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Join us for Jazz Vespers at Christ Church Deer Park.
This will be an afternoon of live jazz, reflective readings, prayers for our city and the world, and a jazzy congregational hymn! It is one of their most popular services - with wonderful music, and with some of the finest jazz artists in Canada.
For those who have been so far, these events have been surprisingly delightful, the musicians who appear are of the highest quality anywhere! The readings appeal to anyone with even the slightest of an inclining of humanity to them - meant to inspire and uplift.
Performance scheduled for today: Canadian Jazz Quartet
Gary Benson, guitar;
Don Vickery,drums
Frank Wright, vibes;
Duncan Hopkins, bass
Service begins at 4:30 p.m. (Usually runs until 6 pm)
Please be at the church by 4:00 p.m. I will try to be there a bit early and greet you at the door.
Otherwise, we usually sit at the front on the left hand side, if I arrive late.
There is no admission charge, but a collection will be collected.
It would be great if we had a large turn out for this event. It is a lovely church and a lovely very inexpensive afternoon of high quality jazz and they deserve our support to help keep this event going.
Please tell your friends and colleagues.
Christ Church Deer Park is located on the west side of Yonge a few blocks north of St Clair. Very close to the subway for those who are TTCing it.
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April 29, 2016
Husband Wins Right to Tell Wife's Story of Assisted Death
(The Globe and Mail) – The death of Hanne Schafer was by any definition a nightmare. Suffering from the painful, degenerative neurological disease ALS, the 66-year-old could communicate only by typing with some of the fingers on her left hand. … Read More

subset: commoncrawl


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MANCHESTER, UK and HILLSBORO, Ore., Sept. 4, 2012 (GLOBE NEWSWIRE) -- The University of Manchester and FEI (Nasdaq:FEIC) are pleased to announce the installation of one of the world's most powerful high-resolution microscopes―the Titan™ G2 80-200 scanning transmission electron microscope (S/TEM)―at the University's School of Materials. The procurement of the new S/TEM from FEI was funded as part of an £8 million ($12.8 million USD) UK government investment for nuclear materials research at Manchester's Dalton Nuclear Institute.
University Of Manchester Installs New Ultra-Powerful Microscope From FEI
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In simple terms, how would you explain (perhaps with simple examples) the difference between fixed effect, random effect and mixed effect models?
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Blogger Andrew Gelman says that the terms 'fixed effect' and 'random effect' have variable meanings depending on who uses them (link). Perhaps you can pick out which one of the 5 definitions applies to your case. In general it may be better to either look for equations which describe the probability model the authors are using (when reading) or write out the full probability model you want to use (when writing).
Fixed effect: Something the experimenter directly manipulates and is often repeatable, e.g., drug administration - one group gets drug, one group gets placebo.
Random effect: Source of random variation / experimental units e.g., individuals drawn (at random) from a population for a clinical trial. Random effects estimates the variability
Mixed effect: Includes both, the fixed effect in these cases are estimating the population level coefficients, while the random effects can account for individual differences in response to an effect, e.g., each person receives both the drug and placebo on different occasions, the fixed effect estimates the effect of drug, the random effects terms would allow for each person to respond to the drug differently.
General categories of mixed effects - repeated measures, longitudinal, hierarchical, split-plot.
There are good books on this such as Gelman and Hill. What follows is essentially a summary of their perspective.
First of all, you should not get too caught up in the terminology. In statistics, jargon should never be used as a substitute for a mathematical understanding of the models themselves. That is especially true for random and mixed effects models. "Mixed" just means the model has both fixed and random effects, so let's focus on the difference between fixed and random.
Mathematically, the difference between fixed and random effects modeling is that the latter uses a multilevel approach to estimate the variation in a response across multiple groups of observations.* This means that, if you have few data points in a group, the group's effect estimate will be based partially on the more abundant data from other groups. This is known as partial pooling, and it's a nice compromise between completely pooling all groups, which masks group-level variation, and treating all groups completely separately, which could give poor estimates for low-sample groups.
An example should help prime your intuition. Suppose you want to estimate average US household income by ZIP code. You have a large dataset containing observations of households' incomes and ZIP codes. Some ZIP codes are well represented in the dataset, but others have only a couple households.
For your initial model you would most likely take the mean income in each ZIP. This will work well when you have lots of data for a ZIP, but the estimates for your poorly sampled ZIPs will suffer from high variance. You can mitigate this by using a shrinkage estimator (aka partial pooling), which will push extreme values towards the mean income across all ZIP codes.
But how much shrinkage/pooling should you do for a particular ZIP? Intuitively, it should depend on the following:
If you model ZIP code as a random effect, the mean income estimate in all ZIP codes will be subjected to a statistically well-founded shrinkage, taking into account all the factors above.
The best part is that random and mixed effects models automatically handle (4), the variability estimation, for all random effects in the model. This is harder than it seems at first glance: you could try the variance of the sample mean for each ZIP, but this will be biased high, because some of the variance between estimates for different ZIPs is just sampling variance. In a random effects model, the inference process accounts for sampling variance and shrinks the variance estimate accordingly.
Having accounted for (1)-(4), a random/mixed effects model is able to determine the appropriate shrinkage for low-sample groups. It can also handle much more complicated models with many different predictors.
If this sounds like hierarchical Bayesian modeling to you, you're right - it is a close relative but not identical. Mixed effects models are hierarchical in that they posit distributions for latent, unobserved parameters, but they are typically not fully Bayesian because the top-level hyperparameters will not be given proper priors. For example, in the above example we would most likely treat the mean income in a given ZIP as a sample from a normal distribution, with unknown mean and sigma to be estimated by the mixed-effects fitting process. However, a (non-Bayesian) mixed effects model will typically not have a prior on the unknown mean and sigma, so it's not fully Bayesian. That said, with a decent-sized data set, the standard mixed effects model and the fully Bayesian variant will often give very similar results.
*While many treatments of this topic focus on a narrow definition of "group", the concept is in fact very flexible: it is just a set of observations that share a common property. A group could be composed of multiple observations of a single person, or multiple people in a school, or multiple schools in a district, or multiple varieties of a single kind of fruit, or multiple kinds of vegetable from the same harvest, or multiple harvests of the same kind of vegetable, etc. Any categorical variable can be used as a grouping variable.
I have written about this in a book chapter on mixed models (chapter 13 in Fox, Negrete-Yankelevich, and Sosa 2014); the relevant pages (pp. 311-315) are available on Google Books. I think the question reduces to "what are the definitions of fixed and random effects?" (a "mixed model" is just a model that contains both). My discussion says a bit less about their formal definition (for which I would defer to the Gelman paper linked by @JohnSalvatier's answer above) and more about their practical properties and utility. Here are some excerpts:
The distinction is only meaningful in the context of non-Bayesian statistics. In Bayesian statistics, all model parameters are "random".
Not really a formal definition, but I like the following slides: Mixed models and why sociolinguists should use them (mirror), from Daniel Ezra Johnson. A brief recap' is offered on slide 4. Although it mostly focused on psycholinguistic studies, it is very useful as a first step.
I came to this question from here, a possible duplicate.
There are several excellent answers already, but as stated in the accepted answer, there are many different (but related) uses of the term, so it might be valuable to give the perspective as employed in econometrics, which does not yet seem fully addressed here.
Consider a linear panel data model: $$ y_{it}=X_{it}\delta+\alpha_i+\eta_{it}, $$ the so-called error component model. Here, $\alpha_i$ is what is sometimes called individual-specific heterogeneity, the error component that is constant over time. The other error component $\eta_{it}$ is "idiosyncratic", varying both over units and over time.
A reason to use a random effects approach is that the presence of $\alpha_i$ will lead to an error covariance matrix that is not "spherical" (so not a multiple of the identity matrix(, so that a GLS-type approach like random effects will be more efficient than OLS.
If, however, the $\alpha_i$ correlate with the regressors $X_{it}$ - as will be the case in many typical applications - omitting these individual-specific intercepts will lead to omitted variable bias. Then, a fixed effect approach which effectively fits such intercepts will be more convincing.
The following figure aims to illustrate this point. The raw correlation between $y$ and $X$ is positive. But, the observations belonging to one unit (color) exhibit a negative relationship - this is what we would like to identify, because this is the reaction of $y_{it}$ to a change in $X_{it}$.
Also, there is correlation between the $\alpha_i$ and $X_{it}$: If the former are individual-specific intercepts (i.e., expected values for unit $i$ when $X_{it}=0$), we see that the intercept for, e.g., the lightblue panel unit is much smaller than that for the brown unit. At the same time, the lightblue panel unit has much smaller regressor values $X_{it}$.
So, random effects or pooled OLS would be the wrong strategy here, because it would result in a positive esimate of $\delta$, as these two estimators basically ignore the colors (RE only incroporates the colors for the estimate of the variance covariance matrix).


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Six months after the Arkansas State Medical Board reprimanded and fined Oldenberg and suspended and revoked her license to practice medicine, Kissee has filed his court plea to reverse the action he calls a "death penalty" against his client.
Kissee, who appealed the Medical Board penalties to Sharp Circuit Court on Oct. 27, 2010, has filed a 56 page brief accusing the Medical Board of committing twelve errors as it took disciplinary action against Oldenberg.
Medical Board Attorney Michael Trice has responded with a 24 page brief defending the Board's actions.
The written briefs will be a guide as Circuit Judge Kevin King considers the arguments and case law cited, and makes a ruling in Oldenberg's case.
Dr. Denise Oldenberg, who specializes pain management, has had offices in Salem, Horseshoe Bend, and, most recently, Cherokee Village over the past 22 years.
Her approach of prescribing high amounts of narcotic drugs to patients with chronic pain has led to state scrutiny many times over the years.
On Sept. 8, 2010, Oldenberg appeared before the Medical Board in Little Rock, representing herself without an attorney. She was charged with violating agreements with the Board to submit reports showing all Schedule II narcotic drugs she prescribed to patients and prescribing Schedule II drugs, after agreeing not to, while charges against her were pending.
While an Oct. 9 Board decision permanently revoked her medical license, Judge King ruled on Nov. 18 that, while her court appeal was pending, Oldenberg could continue to practice, as long as she did not prescribe Schedule II narcotics.
In his brief, Kissee begins by telling the court it, "may reverse or modify the Board's decision if the substantial rights of the petitioner have been prejudiced..."
Kissee goes on to compare Oldenberg's Medical Board hearing to the trial of the Knave of Hearts in Alice in Wonderland.
The brief describes how The White Rabbit reads a poem which claims the Knave of Hearts stole some tarts made by the Queen.
The King, who serves as judge, calls for a jury, made up of animals and birds, to make a verdict.
While the White Rabbit says, "Not yet, not yet!" and a witness is called, the Queen finds the Knave guilty.
Kissee writes, "What's the difference between this 1860's trial in Lewis Carroll's novel and the Arkansas State Medical Board Hearing of the charges against Denise Oldenberg, M.D., October, 2010? The Board Members (Judges and Jurors) were not impartial and their decisions were driven by- what? Abuse of power is still common."
Kissee goes on to list what he alleges are critical Board errors:
*The Board allowed its attorney, Trice, to serve as prosecutor and their advisor, a violation of due process.
*The Board failed to submit allegations of "improper prescribing" to the Pain Management Review Committee, for guidance, as required by law.
*The Board found Oldenberg guilty of "over-prescribing," even though the board has failed to set standards to describe and define "over-prescribing."
*The Board's "expert witnesses," who testified against Oldenberg, were not specialists or experts in their fields.
*The Board took emergency action against Oldenberg when no emergency existed.
*The Board falsely claimed it had levied six prior convictions against Oldenberg, when a court dismissed one conviction and all others were dropped or not sustained.
*The Board found Oldenberg guilty of "gross negligence" without providing "substantial" evidence she was guilty of inadequate patient monitoring and record keeping.
*The Board's deliberations were "biased" and "outrageous" and "showed medical ignorance."
As an example of the Board's alleged "abuse of power," Kissee notes the Board recorded the hearing in which witnesses testified against Oldenberg, but did not record its own deliberations, during which severe penalties were levied.
Kissee insists revoking Oldenberg's license because "She violated (allegedly) the consent order with one established patient prescribing two Schedule II controlled substances" was much too severe a penalty.
"The Board revoked her (Oldenberg's) license for a simple violation of a consent order. Her practice is almost destroyed. Her life as a doctor destroyed after 22 years of practice unless she receives this relief. There is nothing to justify such harsh, drastic action," Kissee writes.
Medical Board Attorney William Trice's brief seems to skoff at Kissee's laundry list of complaints.
Trice explains the Board has the legal right "to discipline or sanction licensees (physicians), who have violated the Medical Practices Act or the Rules and Regulations of the Board."
According to Trice, the Board held a disciplinary hearing into "various offenses" against Oldenberg and it "entered different sanctions with different levels of severity, depending on which violation the Board found Dr. Oldenberg committed."
Trice states the Board acted within its powers as a state agency and claims Kissee makes no claim in his appeal "that the sanctions imposed were beyond the statutory authority granted to the Board."
Trice states that expert witnesses who testified against Oldenberg based their testimony on their expertise, after reviewing patient records and prescribing records.
He notes that "Dr. Oldenberg's witness, Dr. Ronald Meyers, testified that he had not even reviewed the patient records."
Trice indicates that, while the appeal raises many issues, the primary issue before the court is "whether the Board made incorrect findings of fact in the disciplinary hearing itself, and were the sanctions imposed within the Board's authority."
Trice claims the Board's actions were taken after "a vast amount of Exhibits to include medical records and prescriptions and expert testimony that was given and the Administrative Procedure Action was complied with."
The discipline, according to Trice, was also based on, "The Board's history with Denise Oldenberg, M.D. and the numberous consent orders the Board has entered into with her, where the Board has tried to rehabilitate her and provide her education..."
Trice disputes the claim that revoking Oldenberg's license "was too severe."
"Due to the volume of evidence it was not too severe in the opinion of the Board. Dr. Oldenberg tends to not mention, that out of the various negative findings against her by the Board, it only revoked her license for violating two Consent Orders she had entered into with the Board."
Is Oldenberg trapped in an Alice in Wonderland bad dream, as Kissee's brief claims?
Trice responds, "The Brief of Dr. Oldenberg MD, pages 3, 4, 5, argues by some sort of analogy the Lewis Carroll's "Alice in Wonderland." Said argument is as interesting and bizarre as Lewis Carroll's work."
With briefs filed, the next step in this appeal will be a hearing to allow attorneys to present oral arguments to Judge King. The hearing date has not been set.
"It is all in a judge's hands and I feel very good about the future," Denise Oldenberg told Areawide News. "My brief proves the Medical Board did not follow its own rules and the punishment it handed out was much too severe for minor violations of a Consent Order."
While Oldenberg was given the right to practice medicine during her appeal, her office is open only one or two days a week to serve long time patients.
"Since I cannot prescribe pain medications, I have tried to help my patients find other doctors who can really help them," Oldenberg said. "About all I can do for my patients is treat their diabetes, high blood pressure or things like that."
The hearing date for oral arguments has not been set.


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By | Julie Sun '14
Shanghai, China
Chemistry (biochemistry emphasis)
Auxin is a hormone that regulates the development and growth of plants. In our research we used small organic molecules as tools to probe a set of protein-protein interactions that occur when a cell responds to auxin. Our investigation has led to a better understanding of plant growth, which could in turn lead to advances in agriculture, biofuels, and forest management.
My organic chemistry class prepared me to understand the basics of synthesis, and my biology courses helped me to appreciate the dynamics of protein-protein interactions in hormone-response pathways. At Macalester, classes not only teach students the scientific knowledge, but also encourage us to dive into the research literature.
Being a science major at Macalester is a great experience. Olin-Rice Science Center is a great place for students to get to know each other and work together in groups. Also, my professors are extremely accessible—answering questions, mentoring and advising us.
Because Macalester is located just minutes away from University of Minnesota, I have regularly been able to take advantage of chemistry seminars held there.
In addition, thanks to Macalester's has close relationships with the Mayo Clinic, I was able to participate last year in the Mayo Innovation Scholars Program. Together with three other students—one biology and two economics majors—I evaluated the science and marketability of a Mayo Clinic product and learned how to transform bench research into a useful medical tool.
January 22 2014Back to top
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So it is time to you incorporate these people into your society. THere are millions of Lebanese immingrants around the world and they became normal citizens. Why dont you show a little bit of compassion and make this 500.000 Lebanese? Or do you believe they will ever return to Tel Aviv or Haifa to their grandparent's houses? The refugees issue cannot be used endlessly for all your problems. A million Jews were exelled from arab lands. These people were received and made into citizens. Why dont you follow this example?
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CNN: Ex-Texas Gov. Perry endorses Trump, says he's open to VP run (Reuters)
from the article: Lebanon army dismantles 4 rockets aimed at Israel


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Marco Rubio became the latest 2016 presidential candidate to leave the race after losing his home state of Florida. Here's a look at him and the other former candidates who have also ended their campaigns.
During an interview on Dec. 21, 2015, South Carolina Sen. Lindsey Graham said he was suspending his presidential campaign.


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Petit Palace Madrid Aeropuerto, Madrid
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Woman arrested for DWIPublished 10:54am Friday, May 3, 2013
Deputies respond to vehicles stuck in snow, in ditch
Freeborn County Sheriff's Office deputies responded to at least two dozen reports of vehicles stuck in the snow or that had traveled into the ditch on Thursday.
Police respond to downed lines, trees
Albert Lea police responded to at least 30 reports of downed power lines or downed trees, according to reports.
Woman arrested for DWI
Albert Lea police arrested Pamela Jean Ready, 56, for driving while intoxicated after receiving a report of a suspicious person in a vehicle at 205 N. Ermina Ave. at 4 p.m. Wednesday, according to reports.
Car broken into
A car was reported broken into at 805 Freeborn Ave. at 7:18 a.m. Thursday, according to Albert Lea police.
Vehicles reported damaged
Vehicles were reported damaged at Motor Inn Co., 2114 E. Main St. in Albert Lea, 11:15 a.m. Thursday, police reported.
Fire reported
A small electrical fire was reported at Perkins, 2215 E. Main St., at 9:20 p.m. Thursday, according to Albert Lea police. Reports indicated the Albert Lea Fire Department responded and put out the fire. It was unclear as of press time where the fire originated.
Man cited for criminal damage
Albert Lea police cited Jeremiah Edward Fenney, 29, for criminal damage after receiving a report of potential break-in at 509 Ulstad Ave. at 12:45 a.m. today, according to reports.


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This profile was last updated on 2/3/15 and contains information from public web pages and contributions from the ZoomInfo community.
Raul RamirezWrong Raul Ramirez?
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ProPub_Iteration_NT.402[01] SEIDXWK-19


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A ruling in the sales tax lawsuit against the city of Purdy has taken a significant change of course and is now heading toward a new hearing. Circuit Judge Robert Wiley has reversed his decision against the city.
Judge Wiley had issued an injunction on April 29 against the city for having two one-cent sales taxes for the same purpose with a final judgment against the city. The injunction stemmed from a lawsuit filed by Farmington attorney Tom Burcham, who is pursuing litigation around the state claiming stacked sales taxes are illegal, despite voter approval.
On Aug. 20, Judge Wiley issued a final ruling against the city.
According to Don Trotter, city attorney for Purdy, Judge Wiley issued his final judgment ruling before he received the city's rebuttal to Burcham's claims.
The city had hired the St. Louis law firm of Cunningham, Vogel and Rost as special legal counsel in the city's case. Trotter said the city's response, running close to 80 pages, was subsequently filed.
Judge Wiley reviewed the Purdy case as presented, and on Aug. 28, rescinded his final judgment in the case. Wiley subsequently lifted the original injunction.
"The court on its own motion set aside the final judgment, based on 'new case authority in the briefs just submitted.' That is extremely unusual," Trotter said.
Purdy's response was prepared with the assistance of co-counsel Dan Vogel from the St. Louis firm.
"Dan Vogel did a great job," Trotter added.
The case will now be heard again in court. Trotter said Burcham, who recently filed suits against the cities of Granby and Joplin based on Judge Wiley's ruling, has been asked to respond to the legal arguments cited in the Purdy rebuttal. Once Burcham's response has been submitted, the new hearing will be scheduled.
Trotter said the Purdy City Council was very encouraged by Judge Wiley's latest decision. Trotter remained confident that the legal foundation developed with the assistance of the St. Louis law firm would prevail.
Burcham has applied to the 39th Judicial Circuit to be repaid for legal fees for his time spent on the case.
In light of the lawsuit, the Purdy City Council dramatically restructured its budget for the fiscal year that began on July 1. Three-quarters of funding for the duties of the city clerk were shifted from the general fund onto the water and sewer funds.
The new budget also instituted a 3 percent increase for the cost of water over the 3,000 base amount. The base sewer rate was increased by $1, plus the cost of every subsequent 1,000 gallons was increased by an additional 75 cents.
If the city prevails in the lawsuit, the squeeze caused by the loss of half the city's sales tax income would reduce the pressure to make up the difference with utility rates.


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April Denise Redus and Adam Carl Sisco will be married June 21 at the Oak Hill Missionary Baptist Church located on FF Highway, off 160 Highway at Alton, Mo.
April is the daughter of Diann and Bruce Pickett of Myrtle, Mo., and Irvin (Buster) and Carol Redus of Gatewood, Mo. Adam is the son of Dennis and Judy Sisco of Alton.
The ceremony will begin at 2 p.m. and the reception will follow.
Adam and April extend an invitation to all friends and family to join them in this happy event in their lives.


text:
Two Marshall players were honorable mention selections to the Missouri High School Baseball Coaches' Association Class 3 all-state team for their performances during the 2012 season.
Senior third baseman Jordan Pannell led the Owls with a .364 batting average and was second on the club in on-base percentage at .477. He had 32 hits and drove in 23 runs in 88 at-bats, with 15 extra-base hits -- including 10 doubles and three homers.
Senior pitcher Aaron Skinner topped Marshall (17-12), which finished fourth in its first trip to the MSHSAA Championships, with a 6-3 record and 2.73 earned-run average. The southpaw struck out 58 batters in 51-plus innings pitched.


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|Publication number
|Publication type
|Application number
|Publication date
|May 7, 1991
|Filing date
|Feb 15, 1989
|Priority date
|Feb 22, 1988
|Fee status
|Also published as
|Publication number
|Teruyuki Nagata, Koju Okazaki, Nobuyuki Kajimoto, Tohru Miura, Yoshinobu Kanemura, Katsuyoshi Sasagawa
|Original Assignee
|Mitsui Toatsu Chemicals, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (9), Referenced by (20), Classifications (19), Legal Events (7)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention:
The present invention relates to a plastic lens and a process for making the plastic lens. More particularly, the invention relates to a process for making a plastic lens having urethane bonds or S-alkyl thiocarbamate bonds, and a lens produced by the process.
2. Description of the Prior Art:
It is known to use diethylene glycol-bis(allylcarbonate) (hereinafter referred to as DAC), PMMA and polycarbonate for preparing lenses. It is known to use an internal mold releasing agent such as butyl phosphate to improve the mold releasing properties upon molding these materials. However, internal molding agents are not required and result in impaired appearance of molded articles [Seiichi Mima, Polymer Digest, 3, 39 (1984); etc.].
Polyurethane base lenses exhibit high refractive described materials. However, polyurethane adheres to a mold upon molding, and thus it is difficult to release the lens from the mold after polymerization. With this phenomenon in view, the present inventors previously proposed a process in which an external mold releasing agent is used (Japanese Patent Laid-Open No. 267316/1987, etc.) and a process in which a polyolefin resin mold is used (Japanese Patent Laid-Open No. 236818/1987) to improve mold releasing properties.
However, these foregoing processes are still insufficient in casting polymerization of polyurethane base lenses.
In a process in which an external mold releasing agent is used, a surface treating material on the inner surface of a mold is transferred to the surface or interior of the polymerized lens, thus producing irregularity or unevenness on the surface of the lens or turbidity within the lens. Further, whenever the mold is used repeatedly, it requires mold releasing treatment, this making the process complicated for use in industrial applications and thus is very uneconomical due to the low productivity of the lens.
A polyolefin resin mold is deformed at elevated temperature so that the resulting molded lens has poor surface profile regularity. Thus, the lens is not suitable for use in applications in which a high degree of profile regularity is required.
The present invention overcomes the problems and disadvantages of the prior art by providing a process for producing a plastic lens having a high refractive index and exhibiting superior properties over prior art lenses.
It is an object of the invention to provide an efficient process for preparing a plastic lens which is suitable for use on an industrial scale.
It is a further object of the invention to provide a process for preparing a plastic lens which has a high degree of profile regularity and excellent optical characteristics, and a lens produced by the process.
It is also an object of the invention to provide a process for preparing a plastic lens that has a high refractive index, is lightweight, has excellent impact resistance and weatherability.
Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention will be realized and attained by means of the instrumentalities and combinations, particularly pointed out in the appended claims.
To achieve the objects and in accordance with the purpose of the invention, as embodied and broadly described herein, the invention provides a process for producing a plastic lens having a high refractive index comprising forming a mixture of (a) one or more of sulfurcontaining aromatic polyisocyanate compounds; (b) one or more of active hydrogen compounds selected from the group consisting of polyol compounds and polythiol compounds; and (c) at least one internal mold releasing agent; pouring the mixture into a mold and polymerizing the same to form a plastic lens. The process of the invention can be carried out efficiently and economically on an industrial scale and provides a plastic lens having a high refractive index, a high degree of profile regularity, excellent impact resistance and excellent optical characteristics, and being lightweight.
Reference will now be made in detail to the present preferred embodiments of the invention. Exemplary suitable internal mold releasing agents for use in the present invention include fluorine-base nonionic surface active agents, silicon-base nonionic surface active agents, quaternary alkylammonium salts, acidic phosphates, liquid paraffins, waxes, higher fatty acids and metal salts thereof, higher fatty acid esters, higher fatty alcohols, bisamides, polysiloxanes, and aliphatic amine ethylene oxide additives. The internal mold releasing agents are selected in view of the combination of monomers and polymerization conditions employed, as well as the economical efficiency, and ease of handling of particular materials. The internal mold releasing agents may be used singly or as a mixture of two or more thereof.
The fluorine-containing nonionic surface active agent and silicon-containing nonionic surface active agent which may be used as the internal releasing agent in the process of the present invention are compounds each containing respectively a perfluoroalkyl group and a dimethylpolysiloxane group in the molecule. These compounds also contains individually a hydroxyalkyl group and a phosphoric ester group.
Commercially available suitable fluorinecontaining nonionic surface active agents include UNIDAIN™ DS-401 (product of Daikin Kogyo Co., Ltd.), UNIDAIN™ DS-403 (product of Daikin Kogyo Co., Ltd.), F-TOP™ EF122A (product of Shin Akita Chemical Co., Ltd.), F-TOP™ EF126 (product of Shin Akita Chemical Co., Ltd.) and F-TOP™ EF301 (product of Shin Akita Chemical Co., Ltd.). A commercially available suitable silicon-containing nonionic surface active agent is Q2-120A, a trial product of the Dow Chemical Company.
The quaternary alkylammonium salt useful in the practice of the present invention is generally known as a cationic surface active agent and includes the halides, phosphates and sulfates of quaternary alkylammoniums. Exemplary suitable chlorides include trimethylcetylammonium chloride, trimethylstearylammonium chloride, dimethylethylcetylammonium chloride, triethyldodecylammonium chloride, trioctylmethylammonium chloride and diethylcyclohexyl-dodecylammonium chloride.
Exemplary suitable acidic phosphates useful in the practice of the present invention include isopropyl acid phosphate, diisopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, octyl acid phosphate, dioctyl acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate, tridecanol acid phosphate, and bis(tridecanol-acid) phosphate.
Exemplary suitable metal salts of higher fatty acids useful in the process of the present invention include zinc salts, calcium salts, magnesium salts, nickel salts and copper salts of stearic acid, oleic acid, octanoic acid, lauric acid, behenic acid and ricinoleic acid, such as zinc stearate, zinc oleate, zinc palmitate, zinc laurate, calcium stearate, calcium oleate, calcium palmitate, calcium laurate, magnesium stearate, magnesium oleate, magnesium laurate, magnesium palmitate, nickel stearate, nickel oleate, nickel palmitate, nickel laurate, copper stearate, copper oleate, copper laurate and copper palmitate.
Exemplary suitable higher fatty acid esters useful in the practice of the process of the present invention include esters of higher fatty acids such as stearic acid, oleic acid, octanoic acid, lauric acid and ricinoleic acid and alcohols such as ethylene glycol, dihydroxypropane, dihydroxybutane, neopentyl glycol and dihydroxyhexane.
The internal mold releasing agent is present in the process of the invention in an amount from about 0.1 to about 10,000 ppm, preferably from about 1 to about 5,000 ppm based on the total weight of the monomer mixture. If the amount is less than 0.1 ppm, it will be difficult to release the lens from the mold. Any amounts in excess of 10,000 ppm will lead to the formation of haze in the resulting lenses, early release of the resulting lenses from a mold during polymerization, and deterioration of profile regularity on the surface of the resulting lenses.
Exemplary suitable sulfur-containing aromatic polyisocyanate compounds include aromatic sulfide-type isocyanate compounds such as diphenylsulfide-2,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatedibenzylthioether, bis(4-isocyanatemethylbenzene)sulfide and 4,4'-methoxybenzenethioethyleneglycol-3,3'-diisocyanate; aromatic disulfide-type isocyanates such as diphenyldisulfide-4,4'-diisocyanate, 2,2'-dimethyl-diphenyl-disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl-disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl-disulfide-6,6'-diisocyanate, 4,4'-dimethyldiphenyl-disulfide-5,5'-diisocyanate, 3,3'-dimethoxydiphenyl-disulfide-4,4'-diisocyanate and 4,4'-dimethoxydiphenyl-disulfide-3,3'-diisocyanate; aromatic sulfone-type isocyanates such as diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidinsulfone4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylsulfone-2,4'-diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate-dibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di-tertbutyldiphenylsulfone-3,3'-diisocyanate, 4,4'-methoxybenzene-ethylenedisulfone-3,3'-diisocyanate and 4,4'-dichlorodiphenylsulfone-3,3'-diisocyanate; sulfonic ester-type isocyanates such as 4-methyl-3-isocyanatebenzenesulfonyl-4'-isocyanate-phenol ester, 4-methoxy-3-isocyanatebenzenesulfonyl-4'-isocyanate-phenol ester; aromatic sulfonic amides such as 4-methyl-3-isocyanatebenzene-sulfonylanilide-3'-methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-methoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, and 4-methyl-3-isocyanatebenzenesulfonyl-anilide-4-methyl-3'-isocyanate; sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate; and 1,4-dithian-2,5-diisocyanate.
Halogen-substituted compounds such as chlorine-substituted, bromine-substituted, alkyl-substituted, alkoxy-substituted and nitro-substituted bifunctional or polyfunctional aromatic polyisocyanated compounds and prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biuret-modified products and dimerization or trimerization products of aromatic polyisocyanate compounds are also suitable for use in the process of the invention.
These polyisocyanate compounds may be used singly or as a mixture of two or more thereof.
Exemplary suitable polyol compounds for use in the process of the present invention include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol, inositol, hexanetriol, triglycerol, diglycerol, triethylene glycol, polyethylene glycol, tris(2-hydroxyethyl)isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,02.6 ]decane-dimethanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,1]-dodecanediol, bicyclo[4,3,0]-nonanedimethanol, tricyclo[5,3,1,1]dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1]-dodecanol, spiro[3,4]-octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di(2-hydroxyethoxy)benzene, bisphenol A-bis-(2-hydroxyethyl ether), tetrabromo-bisphenol A, tetrabromo-bisphenol A-bis(2-hydroxyethyl ether), dibromoneopentyl glycol, and epoxy resins.
Condensation products of the above-described polyols with organic polybasic acids such as oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimeric acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-bromoglycolic acid, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid and bromophthalic acid, addition products of the above-described polyols with alkylene oxides such as ethylene oxide and propylene oxide, addition products of alkylene polyamines with alkylene oxides such as ethylene oxide and propylene oxide are also suitable for use in the process of the invention.
Halogen-substituted polyol compounds such as chlorine-substituted and bromine-substituted polyol compounds may also be employed.
Exemplary suitable polythiol compounds having no sulfur atom except the mercapto group for use in the invention include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane2,3-dithiol, bicyclo[2,2,1]-hepta-exo-cis-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid-bis(2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid(2-mercaptoethyl ester), 2,3-dimercapto-1-propanol(2-mercaptoacetate), 2,3-dimercapto-1-propanol(3-mercaptoacetate), diethyleneglycol-bis(2-mercaptoacetate), diethyleneglycol-bis(3-mercaptopropionate), 1,2-dimercaptopropylmethyl ether, 2,3-dimercaptopropylmethyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl)ether, ethyleneglycol-bis(2-mercaptoacetate), ethyleneglycol-bis(3-mercaptopropionate), trimethylolpropane-tris(2-mercaptoacetate), trimethylolpropane-tris(3-mercaptopropionate), pentaerythritol(3-mercaptopropionate), and pentaerythritol-tetrakis(3-mercaptopropionate), and the halogen substituted aliphatic polythiol compounds such as chlorine and bromine substituted aliphatic polythiols.
Aromatic polythiol compounds such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2-bis(mercaptomethyleneoxy)benzene, 1,3-bis(mercaptomethyleneoxy)benzene, 1,4-bis(mercaptomethyleneoxy)benzene, 1,2-bis(mercaptoethyleneoxy)benzene, 1,3-bis(mercaptoethyleneoxy)benzene, 1,4-bis(mercaptoethyleneoxy)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 1,2,3-tris(mercaptomethyleneoxy)benzene, 1,2,3-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,2,3-tris(mercaptoethyleneoxy)benzene, 1,2,4-tris(mercaptoethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene, 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2,4,5-tetrakis(mercaptoethyl)benzene, 1,2,3,4-tetrakis(mercaptomethyleneoxy)benzene, 1,2,3,5-tetrakis(mercaptomethyleneoxy)benzene, 1,2,4,5-tetrakis(mercaptomethyleneoxy)benzene, 1,2,3,4-tetrakis(mercaptoethyleneoxy)benzene, 1,2,3,5-tetrakis(mercaptoethyleneoxy)benzene, 1,2,4,5-tetrakis(mercaptodimercaptobiphenyl, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithil, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol and 2,4-di(p-mercaptophenyl)pentane, halogen-substituted aromatic polythiols including the chlorine or bromine substituted polythiols such as 2,5-dichlorobenzene1,3-dithiol, 1,3-di(p-chlorophenyl)propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene, and heterocyclic polythiols such as 2-methylamino-4,6-dithiolsym-triazine, 2-ethyl-amino-4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiolsym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzyloxy-4,6-dithiol-sym-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine, and halogen substituted polythiols such as chlorine substituted and bromine substituted polythiols are also suitable for use in the process of the present invention.
Exemplary suitable polythiol compounds having at least one sulfur atom in addition to the mercapto groups include 1,2-bis(mercaptomethylthio)benzene, 1,3-bis(mercaptomethylthio)benzene, 1,4-bis(mercaptomethylthio)benzene, 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)disulfide, and the esters of these polythiols with thioglycolic acid and mercaptopropionic acid, aromatic polythiols such as hydroxymethylsulfide-bis(2-mercaptoacetate), hydroxymethylsulfide-bis(3-mercaptopropionate), hydroxyethylsulfide-bis(2-mercaptoacetate), hydroxyethylsulfide-bis(3-mercaptopropionate), hydroxypropylsulfide-bis(2-mercaptoacetate), hydroxypropylsulfide-bis(3-mercaptopropionate), hydroxymethyldisulfide-bis(2-mercaptoacetate), hydroxymethyldisulfide-bis(3-mercaptopropionate), hydroxyethyldisulfide-bis(2-mercaptoacetate), hydroxyethyldisulfide-bis(3-mercaptopropionate), hydroxypropyldisulfide-bis(2-mercaptoacetate), hydroxypropyldisulfide-bis(3-mercaptopropionate), 2-mercaptoethylether-bis(2-mercaptoacetate), 2-mercaptoethylether-bis(3-mercaptopropionate), 1,2,3,4-tetrakis(mercaptomethylthio)benzene, 1,2,3,5-tetrakis(mercaptomethylthio)benzene, 1,2,4,5-tetrakis(mercaptomethylthio)benzene, 1,2,3,4-tetrakis(mercaptoethylthio)benzene, 1,2,3,5-tetrakis(mercaptoethylthio)benzene and 1,2,4,5-tetrakis(mercaptoethylthio)benzene, and the nucleusalkylated products of these polythiols.
Aliphatic polythiols such as bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3mercaptopropylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithian, 1,4-dithian-2,5-diol-bis(2-mercaptoacetate), 1,4-dithian-2,5-diol-bis(3-mercaptopropionate), thiodiglycolic acid-bis(2-mercaptoethyl ester), thiodipropionic acid-bis(2-mercaptoethyl ester), 4,4-thiodibutyric acid-bis(2-mercaptoethyl ester), dithiodiglycolic acid-bis(2-mercaptoethyl ester), dithiodipropionic acid-bis(2-mercaptoethyl ester), 4,4-dithiodibutyric acid-bis(2-mercaptoethyl ester), thiodiglycolic acid-bis(2,3-dimercaptopropyl ester), thiodipropionic acid-bis(2,3-dimercaptopropyl ester), thiodiglycolic acid-bis-(2,3-dimercaptopropyl ester) and dithiodipropion-bis(2,3-dimercaptopropyl ester), heterocyclic compounds such as 3,4-thiophenedithiol, bithmuthiol and 2,5-dimercapto1,3,4-thiadiazole, and halogen substituted polythiols such as chlorine substituted and bromine substituted compounds may also be employed in the process of the present invention.
These active hydrogen compounds may be used singly or as a mixture of two or more thereof.
The molar ratio of the functional groups of the sulfur-containing aromatic polyisocyanate compound to the active hydrogen compound is from about 0.5 to about 3.0, preferably from about 0.5 to about 1.5 NCO/(SH+OH).
The plastic lens of the present invention is made of a resin containing principally urethane bonds each comprising anisocyanate group and a hydroxyl group or S-alkyl thio-carbomate bonds each comprising an isocyanate group and a mercapto group. As a matter of course, the resin may contain allophanate bonds, urea bonds, biuret bonds, in addition to the above-described two kinds of bonds.
The urethane bonds or S-alkyl thiocarbamate bonds may be further reacted with isocyanate groups to increase the cross-linking density. In this case, the reaction temperature should be raised to at least 100� C. and the isocyanate component should be used in an excess amount. Further, an amine or the like may be used in combination to partially form urea bonds or biuret bonds. It is however necessary to pay particular attention to coloring when an aromatic polyisocyanate compound is reacted with a compound other than a polyol or polythiol compound.
Agents such as a chain-extender, cross-linking agent, light stabilizer, ultraviolet absorber, anti-oxidizing agent, oil soluble dye and filler may be added to achieve desired properties in the lens.
The reaction velocity rate may be controlled by adding a reaction catalyst used in the production of polyurethane or S-alkyl thiocarbamate and is wellknown in the art.
The plastic lens of the present invention can be obtained by a casting polymerization process. Specifically, one or more of sulfur-containing aromatic polyisocyanate compounds, one or more of active hydrogen compounds and at least one internal mold releasing agent are mixed to form a mixture, and the resulting mixture is poured into a mold and is polymerized.
The polymerization temperature and time depend on the types of monomers and additives employed including the mold releasing agent. However, the polymerization time is generally from about 0.5 to about 72 hours at a polymerization temperature of from about -20� C. to about 200� C., preferably from about room temperature to about 150� C., most preferably from about 50� C. to about 120� C. It is also possible to anneal the polymerized lenses, if necessary.
The plastic lenses of the present invention have high degrees of profile regularity and excellent optical characteristics, are lightweight and superb in impact resistance, and are hence suitable for use in optical elements such as eyeglass lenses and camera lenses.
The plastic lens of the present invention may undergo physical or chemical treatment such as surface abrasive finishing, antistatic treatment, hard coat treatment, non-reflective coat treatment, coloring treatment and dimming treatment in order to improve or impact such properties such as anti-reflection, high hardness, abrasion resistance, chemical resistance, fog resistance and fashionability, as required.
The present invention will be further clarified and described in more detail by the following Examples and Comparative Examples which are intended to be purely exemplary of the invention. The performance tests of the resultant lenses, refraction index, Abbe's number, mold releasing property and appearance were measured in accordance with the following testing methods.
Refraction index and Abbe's number: Measured at 20� C. by means of a Pulfrich refractometer.
Mold releasing property: After completion of polymerization, a TEFLON™ made wedge was driven between a lens and a mold. Mold releasing property was evaluated as follows: released easily without any resistance--(O); and not released wholly or even partially--(X).
Appearance: observed with the eye.
After mixing 24.2 g (0.09 mole) of diphenylsulfide-4,4'-diisocyanate, 8.0 g (0.06 mole) of trimethylolpropane and 0.032 g (1,000 ppm) of isopropyl acid phosphate, the resulting mixture was poured into a mold composed of a glass mold and a gasket. The mixture was heated slowly from room temperature to 120 taking 28 hours to complete the polymerization. After polymerization, a lens was released with ease. The lens thus-obtained was colorless and transparent and had excellent profile regularity. It had a refraction index of nD 20 =1.61, an Abbe's number of νD 20 =32 and a specific gravity of 1.27.
Lenses were made in accordance with the compositions given in Table 1 in the same manner as in Example 1. The results of performance tests are shown in Table 1
Lenses were made in accordance with the compositions given in Table 2 in the same manner as Example 1 except for the mold treatment shown in Table 2. The results are given in Table 2.
In Comparative Examples, lenses were poorly released from molds due to the absence of any internal mold releasing agent, so that the lenses thus released had irregularities on their surfaces.
In Table 2, the description in the column "Mold treatment" signifies as follows:
(1) No treatment:
A glass mold was used in the absence of mold releasing agent.
(2) External mold releasing treatment:
The inner surface of a glass mold was coated with an external mold releasing agent, YSR-6209 manufactured by Toshiba Silicone Co., and baked.
(3) External mold releasing treatment & reuse:
A glass mold was subjected to the external mold releasing treatment and used for polymerization. Thereafter, it was used again for polymerization without any treatment.
(4) Use of PP-mold:
Polypropylene was injection-molded to form a mold, which was used in place of the glass mold.
Other embodiments of the invention will be apparent to the skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claim.
TABLE 1Internal mold Mold Polyisocyanate Active hydrogen releasing agent releasing Refractive Abbe's Example (mole) compound (mole) (ppm) property Appearance index number 1 diphenylsulfide- trimethylolpropane (0.06) isopropylacid- ○ good profile regularity 1.61 32 4,4'-diisocyanate (0.09) phosphate (1,000) colorless & transparent 2 diphenylsulfide- tris(2-hydroxyethyl)- trioctylmethyl- ○ good profile regularity " " 4,4'-diisocyanate (0.09) isocyanurate (0.06) ammoniumchloride (500) colorless & transparen t 3 ##STR1## ##STR2## trioctylmethyl-ammoniumchloride (500) ○ good profile regularityco lorless & transparent 1.68 29 4 ##STR3## ##STR4## Q2-120A (Dow) (200) ○ good profile regularitycolorless & transparent 1.64 32 5 ##STR5## ##STR6## dibutylacid-phosphate (500) ○ good profile regularitycolorless & transparent 1.68 28 6 ##STR7## ##STR8## Unidain DS-403(Daikin) (100) ○ good profile regularitycolorless & transparent 1.62 32 7 ##STR9## diethylene glycol (0.02)+trimethlolpropane (0.02) isopropylacid-phosphat e (800) ○ good profile regularitycolorless & transparent 1.60 32 8 ##STR10## C(CH2 SCH2 CH2 SH)4 (0.01)+trimethylolpropane (0.02) isopropylacid-phosphate (800) ○ good profile regularitycolo rless & transparent 1.64 30 9 ##STR11## ##STR12## isopropylacid-phosphate (800) ○ good profile regularitycolorless & transparent 1.63 29 10 ##STR13## ##STR14## isopropylacid-phosphate (800) ○ good profile regularitycolorless & transparent 1.62 30 11 ##STR15## ##STR16## isopropylacid-phosphate (800) ○ good profile regularitycolorless & transparent 1.63 32
TABLE 2__________________________________________________________________________Compara- Mold Refrac-tive Polyisocyanate Active hydrogen Mold releasing tive Abbe'sExample (mole) compound (mole) treatment property Appearance index number__________________________________________________________________________ ##STR17## trimethylolpropane (0.02) no treatment X surface irregularity, colorless --transparent --2 ##STR18## trimethylolpropane (0.02) external mold releasing treatment ○ surface irregularity, colorless 1.61ansparent 323 ##STR19## trimethylolpropane (0.02) external mold releasing treatment & reuse (Comp. Ex. 2) X -- -- --4 ##STR20## trimethylolpropane (0.02) use of PP mold ○ poor profile regularity, colorless 1.61amsparent 325 ##STR21## ##STR22## no treatment X -- -- --6 ##STR23## ##STR24## external mold releasing treatment ○ surface irregularity, colorless 1.64amsparent 327 ##STR25## ##STR26## external mold releasing treatment & reuse (Comp. Ex. 6) X -- -- --8 ##STR27## ##STR28## use of PP mold ○ poor profile regularity, colorless 1.64ansparent 329 ##STR29## ##STR30## no treatment X -- -- --10 ##STR31## ##STR32## external mold releasing treatment ○ surface irregularity, colorless 1.68ansparent 2911 ##STR33## ##STR34## external mold releasing treatment & reuse (Comp. Ex. 10) X -- -- --12 ##STR35## ##STR36## use of PP mold ○ poor profile regularity, colorless 1.68ansparent 29__________________________________________________________________________
|Cited Patent
|Filing date
|Publication date
|Dec 3, 1947
|Feb 20, 1951
|John O Beattie
|Manufacture of plastic lenses from monomeric materials
|Feb 11, 1974
|Mar 16, 1976
|Buckbee-Mears Company
|Increasing the yield of cast plastic lenses
|Feb 27, 1978
|Mar 27, 1979
|Buckbee-Mears Company
|Industrial production of cast plastic lenses
|Feb 12, 1981
|Aug 3, 1982
|Showa Denko K.K.
|Plastic lens
|Apr 6, 1984
|Aug 13, 1985
|Method for the preparation of hydrophilic gels by monomer casting
|Mar 24, 1986
|Aug 25, 1987
|Mitsui Toatsu Chemicals, Incorporated
|S-alkyl thiocarbamate base lens resin
|Feb 27, 1987
|Oct 4, 1988
|Mitsui Toatsu Chemicals, Incorporated
|High-refractivity plastic lens resin formed by reacting at least one polyisocyanate with at least one polythiol
|Nov 5, 1987
|Dec 13, 1988
|Mitsui Toatsu Chemicals, Incorporated
|High-refractivity plastic lens resin formed from a polyisocyanate and a polythiol
|Title not available
|Citing Patent
|Filing date
|Publication date
|Jan 31, 1991
|Jun 30, 1992
|Mitsui Toatsu Chemicals, Inc.
|Highly-refractive plastic lens and process for making the lens
|Mar 23, 1993
|Aug 29, 1995
|Daiso Co., Ltd.
|Cyclic sulfide compound, polymerizable compositions for optical products and optical products formed thereof
|Mar 14, 1995
|Jan 16, 1996
|Daiso Co., Ltd.
|Cyclic sulfide compound, polymerizable compositions for optical products and optical products formed thereof
|Nov 20, 1995
|Jun 3, 1997
|Hoya Corporation
|Process for the production of polyurethane lens
|Feb 18, 1997
|Apr 28, 1998
|Hoya Corporation
|Process for the production of polyurethane lens
|Dec 8, 1998
|Oct 5, 1999
|Essilor International (Compagnie Generale D'optique)
|Internal mold release compositions containing phosphate esters
|Apr 30, 1999
|Aug 14, 2001
|Hoya Corporation
|Process for the production of polyurethane lens
|Apr 6, 2001
|Dec 16, 2003
|Johnson & Johnson Vision Care, Inc.
|Silicon carbide IR-emitter heating device and method for demolding lenses
|Aug 24, 2010
|Novartis Ag
|Method for making contact lenses
|Jul 13, 2010
|Jan 10, 2012
|Novartis Ag
|Method for making contact lenses
|May 14, 2013
|Novartis Ag
|Method for making contact lenses
|Nov 23, 2011
|Jun 30, 2015
|Novartis Ag
|Lens molds having atmospheric plasma coatings thereon
|Apr 5, 2002
|Dec 12, 2002
|Pegram Stephen C.
|Ir-emitter heating device and method for demolding lenses
|Aug 8, 2006
|Feb 15, 2007
|Guigui Wang
|Method for making contact lenses
|Dec 18, 2008
|Jun 25, 2009
|John Dallas Pruitt
|Method for making contact lenses
|Aug 10, 2006
|Feb 22, 2007
|Novartis Ag
|Method for making contact lenses
|Dec 18, 2008
|Jul 9, 2009
|Novartis Ag
|Method for making contact lenses
|Nov 8, 2011
|May 18, 2012
|Novartis Ag
|Method for making contact lenses
|Nov 23, 2011
|Jun 7, 2012
|Novartis Ag
|Lens molds having atmospheric plasma coatings thereon
|Oct 30, 2014
|May 7, 2015
|Novartis Ag
|Method for producing ophthalmic lenses
|U.S. Classification
|264/2.3, 264/1.1, 523/106
|International Classification
|Cooperative Classification
|European Classification
|Apr 1, 1989
Owner name: MITSUI TOATSU CHEMICALS, 3-CHOME, JAPAN
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|Apr 4, 1989
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|Apr 13, 1993
|Certificate of correction
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Skip to comments.Gunman Kills Five Women In Chicago Store
Posted on 02/02/2008 7:46:53 PM PST by blam
Gunman kills five women in Chicago store
By Tim Shipman in Chicago
Last Updated: 2:36am GMT 03/02/2008
Five people were shot dead at a women's clothing store in a Chicago suburb on Saturday.
Police evacuated the mall and sealed off the car park after at least five shots were fired
The victims, all women, were killed inside the Lane Bryant store at Brookside Marketplace shopping centre at Tinley Park, south of Chicago.
Police evacuated the mall and sealed off the car park after at least five shots were fired shortly before noon.
It is thought that the shooting occurred after a robbery went wrong and there were reports that the raider had taken some of the victims hostage in the plus-sized clothing store.
Police said that security cameras in the store had allowed them to tentatively identify the man, who is understood to have a history of armed robbery and a murder conviction.
The killer fled the scene after the shooting. A police dogs unit and helicopter were last night working to track down the suspect.
Armed officers also searched neighbouring stores in the area and cars in the parking lot.
Tinley Park Police Sgt TJ Grady said that they were looking for a 5ft 8in tall black man, weighing between 16 and 20 stone and wearing a waist-length black coat, a black knit cap, dark jeans and with braids in his hair.
One victim was was taken to the nearby St James Hospital and Health Care Centres for treatment to gunshot wounds but died later.
Sgt Grady said: "Responding units entered the store and found multiple victims that had been shot and killed.
"No motive has been established. Every store was immediately canvassed and a search by air, too, has given us every indication that the offender has left the scene."
Shoppers said that they were baffled by the motive behind the shooting as it had happened relatively early in the day, about 10.45, while shops would have had quite small amounts of money in their cash registers.
Residents of the predominantly white community of Tinley Park, which describes itself as Chicago's "fastest growing suburb" and has a population of about 58,000, said that they that were shocked by the shooting.
According to FBI crime statistics there was not a single murder in Tinley Park in 2007.
The other violent crime statistics are also low - four sexual assaults, 15 robberies and 38 assaults.
Greg Grace, from nearby Frankfort, who was in the parking lot outside Lane Bryant, said that he saw several stretchers being wheeled into the store. The stretchers were later wheeled out - carrying no wounded survivors.
The mayor, Edward Zabrocki, went to the scene and - looking very shaken - said: "We're very sad about this. We're a victim of our society that we live in."
One witness at the scene described how police officers responded quickly to news of the shootings and hunted the gunman through other stores on the strip mall, with guns drawn and sniffer dogs in tow.
Another witness, Tracy Caccavella, said that she was in a nearby PetSmart store when police burst in with their guns drawn. She said that the officers ordered the store's staff not to let in any more customers before conducting a 20-minute search.
The multiple killing comes a month after nine people died in a shooting at a shopping mall in Omaha, Nebraska.
Nineteen-year-old Robert Hawkins killed eight people, wounded four, then shot himself at the Westroads Mall on December 5 last year.
It was the deadliest shooting in Nebraska since the rampage of Charles Starkweather, who killed 11 people in 1958.
Neither do I. What in the world happened here?
Murder conviction?!!! And he was out on the streets?!!!
I saw it posted twice earlier but for some reason it was pulled by the Mods.
-—Tinley Park Police Sgt TJ Grady said that they were looking for a 5ft 8in tall black man, weighing between 16 and 20 stone-—
WTF? 16 and 20 stone? Is the stone a popular unit of measure out Chicago way?
Why the frick don't they tell the deserving public if the bastard is black, white, Latino, etc.? If they know who he is, why isn't his mug shot being posted on all media??
So did I! Why would the Mods pull 2 threads?
Illinois, one of the only two states that has total prohibition of concealed carry. And this will be the last to state to ever get it (it never will). The Chicago media will see to that.
It was posted (a couple of times) earlier in the day. That said, I don't understand this: "It is thought that the shooting occurred after a robbery went wrong ..."
Yeah, like a robbery can "go right"? The guy showed up with a gun, so he clearly was going to do whatever it took to get him the contents of the cash drawer. However, I suspect he probably knew somebody at the shop, or possibly even had been an employee at some point, and he killed them so they couldn't identify him or possibly because he had a grudge against them.
Supposedly this guy is already a convicted felon (armed robbery), so you can see how well our justice system has protected us.
Can someone please build a wall around Chicago and keep the savages in, doubt seriously if the perp lived in Tinley Park.
"Tinley Park Police Sgt TJ Grady said that they were looking for a 5ft 8in tall black man, weighing between 16 and 20 stone and wearing a waist-length black coat, a black knit cap, dark jeans and with braids in his hair."
From the article you obviously didn't read.
Makes sense to UK readers of the Telegraph.
Gee, do you think Whoever let this human vermin out was a D?
Frickin' libs...The gun grabbers will kill us all, indirectly, I mean...If I were livin' in IL, I'd be carryin'. law or no law...Life is simply too valuable...
"the plus-sized clothing store"
Was this little bit of info really needed?
That being said, it looks like the tough anti gun laws in Chicago really worked well. The law abiding citizens are again the victims.
This is a story from the United Kingdom, Great Britain, England...across the pond.
A 'stone' is measured there as 14 pounds...three barley corns to the inch..
Pip pip cheerio!
Times UK????????
So rather than removing posts and warning posters the Mods deleted the whole thread??
ONE murder conviction should keep a person, at the very LEAST, in prison for life.
Since it doesn't...five UNNECESSARILY DEAD people
Why was this guy back on the streets? Liberalism is a mental disorder and innocent people die as a result.
errrrr Telegraph UK ??????? I meant.
No, The Telegraph (UK)
I guess we'll have to wait and see if this thread gets yanked, too.
This is from the UK Telegraph so it must be a measure in England. I don't get it, though.
I couldn't find if they caught the guy. Is he still on the loose or in custody?
And someone allowed his history to repeat itself.
See post .....#21
I think it was pulled because too many people made fat jokes about Lane Bryant customers.
I used to carry all the time (S&W Model 10 snub or Walther PPK/S). If caught, it was just a $500 fine and loose the gun. Now 10 years later its a "class X felony". You won't even be able to buy .22 long rifle cartridges at Wal-Mart.
He had a criminal record and previous murder conviction. I wonder if he was released from an Arkansas prison by Huckabee.
Another gun free and defenseless victim zone succeeds in protecting their patrons. [/sarcasm]
I was looking for it also. I guess one of us could have posted it...
A number of threads remain. There may be problems with title search.
Was this little bit of info really needed?
It goes to motive. Seeing as how the government is now considering laws to punish the obese, the fellow was actually thinning out the public at-large.
Just like I said over on the other thread about the teen scumbags who stole a girl scout's money, people just tolerate too much bad behavior. This piece of garbage was a convicted killer but he was out on the street?? We will probably hear the usual outrage now that this shouldn't have happened. Yet every time it does happen, nothing changes. Criminals will get even softer treatment when a Democrat president is appointing federal judges too. Voters don't think of things like that.
there are a few threads
I am still curious as to why this is not being reported in the US media. Has anyone seen or heard anything about it, other than this thread?
You can rant, or you can read the story. I read, you rant.
"a 5ft 8in tall black man"
Whatever happened to metric? All I ever hear is criticism for the US sticking to English units.
yes - all over. But the election news is taking priority
That's between 224 and 280 pounds here in the good 'ol U.S. of A.
1 Stone = 14 pounds
It's been top of the news most of the day on radio. Primary coverage and the Super Bowl are vying for attention with it.
Only in the UK paper. Not online on the US sources.
I could swear that earlier on Fox and MSNBC.com, I read that he was much taller, and they gave his weight in pounds. All that information is missing from the updated articles now, and they've been relegated to secondary news. You have to look for the articles.
I don't understand why the description is missing now. I understand the PC crap can't racially profile and all, but even his height and weight. What are people supposed to do, call the police on every male they see?
Yeah, in Chicago they use that to figure out how much concrete it will take to keep the body at the bottom of the lake.
wonder if this guy was let out early by Governor Ryan. remember the governor that commuted all the death sentences. i think he let alot of people out too.
There is a segment of society that firmly believes in the death penalty... for the innocent, that is.
Story here...do not know if it requires sign-up.
This is why Kaleeeeeeforneeeeeya has a 3-strikes law.
That was a silly thing for me to say—I never watch tv, and since it's Saturday, I haven't even had the radio on!
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Vt. man charged with murder found incompetentJanuary 28,2014The Associated Press
BURLINGTON -- A judge has determined that a man accused of killing a Vermont social worker in her Burlington home in 2010 is incompetent to stand trial.
Jose Pazos has undergone several psychological evaluations since he was arrested.
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Deputy Chittenden County State's Attorney Mary Morrissey said Monday the state will argue for Pazos' hospitalization so he can receive medication that eventually would enable him to be competent, the Burlington Free Press reports.
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