylene glycol monobutyl ether, diethylene glycol single-butyl ether or triethylene glycol etc.These materials can use separately, also can mix more than 2 kinds and use.In these materials, from the specific phenyl ether of further raising to the compatibility of resin dirt and the composition of detergent viewpoint to the wetability of resin dirt, preferred ethylene glycol, diethylene glycol single-butyl ether or triethylene glycol, more preferably diethylene glycol single-butyl ether or triethylene glycol.In addition, water-miscible organic solvent refers to dissolve at least under 20 ℃ organic solvent more than the 1.5 weight % among the application in water.
Never reduce the stability of composition of detergent and composition of detergent given for the sufficient compatibility of resin dirt and the viewpoint of wetability set out, the content of water-miscible organic solvent is preferably 5～150 weight portions, more preferably 10～120 weight portions, 50～120 weight portions more preferably with respect to above-mentioned specific phenyl ether 100 weight portions.
As the pH conditioning agent, can enumerate alkali compounds or acid compound etc.As alkali compounds, can enumerate ammonia, potassium hydroxide, water-soluble organic amine or quaternary ammonium hydroxide etc.As acid compound, can enumerate inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, organic acids such as acetic acid, oxalic acid, butanedioic acid, glycolic, malic acid, citric acid or benzoic acid etc.
As anticorrisive agent, can enumerate benzalkonium chloride, benzethonium chloride, 1,2-benzisothiazole-3-ketone, (5-chloro-) 2-methyl-4-isothiazoline-3-ketone, hydrogen peroxide or hypochlorite etc.
From improving the viewpoint of the fissility that is attached to the resin dirt on the surface of glass die that above-mentioned specific phenyl ether brings, pH preferably is adjusted into suitable value, pH under 25 ℃ of composition of detergent is preferably 5～11, more preferably 6～10, more preferably 7～9, and pH can use pH meter (East Asia electric wave Industrial Co., Ltd, HM-30G) to measure.
In addition, the content the when content of each composition of above-mentioned explanation is use, said detergent composition also can preserve and supply with the state that concentrates in not damage its stable scope.At this moment, be preferred from reducing the aspect of making cost of transportation.Concentrate suitably dilutes the back use with above-mentioned solvent as required and gets final product.
When said detergent composition was above-mentioned concentrate, from the viewpoint of the manufacturing cost of transportation that reduces composition of detergent, the content of specific phenyl ether was preferably more than the 20 weight % in the above-mentioned concentrate, also can be 100 weight %.In addition, during with the above-mentioned concentrate of solvent dilution, the viewpoint that never makes its gelation and obtain uniform solution is set out, preferred above-mentioned concentrate contains above-mentioned preferred water-miscible organic solvent, and its content is preferably 5～150 weight portions, more preferably 10～120 weight portions, 50～120 weight portions more preferably with respect to phenyl ether 100 weight portions in the concentrate.
The preparation method's of said detergent composition a example then, is described.
The manufacture method of said detergent composition is not limited to them, for example can be by any preparation that becomes to assign to that mixes specific phenyl ether, solvent and use as required.
(embodiment 2)
Then, an example of the method that glass mold is cleaned of having used said detergent composition and used the example of manufacture method of the plastic lens of this method is described.
Fig. 1 represents the flow chart of an example of the manufacture method of plastic lens of the present invention.Flow chart shown in Figure 1 is the flow chart that describes with the manufacture method of plastic lens as the glasses of an example of plastic lens manufacture method of the present invention.
As shown in Figure 1, the manufacture method of plastic lens of the present invention example contains following operation: the internal grinding operation (S7) of the cleaning process (S3) of the forming process of shaping plastic lens substrate (S1), stripping process (S2), glass mold, the periphery grinding process (S4) of plastic lens substrate, annealing operation (S6), plastic lens substrate, dyeing process (S9), hard conating form operation (S13), anti-reflection layer forms operation (S15) and stain-proofing layer forms operation (S16).
Internal grinding operation (S7), dyeing process (S9), anti-reflection layer form operation (S15), stain-proofing layer formation operation (S16) is not necessary, can not have.In the cleaning process of plastic lens substrate or plastic lens (S5, S8, S10, S12, S14), as rinsing liquid, use pure water etc. usually.
At first, in forming process (S1), dispose 1 pair of glass mold opposite to each other with the interval of stipulating, between 1 pair of glass mold, dispose for example gasket seal of ring-type.Then, use maintenance instrument such as clip to keep this state.Thus, by 1 pair of glass mold and gasket seal, form the plastic lens shaping dies with cavity.
Then, inject polymerizable composition, polymerizable composition as the plastic lens substrate raw material in the cavity.Then, make polymerizable composition, polymerizable composition carry out polymerization by for example thermal polymerization.
The plastic lens substrate that obtains by polymerizable composition, polymerizable composition generation polymerization preferably contains the polymerism resin more than a kind that is selected from sulfur-containing polyurethane resin, sulfur-bearing epoxy resin, poly-sulfo-(methyl) acrylate and the episulfide resin.When plastic lens substrate contains these resins, refractive index can be made and for example be the plastic lens more than 1.55, thin plastic lens can be made.
As glass mold, use employed glass mold in the shaping as plastic lens substrate in the past and known mould gets final product.For example glass mold preferably by by ion-exchange with a part of Na in the glass
+Be replaced as K
+, the chemically reinforced glass that produces compression stress near surface is constituted.
Gasket seal uses in the past as the gasket seal that constitutes the plastic lens shaping dies and known pad gets final product.In addition, also can use and fixing substitute the sealing pad with adhesive tape.Fixing also be to use in the past as the adhesive tape that constitutes the plastic lens shaping dies and known adhesive tape gets final product with adhesive tape.
Then, remove the maintenance instrument to the maintenance of shaping dies, carry out the stripping process (S2) that shaping dies is taken off from plastic lens.
Then, carry out the cleaning process (S3) of glass mold.In the cleaning process of this glass mold (S3), use the washing of the glass mold of said detergent composition to carry out more than 1 time, preferably carrying out more than 2 times, used the rinsing of rinsing liquid to carry out more than 1 time, preferably carrying out more than 2 times, more preferably carry out 3～13 times.In addition, in the cleaning process of actual glass mold, potcher for example is 5～24 grooves sometimes, in most cases uses 13～18 grooves, glass mold preferably repeat 3～13 times in these grooves dipping and take off liquid after carry out rinsing.
The flow process of an example of above-mentioned cleaning process has been shown in the following table 1.In the example shown in the table 1, at first use said detergent composition to come the 1st washing procedure of cleaning glass mould to glass mold.Then, according to the degree of residual dirt or the dirt that adheres to again, use said detergent composition to come the 2nd washing procedure of cleaning glass mould, perhaps used the rinsing process of rinsing liquid.When carrying out the 2nd washing procedure, after to glass mold carry out more than 1 time, preferred rinsing process repeatedly.
As employed rinsing liquid in the rinsing process, when the composition of detergent of stating water-based in the use comes the cleaning glass mould, be water in principle, from being easy to the viewpoint of rinsing, preferred running water, ion exchange water, pure water etc.But the composition of detergent that is brought into glass mold from washing procedure is accumulated in the tank sometimes, below the preferred 10 weight % of its amount for rinsing liquid, more preferably below following, the further preferred 3 weight % of 5 weight %.
The preferred range of composition of detergent can wait suitably according to the pollution level of plastic lens substrate and adjust, for example from improving the viewpoint of washing performance, reduction water evaporation quantity, be preferably 20 ℃～90 ℃, more preferably 35～80 ℃, more preferably 50～70 ℃.Being attached to the viewpoint of the fissility of the resin on the surface of glass die from raising, wash time is preferably 30 seconds～and 60 minutes, more preferably 1～30 minute, more preferably 2～15 minutes, further be preferably 2～5 minutes.
Be not particularly limited for washing methods, can use normally used known method.For example can enumerate spray method, dipping ultrasonic washing method etc. in infusion process, dipping suspension system, dipping paddling process, dipping foam-forming method, the liquid.
When using above-mentioned plastic lens shaping dies to come the cleaning glass mould with composition of detergent, and then the method that glass mold is cleaned of the present invention is for example carrying out the 2nd washing procedure or rinsing process after the 1st washing procedure.The plastic lens shaping dies that uses in the 1st washing procedure is preferably more than 55 ℃ with the temperature of composition of detergent.In the 2nd washing procedure, preferred serviceability temperature is come cleaning glass mould with the low plastic lens shaping dies more than 20 ℃ of composition of detergent with composition of detergent than employed plastic lens shaping dies in the 1st washing procedure.Like this, in the 2nd washing procedure, when serviceability temperature than the 1st washing procedure in employed plastic lens shaping dies when using composition of detergent with the low plastic lens shaping dies more than 20 ℃ of composition of detergent, can give thermal shock to glass mold and resin dirt attached thereto.In rinsing process, preferred serviceability temperature is come the rinsing glass mold than employed plastic lens shaping dies in the 1st washing procedure with the low aqueous rinse more than 20 ℃ of composition of detergent.Like this, in rinsing process, when serviceability temperature than the 1st washing procedure in employed plastic lens shaping dies during with the low aqueous rinse more than 20 ℃ of composition of detergent, can give thermal shock to glass mold and resin dirt.
As mentioned above, when giving thermal shock to glass mold and resin dirt, think to make composition of detergent efficient infiltrate into the interface of glass mold and resin dirt well by the poor of the coefficient of thermal expansion that can utilize glass mold and resin dirt.When composition of detergent efficient infiltrates into above-mentioned interface well, can promote peeling off of resin dirt, the result can infer that washing performance increases.
When giving above-mentioned thermal shock to glass mold and resin dirt attached to it, from improving said detergent composition to the infiltrative reason at the interface of glass mold and resin dirt, the temperature of employed composition of detergent is preferably 55～90 ℃, more preferably 60～80 ℃, more preferably 65～70 ℃ in the 1st washing procedure.
When after the 1st washing procedure and then, carrying out the 2nd washing procedure, in the 2nd washing procedure, preferably in the preferred range of said detergent composition, serviceability temperature is come the cleaning glass mould than the low composition of detergent that more than 20 ℃, preferably hangs down more than 25 ℃ of temperature of employed composition of detergent in the 1st washing procedure.Namely, when repeatedly having used above-mentioned plastic lens shaping dies to use the washing procedure of composition of detergent, the plastic lens shaping dies that uses in the x+1 time washing procedure preferably hangs down more than 20 ℃, preferably hangs down more than 25 ℃ with the temperature of composition of detergent than the plastic lens shaping dies that uses in the x time washing procedure with the temperature of composition of detergent.
In addition, when after the 1st washing procedure and then, carrying out rinsing process, in this rinsing process, preferably in the preferred range of following rinsing liquid, serviceability temperature is come the rinsing glass mold than the low rinsing liquid that more than 20 ℃, preferably hangs down more than 25 ℃ of temperature of employed composition of detergent in the 1st washing procedure.Namely, in the repeatedly rinsing process that carries out behind washing procedure, the temperature of employed rinsing liquid is preferably low more than 20 ℃, preferably low more than 25 ℃ than the temperature of employed composition of detergent in the washing procedure before above-mentioned the 1st rinsing process in the 1st rinsing process.At this moment, can utilize coefficient of thermal expansion poor of glass mold and resin dirt, make rinsing liquid efficient infiltrate into the interface of glass mold and resin dirt well.When rinsing liquid efficient infiltrates into above-mentioned interface well, can promote peeling off of resin dirt, spatter property increases as a result.
In more detail, temperature difference is more than 20 ℃ when glass mold and resin dirt attached to it are given, when preferred temperature difference is thermal shock more than 25 ℃, think that the resin dirt produces contraction, at least a portion resin dirt is peeled off from glass surface, composition of detergent infiltrates into by in the above-mentioned gap of peeling off the glass surface that reappears and resin dirt, thereby can promote peeling off of resin dirt.
Therefore, from showing the viewpoint of more excellent clean result, thermal shock is preferably carried out in said detergent composition, thus, in the 2nd washing procedure, so long as the preferred range of said detergent composition, then preferred serviceability temperature is come the cleaning glass mould than the low composition of detergent that more than 20 ℃, preferably hangs down more than 25 ℃ of temperature of employed composition of detergent in the 1st washing procedure.In addition, even if in the rinsing liquid, so long as after the washing that utilizes said detergent composition to carry out, also can obtain to give the effect that thermal shock produces, therefore in the rinsing process that after the 1st washing procedure and then, carries out, so long as it is the preferred range of rinsing liquid, can serviceability temperature lower more than 20 ℃ than the temperature of employed composition of detergent in the 1st washing procedure, preferably low rinsing liquid (pure water etc.) more than 25 ℃ comes the rinsing glass mold.Viewpoint from further raising washing performance, in the 2nd washing procedure in employed composition of detergent or the rinsing process that and then carries out after the 1st washing procedure temperature of employed rinsing liquid so long as the preferred range of composition of detergent or rinsing liquid, then more preferably low more than 25 ℃ than the temperature of employed composition of detergent in the 1st washing procedure, further preferred low more than 30 ℃, further preferably low more than 40 ℃.
When giving thermal shock by after the 1st washing procedure and then, carrying out the 2nd washing procedure and to glass mold and resin dirt, further give thermal shock to glass mold and resin dirt in the repeatedly rinsing process that preferably behind the 2nd washing procedure, carries out.Specifically, in the repeatedly rinsing process that behind the 2nd washing procedure, carries out, carry out rinsing in the above-mentioned preferred range of above-mentioned rinsing liquid, the temperature of the rinsing liquid that uses in the Y+1 time rinsing process is hanged down more than 20 ℃, is preferably hanged down more than 25 ℃ than the temperature of the rinsing liquid that uses in the Y time washing procedure.
And then, in the rinsing process (the 1st rinsing process) that after the 2nd washing procedure and then, carries out, using its temperature is behind the aqueous rinse rinsing glass mold more than 55 ℃, in the rinsing process (the 2nd rinsing process) that carries out after the 1st rinsing process and then, the aqueous rinse that preferred serviceability temperature is hanged down more than 20 ℃ than the temperature of the aqueous rinse of using in the 1st rinsing process is come the rinsing glass mold.Like this, when giving repeatedly thermal shock to glass mold and resin dirt continuously, washing performance further improves.
The glass mold that is attached with the resin dirt generally cleans in series being arranged with the multistage tank systems of a plurality of grooves.About 20～30 glass mold is put into anchor clamps, use conveyer belt automatically to be immersed in successively in each groove.The traveling time of glass mold from groove to groove was generally about 10～60 seconds, give the viewpoint of the effect of bringing from obtaining above-mentioned thermal shock effectively, above-mentioned mobile effect is more short more preferred, be preferably 30 seconds with interior, more preferably 20 seconds with interior, more preferably in 10 seconds.Whole multistage tank systems is disposed under the room temperature, is configured in particularly under 20～30 ℃ the environment.
In addition, sometimes the temperature of glass mold or resin dirt can descend during the movement of glass mold from groove to groove, and preferably the fluid temperature in next groove (thermal shock groove) is lower more than 20 ℃, more preferably low more than 25 ℃ than the temperature that just will enter glass mold before this groove or resin dirt.
Rinsing conditions such as the temperature of rinsing liquid and rinsing time also are not particularly limited, and can wait suitably according to the degree residual or that again adhere to of composition of detergent in glass mold and adjust.For example, the preferred range of rinsing liquid is preferably 5～75 ℃, from the viewpoint of rinsing or reduction water evaporation quantity, more preferably 20～60 ℃, more preferably 30～50 ℃.In addition, 1 time rinsing time is generally about 30 seconds～20 minutes.
For rinse method, can use normally used known rinse method.For example can be used singly or in combination various rinse methods such as infusion process, ultrasonic washing method, dipping ultrasonic washing method, dipping suspension system.
Carry out the cleaning of glass mold on the one hand, on the other hand plastic lens substrate is carried out the grinding (S4) (with reference to Fig. 1) of its periphery.Method for grinding can be any of wet type or dry type.Then, by washing grindstone dust etc. is removed back (S5) from plastic lens substrate, plastic lens substrate is carried out heat treated (annealing), thus acquisition plastic lens (S6).
Then, as required the single face of plastic lens is ground (S7).By through this operation, can make plastic lens reach the required number of degrees.Then, use pure water etc. is removed grinding agent etc., and plastic lens is cleaned (S8).
Then, as required to plastic lens dye (S9).Then, use pure water etc. that the plastic lens after the dyeing is cleaned (S10).Dyeing is used in the past, and known dyeing liquor and colouring method get final product.
Then, by etching two first type surfaces of plastic lens are carried out roughening (S11).Roughening carries out with the adaptation of plastic lens in order to improve hard conating etc.Etching solution for example uses aqueous alkali.Then, rinsing plastic lens such as use pure water form hard conating (S13) to clean back (S12) at two first type surfaces.The formation of hard conating is used in the past, and material known, formation method get final product.
Then, use pure water etc. cleans back (S14) to plastic lens, forms anti-reflection layer and stain-proofing layer (S15, S16) successively.The formation of hard conating and the formation of stain-proofing layer are used in the past respectively, and material known, formation method get final product.
Glasses more than have been described with example of the manufacture method of plastic lens and example of the employed method that glass mold is cleaned wherein, but the purposes of plastic lens is not to be defined in this.The present invention for example also applicable to illumination with, camera with or the manufacture method of the plastic lens of used for optical elements and the employed method that glass mold is cleaned wherein.In addition, the form of plastic lens is not particularly limited, can be spherical lens, non-spherical lens for example, increase progressively lens etc. any.
In addition, to be particularly preferred for refractive index be the manufacturing of the sulfur-bearing plastic lens more than 1.55, more preferably be used for refractive index is the manufacturing of the sulfur-bearing plastic lens more than 1.60, further is preferred for the manufacturing that refractive index is the sulfur-bearing plastic lens more than 1.70 for the method that glass mold is cleaned of the present invention and the manufacture method of using the plastic lens of this method.
Embodiment
[sample]
As the glass mold that is attached with sulfur-containing polyurethane resin dirt, prepared following glass mold: the face that helps plastic lens to be shaped that is about the glass mold of 8cm at the diameter that uses potassium nitrate to carry out chemical enhanced processing is formed with plastic lens resin (MR-8 resin, the Mitsui Chemicals, Inc's system that 10 diameters are about 5mm, sulfur-containing polyurethane resin system, refractive index are 1.60) agglomerate (resin dirt) (0.05g/ diameter 1cm/ each).In addition, plastic lens resin polymerization by the amounting to 24 hours heating of heating under 3 hours, 120 ℃ environment of heating under 2 hours, 100 ℃ environment of heating under 3 hours, 60 ℃ environment of heating under 7 hours, 50 ℃ environment of heating under 6 hours, 40 ℃ environment of heating under 30 ℃ of environment 3 hours, solid state.
[preparation of composition of detergent]
Be various composition of detergent (embodiment 1～15, comparative example 1～8) between 7～9 with the composition shown in the table 2 (ratio of components unit is weight %) preparation pH, use these composition of detergent to come cleaning glass mould (sample), estimate the washing performance of composition of detergent.
[decantation test]
The glass mold (sample) that is attached with sulfur-containing polyurethane resin dirt be impregnated in the composition of detergent of the embodiment 1～15 that remains in set point of temperature, comparative example 1～8, use 2 minutes (the 1st groove) of informed later (Co., Ltd. of Hewlett-Packard system, trade name SILENTSONIC UT-204,39kHz, 200W) washing.
Then, glass mold be impregnated in the composition of detergent of the embodiment 1～15 that remains in set point of temperature, comparative example 1～8, the identical informed later (39kHz, 200W) of employed informed later washs 2 minutes (the 2nd groove) when using with washing in the 1st groove.In addition, the traveling time of glass mold from groove to groove was made as for 10 seconds.
Then, glass mold be impregnated in the ion exchange water of set point of temperature, the identical informed later (39kHz, 200W) of employed informed later when using with washing in the 1st groove, each rinsing is 2 minutes in 2 grooves (the 3rd groove, the 4th groove).
Then, glass mold be impregnated in the ion exchange water of room temperature, the identical informed later (39kHz, 200W) of employed informed later when using with washing in the 1st groove, each rinsing is 2 minutes in 4 grooves (the 5th groove～the 8th groove).
Then, dry after 1 minute, use that (Toyo Seisakusho Co., Ltd, trade name: FV-630) 80 ℃ the heated-air drying of Gong Geiing is 10 minutes by air-supply freeze-day with constant temperature machine.
Table 1
The state of removing of the agglomerate of each plastic lens resin of visualization.As the evaluation criterion of washing performance, with the situation of agglomerate of removing each plastic lens resin fully as 10 minutes, the situation that will remove a part as 5 minutes, situation that will not remove fully as 0 minute.Agglomerate to 10 each plastic lens resins carries out above-mentioned observation, and the summation of the above-mentioned mark of the agglomerate of 10 plastic lens resins index as the expression washing performance is shown in Table 2.In addition, the total value of above-mentioned mark is more big, and the expression scourability is more good, means and has removed plastic lens resin more well.
The result who is put down in writing by table 2 as can be known, when use contains the composition of detergent that is selected from least a kind of phenyl ether in the phenyl ether shown in the phenyl ether shown in the above-mentioned general formula (1) and the general formula (2), even if resin dirt and glass mold are not given under the situation of thermal shock, can be removed the resin dirt that is attached on the plastic lens shaping dies well yet.In addition we know, when use contains the composition of detergent that is selected from least a kind of phenyl ether in the phenyl ether shown in the phenyl ether shown in the above-mentioned general formula (1) and the general formula (2) and gives thermal shock to resin dirt and glass mold, can remove the resin dirt that is attached on the plastic lens shaping dies more well.
As known from the above, according to the present invention, can provide the method that the glass mold to constituting the plastic lens shaping dies that can remove the resin dirt that is attached on the plastic lens shaping dies well cleans and the manufacture method of having used the plastic lens of this clean method.
Washing procedure when the present invention for example is preferred for making plastic lens such as eyeglass lens.
The present invention also can implement in other modes that do not break away from its spirit or substantive characteristics.Whole aspects of the disclosed embodiment of the application are for explanation, rather than be used for to limit.Scope of the present invention is not limited to above-mentioned detailed description, but by shown in the claim.And, comprise in the claims with the means of claim equalization and the change in the scope.
Claims (26)
1. method that the glass mold that constitutes the plastic lens shaping dies is cleaned, it contains the washing procedure that uses the plastic lens shaping dies to wash described glass mold with composition of detergent, described plastic lens shaping dies contains at least a kind of phenyl ether that is selected from the phenyl ether shown in the phenyl ether shown in the following general formula (1) and the general formula (2) with composition of detergent, and the content of described phenyl ether is 2 weight %～20 weight %
In general formula (1), (2), k be 1 or 2, EO be oxyethylene group, AO is that carbon number is 3 and/or 4 oxyalkylene group; N1 and n2 are average addition molal quantity, and n1 and n2 can be different mutually; M1 and m2 are that 3 oxyalkylene group is that PO is the average addition molal quantity of PO when constituting at AO by carbon number, be that 4 oxyalkylene group is that BO is the average addition molal quantity of BO when constituting at AO by carbon number, be the sum of the average addition molal quantity of the average addition molal quantity of PO and BO when AO comprises PO and BO, m1 and m2 can be different mutually; N1 is 3～100 number, and n2 is 3～100 number, and m1 is the number of 0～0.2 * n1, and m2 is the number of 0～0.2 * n2; (EO)
N1(AO)
M1(EO)
N2(AO)
M2EO separately and the arrangement of AO can be blocks, also can be random; When AO comprised PO and BO, the arrangement of PO and BO can be block, also can be random; EO can insert in the arrangement that is made of PO and/or BO with block or random mode.
2. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 1, it further contains the 2nd washing procedure or rinsing process, and then described the 2nd washing procedure namely carries out after the 1st washing procedure at the described washing procedure that uses described plastic lens shaping dies to wash described glass mold with composition of detergent
The described plastic lens shaping dies that uses in described the 1st washing procedure is more than 55 ℃ with the temperature of composition of detergent,
In described the 2nd washing procedure, serviceability temperature is come the cleaning glass mould than the described plastic lens shaping dies that employed described plastic lens shaping dies in described the 1st washing procedure hangs down more than 20 ℃ with the temperature of composition of detergent with composition of detergent,
In the described rinsing process, serviceability temperature is come the described glass mold of rinsing than employed described plastic lens shaping dies in described the 1st washing procedure with the low aqueous rinse more than 20 ℃ of temperature of composition of detergent.
3. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 2, wherein, when after described the 1st washing procedure and then, carrying out the 2nd washing procedure, further contain the repeatedly rinsing process that after described the 2nd washing procedure and then, carries out
The rinsing process that carries out after described the 2nd washing procedure and then is namely in the 1st rinsing process, serviceability temperature is the described glass mold of aqueous rinse rinsing more than 55 ℃, afterwards, namely in the 2nd rinsing process, serviceability temperature is come the described glass mold of rinsing than the low aqueous rinse more than 20 ℃ of temperature of employed described aqueous rinse in described the 1st rinsing process to the rinsing process that carries out after described the 1st rinsing process and then.
4. according to each described method that the glass mold that constitutes the plastic lens shaping dies is cleaned of claim 1～3, wherein, described plastic lens shaping dies further contains water-soluble glycol ether with composition of detergent.
5. the manufacture method of a plastic lens, it contains following operation:
The plastic lens of 1 pair of glass mold that the interval that use contains to stipulate disposes opposite to each other is with the be shaped forming process of plastic lens substrate of shaping dies;
Stripping process with the demoulding from the described plastic lens substrate of described glass mold;
Behind described stripping process, the cleaning process that right to use requires the 1 described method that the glass mold that constitutes the plastic lens shaping dies is cleaned that described glass mold is cleaned,
Wherein, for the plastic lens substrate that repeatedly is shaped, described 1 pair of glass mold reuses through behind the described cleaning process.
6. the manufacture method of plastic lens according to claim 5, wherein, use the polymerism resin more than a kind be selected from sulfur-containing polyurethane resin, sulfur-bearing epoxy resin, poly-sulfo-(methyl) acrylate and the episulfide resin as described plastic lens substrate raw material.
7. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 1 and 2, wherein, described plastic lens shaping dies is 4～15 weight % with the content of the described phenyl ether in the composition of detergent.
8. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 4, wherein, the content of described water-soluble glycol ether is 5～150 weight portions with respect to described phenyl ether 100 weight portions.
9. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 1 and 2, wherein, described plastic lens shaping dies contains solvent with composition of detergent, and described solvent is pure water.
10. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 9, wherein, described plastic lens shaping dies is 80～98 weight % with the content of described solvent contained in the composition of detergent.
11. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 2, wherein, described plastic lens shaping dies is 7～9 with the pH under 25 ℃ of composition of detergent.
12. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 2, wherein, employed described plastic lens shaping dies is 60～80 ℃ with the temperature of composition of detergent in the 1st washing procedure.
13. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 2, wherein, the temperature range of described aqueous rinse is 30～50 ℃.
14. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 3, wherein, described plastic lens shaping dies is 7～9 with the pH under 25 ℃ of composition of detergent.
15. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 3, wherein, employed described plastic lens shaping dies is 60～80 ℃ with the temperature of composition of detergent in described the 1st washing procedure.
16. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 3, wherein, the temperature range of described aqueous rinse is 30～50 ℃.
17. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 1 and 2, wherein, described phenyl ether is the polyoxyethylene-3 of n1=5～50, m1=0, the polyoxyethylene-2 of two (1-phenylethyl) phenyl ethers of 5-or n2=5～50, m2=0,4,6-three (1-phenyl methyl) phenyl ether.
18. the method that the glass mold that constitutes the plastic lens shaping dies is cleaned according to claim 17, wherein, described plastic lens shaping dies is 4～15 weight % with the content of the described phenyl ether in the composition of detergent.
19. the plastic lens shaping dies purposes of composition of detergent in the cleaning of the glass mold that constitutes the plastic lens shaping dies, it contains at least a kind of phenyl ether that is selected from the phenyl ether shown in the phenyl ether shown in the following general formula (1) and the general formula (2), and the content of described phenyl ether is 2 weight %～20 weight %
In general formula (1), (2), k be 1 or 2, EO be oxyethylene group, AO is that carbon number is 3 and/or 4 oxyalkylene group; N1 and n2 are average addition molal quantity, and n1 and n2 can be different mutually; M1 and m2 are that 3 oxyalkylene group is that PO is the average addition molal quantity of PO when constituting at AO by carbon number, be that 4 oxyalkylene group is that BO is the average addition molal quantity of BO when constituting at AO by carbon number, be the sum of the average addition molal quantity of the average addition molal quantity of PO and BO when AO comprises PO and BO, m1 and m2 can be different mutually; N1 is 3～100 number, and n2 is 3～100 number, and m1 is the number of 0～0.2 * n1, and m2 is the number of 0～0.2 * n2; (EO)
N1(AO)
M1(EO)
N2(AO)
M2EO separately and the arrangement of AO can be blocks, also can be random; When AO comprised PO and BO, the arrangement of PO and BO can be block, also can be random; EO can insert in the arrangement that is made of PO and/or BO with block or random mode.
20. the purposes in the cleaning of glass mold according to claim 19, wherein, described phenyl ether is the polyoxyethylene-3 of n1=5～50, m1=0, the polyoxyethylene-2 of two (1-phenylethyl) phenyl ethers of 5-or n2=5～50, m2=0,4,6-three (1-phenyl methyl) phenyl ether.
21. according to claim 19 or 20 described purposes in the cleaning of glass mold, wherein, described plastic lens shaping dies is 4～15 weight % with the content of the described phenyl ether in the composition of detergent.
22. the purposes in the cleaning of glass mold according to claim 19, wherein, described plastic lens shaping dies contains solvent with composition of detergent, and described solvent is pure water.
23. the purposes in the cleaning of glass mold according to claim 22, wherein, described plastic lens shaping dies is 80～98 weight % with the content of described solvent contained in the composition of detergent.
24. the purposes in the cleaning of glass mold according to claim 19, wherein, described plastic lens shaping dies further contains water-soluble glycol ether with composition of detergent.
25. the purposes in the cleaning of glass mold according to claim 24, wherein, the content of described water-soluble glycol ether is 5～150 weight portions with respect to described phenyl ether 100 weight portions.
26. the purposes in the cleaning of glass mold according to claim 19, wherein, described plastic lens shaping dies is 7～9 with the pH under 25 ℃ of composition of detergent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP216436/2008 | 2008-08-26 | ||
| JP2008216436A JP5216483B2 (en) | 2008-08-26 | 2008-08-26 | Cleaning composition for plastic lens mold |
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| CN102091705A CN102091705A (en) | 2011-06-15 |
| CN102091705B true CN102091705B (en) | 2013-08-14 |
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| JP (1) | JP5216483B2 (en) |
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| CN105062706B (en) * | 2015-08-14 | 2018-01-09 | 上海奈拓化工科技有限公司 | Resin optical lens matched moulds glass mold high-precision ultrasound cleaning agent |
| JP7220867B2 (en) * | 2018-11-19 | 2023-02-13 | 株式会社修護 | Material cleaning device |
| CN109570162A (en) * | 2018-11-26 | 2019-04-05 | 蓝思科技股份有限公司 | The cleaning method of vacuum formed box |
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| CN101148635A (en) * | 2006-09-11 | 2008-03-26 | 花王株式会社 | Cleaning agent composition for plastic lens |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0774865B2 (en) * | 1984-05-23 | 1995-08-09 | 千寿製薬株式会社 | Contact lens cleaner |
| JPH09151393A (en) * | 1995-11-29 | 1997-06-10 | Toho Chem Ind Co Ltd | Detergent composition |
| JP2949574B2 (en) * | 1997-01-09 | 1999-09-13 | 花王株式会社 | Cleaning composition for resin stains |
| JPH10270846A (en) * | 1997-03-21 | 1998-10-09 | Ebara Yuujiraito Kk | Degreaser for desmearing |
| JP3420922B2 (en) * | 1997-10-29 | 2003-06-30 | 花王株式会社 | Detergent composition for plastic lens molded glass mold |
| JP3370262B2 (en) * | 1997-11-25 | 2003-01-27 | 花王株式会社 | Cleaning method for plastic lens molded glass mold |
| JP3365942B2 (en) * | 1997-11-25 | 2003-01-14 | 花王株式会社 | Cleaning method for plastic lens molded glass mold |
| JP3233279B2 (en) * | 1998-10-06 | 2001-11-26 | 日本アイ・ビー・エム株式会社 | Cleaning composition and cleaning method |
| JP4189988B2 (en) * | 2001-09-06 | 2008-12-03 | 花王株式会社 | Cleaning method |
| JP2005162780A (en) * | 2003-11-28 | 2005-06-23 | Ibm Japan Ltd | Detergent composition and detergent for liquid crystal cell |
| JP2006124696A (en) * | 2004-10-01 | 2006-05-18 | Kao Corp | Detergent composition |
| JP4853089B2 (en) * | 2006-04-07 | 2012-01-11 | コニカミノルタオプト株式会社 | Method for producing cellulose ester film |
| JP5048277B2 (en) * | 2006-06-07 | 2012-10-17 | ディバーシー株式会社 | Deodorant composition for CIP and method of using the same |
| EP2721134A1 (en) | 2011-06-20 | 2014-04-23 | The Procter and Gamble Company | Liquid cleaning and/or cleansing composition |
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| CN101148635A (en) * | 2006-09-11 | 2008-03-26 | 花王株式会社 | Cleaning agent composition for plastic lens |
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| CN102091705A (en) | 2011-06-15 |
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| KR101585634B1 (en) | 2016-01-14 |
| JP5216483B2 (en) | 2013-06-19 |
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