Innovative efforts should never report to line managers charged with responsibility for ongoing operations. The new project is an infant and will remain one for the foreseeable future, and infants belong in the nursery. Executives in charge of existing businesses or products will have neither the time nor understanding for the infant project.


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#241 / Missing The Meaning
On August 20, 2020, shortly after the end of the Democratic National Convention, and on the eve of the Republican National Convention, Peggy Noonan wrote a column in The Wall Street Journal titled, "The Democrats Miss the Meaning."
Given the timing of the column, and the topic, you will immediately understand that Noonan's column was a critique of the way the Democratic Party presented itself through the four days of the Convention. I have done my own critique, which does make a point that Noonan also makes. This so-called "Convention" was, really, an extended political advertisement. Here's how Noonan puts it:
To be fair in critiquing certain public events you have to be like a judge in the Olympics and factor in degree of difficulty. No one had ever done a Zoom convention before, so no one knew how to do it. Should there be a host each night? Should it be an earnest actress? Does that make us look shallow? Do we want to look shallow?
What hadn't been done before was done rather poorly, with high schlock content. You got the impression no one creative or daring was authorized to be either. It has been compared to a telethon, an infomercial, and fundraising week on public television. Marianne Williamson said it was "like binge watching a Marriott commercial." Mostly it was the Democratic Party talking to itself and playing to its base (emphasis added).
I confess that I have something of a soft spot for Peggy Noonan, despite her right wing and Republican Party allegiences (Noonan was a speechwriter for Ronald Reagan, among other things). What I find appealing in Noonan is that her columns, almost always, seem directed to everyone, not just those on the righthand side of the political spectrum. At least, that's how she tends to come across to me.
When someone is attempting to speak "to" me, and not just "at" me, and this is the way I think about Noonan, I like to believe that I am willing to listen. Theoretically, at least, we shouldn't write off the views of anyone; we should be willing to listen to everyone; however, it's easier to do that when the person you are listening to seems, genuinely, to want to include you in the discussion. Again, I do get that feeling when I am reading what Noonan writes. I don't always agree with Noonan, by any means, but I am almost always willing to listen to her point.
The picture above, of President Barack Obama, was featured as an illustration in the column that I am referencing. President Obama, in my opinion, also comes across, at least to me, as someone who is seeking to talk to everyone, not just those in the political party with which he is associated. If those who are not Democrats routinely discount and ignore what President Obama has to say, and I think many of them do, it is my belief that race is a factor in their dismissive treatment of our former president. The way I see it, President Obama is consistently talking "to" the American people, and to all of them, and not just "at" them. Noonan would seem to agree, in her review of Obama's Convention speech:
Barack Obama's speech will stick in history; it won't just slide away. No former president has ever publicly leveled anything like this criticism at a sitting successor: "I did hope, for the sake of our country, that Donald Trump might show some interest in taking the job seriously, that he might come to feel the weight of the office and discover some reverence for the democracy that had been placed in his care. But he never did. For close to four years now, he has shown no interest in putting in the work."
This is a former president calling the current one shallow and lazy. He also suggested he's greedy and intellectually incapable. Unprecedented? Yes. Unjustified? No, alas. And I'm not seeing Trump supporters rise up in indignant defense. They know it's true, too (emphasis added).
So, what was Noonan's major critique of the Democratic Party Convention? If Noonan is willing to listen to President Obama calling the current president "lazy," "shallow," and "intellectually incapable," what are we willing to hear from Noonan?
Noonan's point was that the Democratic National Convention did not speak to what everyone in the country is actually worried about:
Do the Democrats understand how hunkered-down many people feel, psychologically and physically, after the past six months? If I asked this right now of a convention planner or participant I think they'd say, "Yes, people feel battered by systemic bias, inequality, and climate change." And I'd say no, they're afraid of foreclosures! They're afraid of a second wave, no schools, more shutdowns, job losses and suddenly the supply lines break down this winter and there are food shortages.
In short, Noonan is suggesting that the Democratic Party seems afraid to focus on policy. As a Bernie Sanders supporter, that does tend to ring true to me. Here is how Noonan expresses it:
First, Democratic Party professionals are funny about policy. They take it seriously but don't think other people do. The past three decades they wound up thinking all politics is about glitz, emotion and compelling characters. Part of the reason they're like this is they never thought Republicans were serious about policy, because if they were, they'd be Democrats. They find it hard to credit the importance of policy in the making of a party's fortunes. They thought Republicans liked Reagan because he was handsome, and George H.W. Bush because he fought in the war. But their elections were policy victories. Charm and humor, stagecraft and showbiz matter, but they're not everything. They're not even half of everything.
Because boomer Democrats thought Republicans won on glitz, they got glitzy in return. It was the central Clintonian insight of 1992: We have to become actors, like the actors we seek to replace.
It only made politics worse and left Democrats unable to speak in public forums of the central point of politics: why you stand where you stand and what you intend to do.
(Fairness forces me to note that socialists love talking about policy, and so does Elizabeth Warren. And that Republican political operatives, as a class, are naturally hostile to the meaning of anything.)
Second, apart from the "We The People" gauziness, there was a nonstop hum of grievance at the convention. To show their ferocious sincerity in the struggle against America's injustices, most of the speakers thought they had to beat the crap out of the country—over and over. Its sins: racism, sexism, bigotry, violence, xenophobia, being unwelcoming to immigrants. The charges, direct and indirect, never let up. Little love was expressed, little gratitude. Everyone was sort of overcoming being born here.
Even Mr. Obama, trying, in a spirit of fairness, to expand the circle of the aggrieved, spoke of "Irish and Italians and Asians and Latinos told: Go back where you come from. Jews and Catholics, Muslims and Sikhs, made to feel suspect . . . black Americans chained and whipped and hanged. Spit on for trying to sit at lunch counters, beaten for trying to vote. . . . They knew how far the daily reality of America strayed from the myth."
The cumulative effect of all this, especially for the young, would prompt an inevitable question: Why would anyone fight to save this place? Who needs it?
If I were 12 and watched, I'd wonder if I had a chance here. If I were 20, they'd have flooded me with unearned bitterness.
Injustice is real, history is bloody. But guys, do you ever think you're overdoing it? Are you afraid that this is all you got? Is that why you don't talk about policy?
I am a Democrat. But I like to think I can listen to criticism and learn from it when it's justified. I believe that Noonan is saying something important.
If Democrats want to prevail in this coming election, justified grievance and the inadequacy of the current president are not going to be enough to win the contest.
In my opinion, it became a virtual certainty that Hillary Clinton would lose the last election in the instant she was quoted as calling those who supported her opponent "deplorables." They weren't. They aren't. They were (and are) Americans who supported her opponent.
Noonan's claim is that the Democratic National Convention shows that the Democratic Party is "talking to itself and playing to its base." If the "base" that the Democratic Party thinks it should be talking to is represented solely by past and present supporters of the two Clintons, then I think the Party is in trouble.* After all, didn't we already try that last time?
Let's not make the same mistake twice.
* Click here for a left wing critique of the DNC. It's not nearly as nice as Noonan's, and it, too, raises valid points. At least in my opinion.
https://www.wsj.com/articles/the-democrats-miss-the-meaning-11597980333

redpajama_set_name: RedPajamaCommonCrawl


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Entries from September 2011
Monday, September 26. 2011
Solomon's bird
Around the 10/09, I was about to have a panic attack, so I listened Hair and thought I should wear proper garments. I then proceded to dance around my bed. The campiness made me feel great! (That bird is in no way an hoopoe.)
Better view of the bird (beware, I look stupid)
Bird: came in with bath products.
Others: thrifted.
I already that idea to do as if before, but I needed Simon Doonan to really get the thing and how it could be liberating instead of a loss of time that would push me to screw my life.
When I feel bad, I can think about Simon Doonan or Tavi Gevinson or similar people, and suppose they are people around which you feel like a good person, that for them people are cookie jars of possible awesomeness instead of being cookie jars of being-a-bad-person-ness. Thinking people are cool as they are won't keep them from becoming even cooler. (I'd been searching for the right "even cooler" picture, this will make it even if it's raining.)
I like how Tavi is using her "influence", and her "public image", all the big words: while others blame fashion's, ie, lack of body diversity on homosexuals (as productors/actors of the fashion world), women (as productors and consumers-observators), youth (consumers) and/or transsexuals (mentioned as a bonus punching-bag, supposed to be neither actors no observators), she actually does something.
I know I'm exaggerating: most people just say die, pretending « fashion » is like that and it won't ever change (but isn't that an ever-changing thing? can't we be a part of its changes? aren't we?); but I already hear people saying that, for example, if there wasn't enough body diversity in fashion, it was because of « those gay designers who wanted women to be masculines », which was « sad because they preferred rounder women, and it made women believe lies about men preferences » (sumthing lyk datz), and implying the problem was that it insulted their body ogling/beauty defining privileges. (btw, I never heard people blaming the fact Alexander Johansson is kind of feminine-looking on lesbian designers, maybe because the kind of people who says these kind of things thinks all the grands couturiers are biomen.)
We can all do something, change something, even if we are a "nobody". We just need to stop thinking about "fashion's problems" as inherent to the thing or having appeared by spontaneous generation.
These are problems issued of precedent existing problems in society, and in a vicious circle it is perpetuating and nourishing these, but we can do something by changing fashion, by changing the way we envisage it and by changing the society around it.
Style can be a mean for self expression, fashion could be anything you want it to be.
Which leads me to say, I just had a taste of WORN. WORN is an independent canadian fashion magazine which relies enormously on its readers to exist, so that possible advisers enjoys no influence on its content: the only advertisements are those by advertisers who really cares about supporting the mag and its readers. Readers who can eventually submit themselves, and offer their articles and artworks.
Wornettes really care about what they write and publish. WORN is about every aspect of fashion: textiles, persons who make it, persons who made it, sociological and psychological aspects, anecdotes and life stories relating to clothes, and a lotta "further ressources" at the end of the articles! (add to that the Books about Looks reviews section)
Articles I read up to then were really --full of references?-- worked on, n°12 editor's letter is really engaged for the Slut Walk, not giving the impression to be there just to look good (most articles on the subject in other magazines give me the impression of being written by slightly detached dudes afraid of being accused of « political correctness »), and there is an haiku about desperate search of the perfect necklaces in yard sales! (who didn't ever? do not raise your hands, that's just a rhetorical question to mention my interest for yard sales and perfect necklaces)
44p., and I find informations and a bibliography otherwise fairly scattered in every places.
(There is an advertisement for Toronto's Maker Faire! It makes me happy, if I did go at a Maker Faire right now, I wouldn't feel like a mismatch.)
Defined tags for this entry: indépendant, magazine de mode, outfit, tenue, worn
Saturday, September 3. 2011
Ready for the Common Man
Vest: La Redoute; top, necklace, pants: thrifted; shoes: André.
Details, if you look well you'll see more flowers on the necklaces' pearls:
The 28/08, I went at a fleamarket. After tooking real care of not spending all my money so I could buy new godasses (I'm french, therefore I can drop french words avec plus de raison que Simon Doonan), I finally bought combat boots that didn't fit at all! It isn't an habitude question, they'll never fit me.
Thinking I could have bought myself a Nintendo 64 instead, or other combat boots that would have fit me, and newer, that the seller proposed for the same price. I have these vinyls for way longer, given by my uncle. I was really surprised listening to Katmandu's Katmandu, I imagined it was a mockery with tamtams, but it was damn great. I listened to it only one time, that was today or yesterday evening, I think the singings and guitar especially were interesting. The cover of the vinyl was sort of pitiful but good in a kitsch way, but the thing on which they wrote the lyrics is a tad better, full of little drawings, like someone's notebook. Seeing these drawings, I thought it was some sort of hippy music, or hippy-themed music, an imitation since it was out in 1984.
Speaking of hippies, I wanted to buy bell-bottom pants for a while since I saw the movie Hair; I know what you're gonna say: " un hippie, une triplex ", you're so la stière.
For the PPMB, I found back that picture from when I was even more of a kid, I think it's interesting in the childhood picture, photo d'enfance, kind of interesting, sadly I don't have the words that fit to accompany it. I'm not wearing my glasses, I'm smiling and I hold someone despite the fact I'm not wanting to — watching it, I could believe it's the last proof of a good memory I'd like to live again, and again and again, and that all the joke was like that — but you must admit I look scared :
Another day, in an amusement park, I wanted to go on a jumping bicycle. My mother was opposing that decision, because I didn't ride a bicycle for a long time, she started hurling louder and louder, fully irrationnal, and I finished crying almost pushed against a wall. Then, we were put back in the car, the girl in the picture and me and were brought somewhere else (home). I looked back and slowly watched the amusement park disappearing, just like in movies.
Defined tags for this entry: childhood memories, outfit, souvenirs d'enfance, tenue


Our House has an Anchor: But what about TV?
Yes, we have a television on the boat. In fact, we have four--one in each bedroom and one in the salon. We are surrounded by televisions. Back when we were landlubbers, we never even had a TV in our bedroom, so being able to watch TV in every room really feels decadent.
As far as content, we have all the same options as land-based tv-watchers. We have a cable outlet at the dock that we can pay the cable company to activate. Or, we can hook up a antenna to pick up the broadcast channels. Or, we can go the satellite route. Our liveaboard neighbors, for example, have a DirecTV satellite dish installed at their dock that they can plug into when they are at the marina.
The antenna is that UFO-looking thing in the middle. It is surrounded by solar panels (more on those in a future post). A regular DirecTV antenna needs to be positioned to point in a very precise direction. That works great for a house, but will not work if the boat moves, either from point A to point B, or even rocking back and forth. Our super antenna, however, can pick up DirecTV anywhere (in most of North America) regardless of what direction we are pointing. So, our full lineup of TV channels comes with us wherever we go, even to a windy anchorage in the Bahamas. It is great.
Better yet, our boat is wired so that all four TVs are wired into the DirectTV receiver. And there is a remote-control extension that allows the remote to work anywhere in the boat--it does not need to be pointing at or in the same room as the receiver. So, we can watch and switch between all gazillion of our channels in any room in our boat.
Our bedroom TV is even better. It is perfectly positioned for watching from the bed, and since we've never had a bedroom TV before, it feels like we are staying in a hotel every night.
Both TVs are definitely smaller than the average house TV (and our other two TVs are even smaller), but because each room in the boat is small, the screens are appropriately proportioned and are easy to see. So, please, don't worry that we are roughing it out here. We can rot our brains in front of the TV just as easily as any of you.


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Ahmad and Rida broke the stereotype of fraudulent online rishta
Ahmad: We've been together six months and before that we both had tried different online apps and websites. We both liked the photos of each other because added very minimal info in our profiles. We spoke through messages for about a month before exchanging numbers and then met after few weeks in person. Although it is not very popular in Pakistani society and culture, we were honest that we met online. Now we are happy about how we met. Sometimes going against the typical cultural norms and stereotypes is fun! The stigma has definitely changed very quickly due to social matrimony websites like Zawaj. One of my cousin have met her spouse online too. We fell in love over our want for a life partner and our enthusiasm for living life in the most exciting ways possible."
Hina finally met Ali on Zawaj
Ali: "My wife and I met on Zawaj in August 2018 and we got married just recently. We're both teachers, but in different fields and institutions. She's a high school science teacher. I'm assistant professor in a private university. She's from Faisalabad (post-graduating MSc), and I'm from Johar Town, Lahore. I think I might still have some of our initial messages. She was about to give up on Zawaj and I thought we may not end up meeting, but I tried anyway. We continued talking and finally decided to meet one day. Well, that lead us to the marriage decision. We got engaged April 2018 and married November 2018. Funny enough, she received call from another person on Zawaj to ask for meeting while we were just celebrating our engagement." Hina: "I never would have met Ali if not used Zawaj. I am sure our paths never would have crossed. Thanks God we both decided to try out online matrimonial network. Meeting him was worth every terrible rishta encounter that I ever had…I had a lot!"
Zara and Faizan married 6 months after meeting on Zawaj
Zawaj: How did you start using Zawaj.pk? Zara: When I moved back to Lahore after completing post-graduation from Birmingham. Talks about my marriage were coming up every now and then at home. I was complaining about how backward Pakistani guys were! I just jumped on the bandwagon. A friend of my sister got her life partner on Zawaj so she suggested, I should give it a try. For my husband, it was just simple. He was looking for a long term relationship in the form of marriage... that's it! Zawaj: How did your relationship start? Zara: I don't even remember showing interest in him, but somehow we started sending messages on the Zawaj. When the conversation took off we did exchange numbers. It was almost like we'd known each other for years! We met a little over two monthss since we started talking. It was all very casual and fun. The rest, as they say, was history! Zawaj: What do you say to people who have doubts about finding life partner online? Zara: There's a stigma attached to online matrimonial platforms. Its mainly because most of our parents still have this traditional way of thinking, that there are 'proper' ways of meeting people. So when you meet someone online, you're taking the risks of flirt and also rebelling against these traditions. Then there's another thinking is that using online platform means you're not confident and good enough to meet people personally, and you need help to start things up. I say go for it. Take the risks. Fall in love. If it fails, then try again. There are no such stats exists to prove that meeting people online and having a relationship could lead to flirt and disastrous ending. When you think about it, meeting people traditionally doesn't guarantee you a lifetime of happiness either. So you can take the risk go online and try your luck on Zawaj!
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28 year old Woman from
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Register NowFind Rishta in Pakistan


To make things uncomplicated and easy those striving for progeny and having little time to perform lengthy Puja-Archana or Tantra-Mantra Prayog, here is a most simple Putra Prapti Mantra, which does not need any kind of worship or time consuming rituals.
The Mantra according to the Tantra works for those striving for progeny and also for those pregnant women who are hoping for a healthy and beautiful child.
There are two versions of the same Mantra shown in the image, both of them work for the same purpose. The woman desiring a child can chant any one of the two Mantras, anytime during the day or night, as many times as she likes. The Mantra can also be chanted during the Menstrual Periods.
Please note, my intention is not to give false hopes to anyone as birth and death is in the hands of God. I have only written what the scriptures say.


text:
Justia Patents InkUS Patent for Process for preparing polymers, polymers, dispersions, inks and uses Patent (Patent # 9,068,092)
Process for preparing polymers, polymers, dispersions, inks and uses
Jul 2, 2012 - Fujifilm Imaging Colorants Limited
A process for preparing a polymer comprising reacting at least the components i) to iii) in any order: i) a compound of the Formula (1): Formula (1) wherein: T1 and T2 independently are HO—, HS— or R1HN—; Q1 and Q2 independently are —NR2—; A1 and A2 independently are an optionally substituted divalent organic linking group; R1 when present is H or an optionally substituted alkyl, aryl or heterocyclyl group; R2 is H or an optionally substituted alkyl, aryl or heterocyclyl group; Z is an HO— group or a group of the Formula (2) or (3); Formula (2) wherein: L is —HN—, —O— or —S—; X is an optionally substituted organic group; Formula (3) wherein: each X independently is an optionally substituted organic group; in both Formulae (2) and (3) the asterisk (*) signifies the point of attachment to the triazine ring: ii) a diisocyanate; iii) an isocyanate reactive compound having at least one ionic group.
Latest Fujifilm Imaging Colorants Limited Patents:
Ink-Jet Printing Process
Process for preparing a dispersion, dispersion, use and method
Dispersions, process for preparing dispersions, inks and uses
Process, dispersions and use
Skip to: Description · Claims · References Cited · Patent History · Patent History
RELATED APPLICATION DATA
This application is a National Stage Application under 35 U.S.C. 371 of co-pending PCT application PCT/GB2012/051544 designating the United States and filed Jul. 2, 2012; which claims the benefit of GB application number 1111585.4 and filed Jul. 7, 2011 each of which are hereby incorporated by reference in their entireties.
This invention relates to a process for preparing polymers containing triazine groups, it further relates to the polymers themselves. It relates to dispersions and inks (especially ink jet printing inks) containing said polymers. It also relates to the use of the polymers for dispersing or comminuting (e.g. milling) a particulate solid so as to form a liquid dispersion.
Inks are often of one of two types, depending on the type of colorant used. Dye-based inks often comprise a dye dissolved in a liquid medium. Pigment inks comprise a pigment dispersed in a particulate form in a liquid medium. Pigment inks tend to have better ozone-fastness and light-fastness than dye-based inks. However, because the pigment is in the form of fine particles there is a tendency for the particles to agglomerate or flocculate whilst the ink is being stored and/or whilst the ink is being used (e.g. printed). Such agglomeration or flocculation before the ink has been printed onto a substrate is highly undesirable, particularly in ink jet printing inks where the printer nozzles are very small and are susceptible to blockage by any oversized particulate matter. Thus, in the ink jet field a great deal of effort has been directed towards attempting to provide sub micron sized pigment dispersions and increase the colloidal stability of these pigment dispersions.
It is also desirable to provide pigment inks which offer high optical density (OD), especially when printed onto plain paper.
Pigment dispersions are often colloidally stabilised by means of a dispersant.
In our own studies on dispersant stabilised pigment inks we have found that it is particularly difficult to prepare inks which simultaneously exhibit good colloidal stability and high OD on plain paper. For example, we have found that dispersant stabilised pigment inks known in the art having a high colloidal stability provide a low OD when printed on to plain paper and vice versa.
We have also found that the few dispersant stabilised pigment inks which do provide inks exhibiting high OD when printed onto plain paper tend to also use dispersants which require significant and undesirably high amounts of organic solvent to assist in dissolving/dispersing the dispersant, for example in the pigment dispersion or comminution step.
Further, it is desirable that a dispersant is effective in the dispersion or comminution process. Quicker comminution (e.g. milling) to submicron particles sizes saves substantial energy and it may also result in less pigment particles having a particles size markedly smaller than the target size. Particles much below the target size are often referred to as fines.
Pigment based inks when printed onto a substrate often produce final images that are not firmly secured to the substrate surface. Prints from pigment based inks often exhibit poor rub fastness, water-fastness or highlighter smear fastness.
Aqueous inks and ink jet printing inks require very different polymers as dispersant from organic inks. The present invention also aims to provide polymers suitable as dispersants for particulate solids in aqueous liquid vehicles. In addition the present invention attempts to provide polymers which can colloidally stabilise dispersions of particulate solids even when large amounts of organic liquid are present in combination with water.
Commercially, there still remains a need for dispersants which can be used to prepare pigment inks and which solve, at least in part, one or more of the abovementioned problems.
Japanese patent publication JP2004-315716 discloses polymers containing triazine rings which are useful as dispersants. This patent publication does not mention introducing ionic groups nor does it provide a disclosure of a process by which ionic groups could be incorporated.
According to a first aspect of the present invention there is provided a process for preparing a polymer comprising reacting at least the components i) to iii) in any order:
i) a compound of the Formula (1):
wherein:
T1 and T2 independently are HO—, HS— or R1HN—;
Q1 and Q2 independently are —NR2—;
A1 and A2 independently are an optionally substituted divalent organic linking group;
R1 when present is H or an optionally substituted alkyl, aryl or heterocyclyl group;
R2 is H or an optionally substituted alkyl, aryl or heterocyclyl group;
Z is an HO— group or a group of the Formula (2) or (3);
(*)-L-X Formula (2)
L is —HN—, —O— or —S—;
X is an optionally substituted organic group;
each X independently is an optionally substituted organic group;
in both Formulae (2) and (3) the asterisk (*) signifies the point of attachment to the triazine ring:
ii) a diisocyanate;
iii) an isocyanate reactive compound having at least one ionic group.
Unless stated to the contrary, in the present patent the words "a" and "an" are meant to include the possibility of using one or more of that item. Thus, a compound of Formula (1) means one or more compounds of Formula (1). Similarly, a diisocyanate means one or more diisocyanates.
Whilst the compounds as described in the first aspect of the present invention have been drawn in one structural formula the compounds and the scope of the claims are also intended to cover several isomers thereof including for example: tautomers, optical isomers, isotopic isomers etc.
Compound of Formula (1)
Preferably, the compound of Formula (1) has no ionic groups. This helps to prevent gelation, or branching and allows the preparation of the polymer having a linear structure. Preferably, the only hydroxyl, thiol or amine groups present in the compound of Formula (1) are those possible from the T1 and T2 groups.
T1 and T2
Preferably, T1 and T2 are each independently HO— or R1HN—, more preferably T1 and T2 are HO—. Accordingly, it is preferred that the compound of Formula (1) is a diamine or a diol, more preferably a diol. When T1 and T2 are both HO— the final polymers are of course polyurethanes.
When T1 and/or T2 is HNR1— it is preferred that the reactivity of this group is relatively low towards halo triazines when compared to amine groups in general. One way of achieving the desired lower reactivity is use primary amines wherein R1 is H. In such a case it is desirable that R2 is not H but is selected from optionally substituted alkyl, aryl or heterocyclyl groups.
R1 and R2
When an R1 or R2 group is an optionally substituted alkyl group, it is preferably optionally substituted C1-20 alkyl.
When an R1 or R2 group is an optionally substituted aryl group it is preferably an optionally substituted phenyl or naphthyl group.
When an R1 or R2 group is an optionally substituted heterocyclyl it may be aromatic (heteroaryl) or non aromatic. When R1 or R2 is heterocyclyl it is preferably a 5- or 6-membered ring containing from 1 to 3 atoms selected from N, S and O in the ring. The remaining atoms being carbon atoms.
Preferred examples of which include optionally substituted pyrrolyl, thiophenyl, furanyl, pyridyl, pyrimidyl, pyrazinyl, triazinyl, imidazolyl, thiazolyl, oxazolyl and pyrazolyl.
Preferably, R2 is H. This is especially so when T1 and T2 are both HO—.
Optional Substituents
When R1 or R2 is not H, the optional substituents for R1 or R2 preferably independently include —NO2, CN, halo (especially Cl, F, Br and I), —NHC(O)C1-6alkyl, —SO2NHC1-6alkyl, —SO2C1-6alkyl, —C1-6alkyl, —OC1-6alkyl, —OC(O)C1-6alkyl, polypropyleneoxide ending in a C1-6alkyl group, polyethyleneoxide ending in a C1-6 alkyl group. It is preferred that all the R1 and R2 groups have no ionic, thiol, amine, hydrazo (H2NNH—) or hydroxyl (HO—) groups. We have found that the presence of such groups in the R1 and R2 position tends to promote unwanted gelation in the subsequent reaction with the diisocyanate in component ii).
The optional substituents for R1 and R2 may also be used as optional substituents for any other group which mentions the possibility of being optionally substituted. Thus for example these groups may be substituents on A1 and A2 groups or for that matter X groups.
Each R2 group is preferably independently a H or C1-6 alkyl group, more preferably all the R2 groups are H. When all the R2 groups are H this means the compound of Formula (1) may be prepared from compounds which have a primary amine group. We have found that the primary amines allow particularly effective reaction with halo triazines so as to prepare the compound of Formula (1) in good yield and purity.
A1 and A2
The groups A1 and A2 may be any optionally substituted divalent organic linking group.
A1 and A2 may be an alkylene, a cycloalkylene, arylene, or heterocyclylene group which may be optionally interrupted by other groups. Of these alkylene groups are preferred. The heterocyclylene groups may be aromatic or non-aromatic. The groups A1 and A2 may be combinations of alkylene, arylene and heterocyclylene groups. The groups A1 and A2 may be interrupted by groups such as —O—, —S—, —CO2—, —NHCO—, —SO2— and —NHSO2—. Preferably A1 and A2 are each independently an arylene, an alkylene or a combination thereof. A1 and A2 may be optionally substituted with one of more or the optional substituents as mentioned for R1 and R2. In some embodiments A1 and/or A2 is/are unsubstituted.
Preferably both the groups A1 and A2 have no ionic, amine, hydrazo (HN2NH—), thiol or hydroxyl groups. This helps to prevent any gelation in the subsequent reaction with the diisocyanate in component ii).
When A1 or A2 is arylene it is preferably divalent naphthylene or phenylene. When A1 is phenylene the linking groups to T1 and Q1 may be arranged in an ortho, meta or more preferably a para position. The same is preferred for A2 wherein the linking groups are now T2 and Q2.
When A1 or A2 is an alkylene group it is preferably a C1-30 alkylene, especially a C1-20 alkylene and most especially a C2-8 alkylene. The alkylene groups may be branched or linear. Preferred examples are —(CH2)1-20— groups, examples of which are (CH2)2, (CH2)3, (CH2)4, (CH2)6 and (CH2)8.
A1 and A2 may be a xylylene group (—CH2-phenylene-CH2—), in which the CH2 groups may be ortho, meta or para with respect to the phenylene ring.
In view of the foregoing, preferably A1 and A2 are independently selected from C1-30 alkylene, a phenylene, a naphthylene and a xylylene group each of which may be optionally substituted. More preferably A1 and A2 are independently selected from optionally substituted C1-30 alkylene groups, preferred examples of which are mentioned above.
Preferred specific examples of A1 and A2 groups are *CH2CH2*, *CH2CH*CH3, *CH2CH*CH2CH3 and ortho, para and meta-phenylene wherein the asterisk marks the point of attachment of the groups in the compound of Formula (1).
The groups A1 and A2 may be different but more preferably they are the same.
Preferably Z is of the Formula (2) or (3).
In the compounds of Formula (2) it is preferred that L is —HN— or —O—, more preferably —HN—.
The optionally substituted organic group X in the Compounds of Formula (2) and (3) may be of any kind without limitation. The organic group may by alkyl, aryl, heterocyclyl or a mixture thereof.
When an X group is an optionally substituted alkyl group, it is preferably optionally substituted C1-20 alkyl.
When an X group is an optionally substituted aryl group it is preferably an optionally substituted phenyl or naphthyl group.
When an X group is an optionally substituted heterocyclyl it may be aromatic (heteroaryl) or non aromatic. When X is heterocyclyl it is preferably a 5- or 6-membered ring containing from 1 to 3 atoms selected from N, S and O in the ring. The remaining atoms being carbon atoms.
The optional substituents may be any of those previously mentioned for R1 and R2 groups.
Whilst it is possible that the group of Formula (2) or (3) has ionic groups it is preferred that such groups are not present. The absence of these groups helps to prevent unwanted branching and gelation of the final polymer. For similar reasons preferably, the optional substituent on all X groups are not an amine, thiol, hydrazo (NH2NH—) or hydroxl groups.
More than one compound of Formula (1) may be present in component i).
Preparation of the Compounds of Formula (1)
The compounds of Formula (1) are preferably prepared in two stages:
The first stage preferably comprises reacting T1A1Q1H and T2A2Q2H with a trihalo-triazine wherein T1, A1, Q1 and T2, A2 and Q2 are as herein before descried and preferred.
Of course, in some cases T1A1Q1H and T2A2Q2H may be the same compound.
As mentioned T1 and T2 are preferably both —OH. Thus for preferred compounds of the Formulae (1) T1A1Q1H and T2A2Q2H are monoamino-monoalcohols.
Especially preferred examples are ethanolamine (HO—CH2CH2—NH2), CH3CH(OH)CH2NH2, CH3CH2CH(OH)CH2NH2, and HO-phenylene-NH2 and HOCH2-phenylene-CH2—NH2. Other suitable examples of monoamino-monoalcohols include 3-amino propanol, 4-amino butanol, 2-amino-2-methyl-1-propanol, 5-amino pentanol, 6-amino hexanol and 8-amino octanol.
The corresponding monoamino-monothiols may also be used.
The halo groups in the trihalo-triazine may be I, Br, Cl or F but are preferably chlorine and thus the preferred trihalo-triazine is cyanuric chloride.
The reaction in stage 1 is preferably performed whilst maintaining moderate to low temperatures. Preferably the trihalo-triazine is suspended in a liquid medium at a temperature of less than 10° C., preferably from −5° C. to 5° C.
It is then preferred to add the compounds of Formulae T1A1Q1H and T2A2Q2H to the trihalo-triazine to form a reaction mixture. On completion of this addition it is preferred to heat the reaction mixture to 30 to 50° C., more preferably 40 to 45° C. This temperature is preferably maintained for a period of 1 to 10 hours, more preferably 2 to 4 hours and especially about 3 hours. The pH for the reaction is preferably from 5 to 9, more preferably from 6 to 7. Any suitable base may be used to obtain this pH. Preferred bases are alkali metal hydroxides, especially sodium hydroxide. Preferably, the reaction is completed by raising the temperature to from 50 to 80° C., more preferably from 50 to 70° C. and especially to around 60° C. Preferably the raised temperature is maintained for a period of 1 to 5, more preferably from 1 to 3 hours and especially about 2 hours.
Preferably, the molar amounts of T1A1Q1H and T2A2Q2H and trihalo-triazine correspond approximately to the theoretical structure (i.e. 1 mole: 1 mole: 1 mole).
The reaction is preferably carried out in a liquid medium which is preferably aqueous, more preferably comprises of water and no other liquid. Organic liquids may also be used, alone or in combination with water. Suitable examples of organic liquids include N-methyl pyrrolidone and sulfolane.
In stage 2 the product of stage 1 can be reacted in a number of ways.
When the compound of Formula (1) has a Z group which is an HO— group the remaining halo group attached to the triazine ring after stage 1 may be hydrolysed. This is preferably performed in an aqueous liquid medium. Preferably an acid or a base is used to accelerate the hydrolysis. Heating to an elevated temperature of between 60° C. to 90° C. is often used to accelerate the hydrolysis. As mentioned before it is more preferred that Z is of the Formula (2) or (3).
When Z is of the Formula (2) the product of stage 1 is preferably reacted with a compound of the Formula HLX wherein L and X are as previously defined and preferred. Preferred compounds of the Formula HLX include alkyl, aryl and heterocyclyl mono alcohols, mono thiols and especially mono amines. Examples of suitable amines include C2-30, especially C3-30 and particularly C4-20 alkyl mono-amines. These may be branched or linear. Other suitable amines include aromatic amines such as aniline, toluidine and trimethyl aniline.
Equally, when Z is of the Formula (3) the product of stage 1 is preferably reacted with a compound of the Formula HN(X)2. Preferred examples of suitable compounds of the Formula HN(X)2 include di-alkyl amines especially C2-30 and more especially C2-20 dialkyl amines. For di-alkyl amines the C2-30 or C2-20 preference relates to the number of carbon atoms in each alkyl chain. Thus, in total a C2-20 dialkyl amine has from 4 to 40 carbon atoms. The alkyl chains may be linear or branched. Aromatic diamines such as diphenylamine may also be used.
The reaction of the compounds of Formula HN(X)2 or HLX with trihalo triazine are preferably performed at a temperature of from 40 to 100, especially from 50 to 90 and most especially from 60 to 80° C. The time for the reaction is preferably from 1 to 16 hours, more preferably from 2 to 16 hours and especially from 4 to 12 hours.
The reactions are also preferably performed at a pH of from 7 to 12 and most preferably at a pH of between 9 to 11.
The above reaction may prepare a single compound of Formula (1) or a number of different compounds having the Formula (1). For example it is possible to use mixtures of compounds of the Formula HLX and HN(X)2 or mixtures of two different compounds of the Formula HLX.
The compounds of Formula (1) may be used directly however it is often preferable to purify the compound of Formula (1). The compound of Formula (1) may be isolated on a filter and washed with pure liquid medium. The compound of Formula (1) may be ultrafiltered using a membrane purification process.
It is sometimes useful to isolate the compound of Formula (1) in a dry form. Preferred drying methods include vacuum drying, oven drying, spray drying and the like.
Diisocyanate
The diisocyanate may be of any kind without any particular limitations. The diisocyanate may be aliphatic, aromatic or a mixture of both. Mixtures of diisocyanates may be used. Preferably, the diisocyanate has no ionic, amino, hydrazo (NH2NH—), thiol or hydroxyl groups. This helps to prevent gelation or branching.
Preferred examples of suitable diisocyanates include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, tetramethylxylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenyl-methane diisocyanate and its hydrogenated derivative, 2,4′-diphenylmethane diisocyanate and its hydrogenated derivative, 1,5-naphthylene diisocyanate and isophorone diisocyanate. Of these isophorone diisocyanate is especially preferred.
It is possible, though not preferable to prepare the polymer by reacting components i), ii) and iii) along with some isocyanates having three or more isocyanate groups and/or some isocyanates having just one isocyanate group. If such isocyanates are used they are preferably only present in minor proportions (e.g. less than 5 wt % of all isocyanates present). More preferably, the only isocyanates used in the preparation of the polymer are diisocyanates.
Component iii)
Component iii) is an isocyanate reactive compound having at least one ionic group.
Of course, as used herein the term isocyanate reactive compound in component iii) means isocyanate reactive compounds other than those of Formula (1).
Preferred examples of isocyanate reactive compounds are those having hydroxyl, thiol, amino and hydrazo (HN2—NH—) groups (as isocyanate reactive groups). Preferably, the isocyanate reactive compound has only two groups selected from hydroxyl, thiol, amino and hydrazo groups. In this way the isocyanate reactive compounds assist in producing a linear polymer.
The isocyanate reactive compounds in component iii) have at least one ionic group. The ionic group may be cationic or more preferably anionic.
Examples of cationic groups include quaternary amine, pyrridinium, guanide and biguanide groups. These may be in the free base or salt form or a mixture thereof. Suitable salt forms include the sulphate, nitrate, halide and carboxylate salts.
Preferred anionic groups are sulfonic acid, carboxylic acid and phosphorus containing acid groups. Of these carboxylic acid and phosphorus containing acid groups are preferred. Carboxylic acid groups prove to be especially suitable. Preferred examples of phosphorus containing acids are phosphoric and especially phosphonic acid groups. In our studies we have found that the phosphorus containing acid groups tend to promote particularly good optical density when inks utilising dispersions of pigments stabilised by the polymers prepared in the present invention are printed onto substrates such as plain paper.
The anionic groups may be in the form of the free acid, they may be in the form of a salt or a mixture thereof. Preferably, prior to and during the preparation of the polymer the anionic groups are in the acid form. Salt forms include those with ammonium, organic ammonium and hydroxyl functional organic ammonium especially alkali metal counter ions. Suitable alkali metals include potassium, sodium and lithium.
Preferred examples of isocyanate reactive compounds having at least one ionic group include diamines, diols and dithiols. Of these diamines and especially diols are preferred.
The isocyanate reactive compounds in component iii) preferably have from 1 to 5, especially from 1 to 3, more especially 1 or 2 and most especially one ionic group.
To introduce carboxylic acid groups dihydroxy alkanoic acids can be used especially 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolpentanic acid. Of these 2,2-dimethylolpropionic acid is preferred.
To introduce sulfonic acid groups bis(2-hydroxyethyl)-5-sodiosulphoisophthalate can be used.
To introduce phosphonic acid groups bis(2-hydroxyethyl)amino methylphosphonic acid can be used.
In one case, only the compounds in component iii) have any ionic groups.
It is possible to use mixtures of two or more different isocyanate reactive compound having at least one ionic group in component iii).
Optional Isocyanate Reactive Compound
It is possible that the polymer is prepared by reacting components i) to iii) and component iv) which is an isocyanate reactive compound having no ionic groups.
The isocyanate reactive compounds having no ionic groups preferably have two groups selected from hydroxyl, thiol, amino and hydrazo (HN2—NH—) groups. Of these dihydrazos, diamines and diols are preferred.
Preferred diols having no ionic groups include ethyleneglycol, 1,2- and 1,3-propyleneglycol, 1,2-; 1,3-; 1,4-; and 2,3-butylene glycols, 1,6-hexanediol and neopentyl glycol, 1,8-octanediol, bis-phenol A, cyclohexane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutyleneglycol and the like. Of these ethylene glycol is especially preferred.
Preferred diamines having no ionic groups include ethylene diamine, 1,2- and 1,3-propane diamine, 1,4-butane diamine, 1,5-pentane diamine, 1,6-hexane diamine, isophorone diamine, cyclohexane diamine, piperaine, 4,4′-methylene bis(cyclohexyl amine) and polyoxyalkylene diamines for example those sold under the Jeffamine™ tradename.
Preferred dihydrazos having no ionic groups include hydrazine and adipic acid dihydrazide.
Preferred Absence of Chromophores
Preferably, no component used in the synthetic preparation of the polymer is or contains a choromophore. More preferably none of the reaction steps is performed in the presence of a chromophore. Chromophore are highly coloured materials e.g. dyes. In this way colourless polymers may be prepared which contain no chromophore groups in their structure.
Groups in the Final Polymer
We have found that the presence of certain groups in the final polymer tends to reduce the final optical density achievable when the polymer is used to prepare a pigment-based ink. Groups of this kind include poly(ethyleneoxy) and polyester groups. Preferably to obtain the best possible optical density, the final polymer has no such groups.
More preferably component iii) and when present component iv) contain no compound which is or has such groups. Thus it is especially preferred that none of the compounds in components iii) and when present component iv) comprises poly(ethyleneoxy) or polyester groups. For example the compounds in component iii) and when present component iv) should not include alcohols, amines or thiols having poly(ethyleneneoxy) or polyester groups.
It is possible that small proportions of isocyanate reactive compounds in component iii) and when present component iv) have one or three or more isocyanate reactive groups. Preferably, the content of such isocyanate reactive compounds having one or three or more isocyanate reactive groups in component iii) and when present component iv) is relatively low (e.g. less than 5 wt % of all isocyanates present) so as not to make the pre-polymer molecular weight too low or make the pre-polymer too branched or gelled.
Preferred Absence of Certain Groups
Preferably, no compound in any of the components i) and ii) has any ionic groups.
Reaction Conditions for Components
The reaction between components is preferably performed in a liquid medium. Preferably, the liquid medium is a good solvent for all the components.
Preferred liquid media for the reaction of the components include 2-pyrrolidone, n-methyl pyrrolidone and sulfolane. The reaction temperature is preferably from 50 to 150° C., more preferably from 70 to 120° C. and especially from 80 to 110° C. The time for the reaction depends on the components used and the presence of catalyst but suitable reaction times are from 1 to 48 hours, more preferably from 2 to 24 hours and especially from 4 to 24 hours. Any suitable catalyst which is used in the preparation of polyurethanes may be used. Preferred examples of catalysts are tin salts and hindered amines.
Optional Purification
The final polymer prepared by the process according to the present invention may be used directly. It may also be purified to remove impurities from the polymer. Examples of suitable purification methods include filtration and washing and especially ultrafiltration.
Preferred Polymer Characteristics
The final polymer preferably has from 0.1 to 10 mmoles, more preferably from 0.5 to 8 mmoles, even more preferably from 0.5 to 5 mmoles and especially from 1 to 3 mmoles of ionic groups per g of polymer. The preferred method of establishing this is by titrimetry, especially potentiometric titration.
Preferably, the final polymer has a weight averaged molecular weight of from 1,000 to 500,000, more preferably from 5,000 to 200,000 and especially from 10,000 to 100,000.
The molecular weight is preferably measured by gel permeation chromatography (GPC). The molecular weight standards employed are preferably polyethylene glycol or more preferably polystyrene. The solvent used for GPC is preferably dimethyl formamide, tetrahydrofuran or acetone.
Preferably, the polymer is soluble in water. More preferably the polymer is soluble in water at 5% by weight when neutralised to 100% stoichiometry with lithium hydroxide. Preferably, the polymer is soluble at 25° C.
The final polymer preferably has anionic groups as previously mentioned and preferred in the section headed Component iii). In the case of the final polymer the anionic groups may be in the acid or more preferably in the salt form. The preferred salt forms are those previously mentioned in the section headed Component iii). A suitable method for preparing these salts is by the addition of a base such as ammonia, an organic amine, an organic alkanolamine or an alkali metal hydroxide. The addition of base is preferably performed after reacting components i) to iii) in the process as defined in the first aspect of the present invention.
Polymer obtained or Obtainable by the Process
According to a second aspect of the present invention there is provided a polymer obtained or obtainable by the process according to the first aspect of the present invention.
Preferably, the polymer is linear. Preferably, the polymer has a structure wherein the only ionic groups present were introduced from component iii).
According to a third aspect of the present invention there is provided a dispersion comprising a polymer according to the second aspect of the present invention, a particulate solid and a liquid vehicle.
The particulate solid in the dispersion preferably has a Z-averaged particle size of from 50 to 300 nm, more preferably from 70 to 200 nm and especially from 80 to 150 nm. The particle size is preferably measured by a light scattering device especially a Malvern Zetasizer™.
Preferably, the dispersion comprises:
i) 0.1 to 40 parts, more preferably 0.1 to 20 parts of the polymer;
ii) 0.1 to 40 parts, more preferably 0.1 to 20 parts of the particulate solid;
iii) 50 to 99.8, more preferably 60 to 99.8 parts of the liquid vehicle;
wherein the sum of the parts i) to iii) is 100 parts and all parts are by weight.
Preferably, the polymer is at least partially adsorbed onto the surface of the particulate solid. In this way the polymer acts as a dispersant so as to colloidally stabilise the particulate solid.
The amount of polymer in the dispersion (or ink) is preferably from 1 to 150%, more preferably from 1 to 40%, especially from 1 to 30% and more especially from 3 to 20% by weight based on the weight of particulate solid.
A preferred method for preparing the dispersions according to the third aspect of the present invention is to disperse, especially to comminute, a composition comprising the polymer according to the second aspect of the present invention, a particulate solid and a liquid vehicle. Dispersion processes include stirring, blending, shaking as well as milling and ultrasonication etc.
By the word comminute we mean only those processes which tend to significantly reduce the particle size of the particulate solid. Comminution includes for example ultrasonication, bead milling, microfluidizing and high pressure homogenising. Comminution does not include low shear dispersion processes such as stirring, shaking, tumbling and the like. Preferably, the polymer according to the second aspect of the present invention is the only dispersant present during the dispersion or comminution step.
Particulate Solid
The particulate solid may be of any kind. Preferably the particulate solid is a pigment. The pigment may comprise and preferably is an inorganic or organic pigment material or mixture thereof which is insoluble in the liquid vehicle. By insoluble we mean having a solubility of no more than 1%, more preferably no more than 0.1% by weight in the liquid vehicle. The solubility is preferably measured at a temperature of 25° C. The solubility is preferably measured at a pH of 8. Preferably, the solubility is measured in water, more preferably deionized water.
The pigment may be organic or inorganic.
A preferred pigment is an organic pigment, for example any of the classes of pigments described in the Third Edition of the Colour Index (1971) and subsequent revisions of, and supplements thereto, under the chapter headed "Pigments". Examples of organic pigments are those from the azo (including disazo and condensed azo), thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone, isodibenzanthrone, triphendioxazine, quinacridone and phthalocyanine series, especially copper phthalocyanine and its nuclear halogenated derivatives, and also lakes of acid, basic and mordant dyes. Preferred organic pigments are phthalocyanines, especially copper phthalocyanine pigments, azo pigments, indanthrones, anthanthrones, and quinacridones.
Preferred inorganic pigments include carbon black (especially gas blacks), titanium dioxide, silicon dioxide, aluminium oxide, iron oxides and sulfides.
For ink jet especially suitable pigments are carbon blacks, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 and C.I. Pigment Yellow 74. Of course there are many alternative pigments.
The pigment is preferably not surface treated so as to covalently bind water-dispersing groups onto its surface. Preferably, the pigment is not dispersible in water without the aid of a dispersant.
Liquid Vehicle for the Dispersion
The liquid vehicle may be wholly organic but preferably is or comprises water (i.e. is aqueous). We have found that the polymer according to the second aspect of the present invention is especially suitable as a dispersant for aqueous liquid vehicles.
In some cases, the liquid vehicle comprises water and optionally one or more water-miscible organic liquids. In some instances it is preferred that the liquid vehicle comprises water and less than 30% by weight, more preferably less than 20% by weight and especially less than 10% by weight of water-miscible organic liquids relative to the total amount of liquids present in the dispersion. In some cases the liquid vehicle for the dispersion comprises of water and no organic liquid. These dispersions facilitate more formulation options.
Preferred water-miscible organic liquids for inclusion into the liquid vehicle include:
i) C1-6-alkanols, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and cyclohexanol;
ii) linear amides, preferably dimethylformamide or dimethylacetamide;
iii) water-miscible ethers, preferably tetrahydrofuran and dioxane;
iv) diols, preferably diols having from 2 to 12 carbon atoms, for example ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol and thiodiglycol and oligo- and poly-alkyleneglycols, preferably diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol;
v) triols, preferably glycerol and 1,2,6-hexanetriol;
vi) mono-C1-4-alkyl ethers of diols, preferably mono-C1-4-alkyl ethers of diols having 2 to 12 carbon atoms, especially 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol, 2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol and ethyleneglycol monoallylether;
vii) cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone.
Preferably, the liquid vehicle comprises water and optionally 1 or more, especially optionally from 1 to 3, water-miscible organic liquids.
Encapsulated Particulate Solids
The dispersions according to the third aspect of the present invention can be used to prepared encapsulated particulate solids. To form an encapsulated particulate solid the polymer in the dispersion is cross-linked in the presence of a particulate solid and a liquid vehicle thereby encapsulating the solid particles, preferably with a cross-linked polymer shell.
The particulate solid is preferably a pigment as mentioned and preferred above. The liquid vehicle is preferably as mentioned above in the section headed liquid vehicle for the dispersion.
The cross-linking can be achieved by using a self cross-linking polymer. More preferably, a cross-linking agent is used to cross-link the polymer. Examples of suitable combinations of cross-linkable groups in the polymer and cross-linking groups in the cross-linking agent are listed in WO 2005/061087 at page 6, Table 1. Of these it is preferred that the cross-linkable group in the polymer is an ionic group especially a —CO2H group and/or a phosphorus containing acid group or salt thereof. For these cross-linkable groups the cross-linking agent is preferably selected from melamines, carbodiimides, oxetanes, isocyanates, aziridines and especially epoxides. Preferably, cross-linking is effected by means of an epoxy cross-linking agent.
Especially suitable encapsulation and cross-linking chemistry can be found in PCT patent publication WO2006/064193.
We have found that the encapsulated particulate solids tend to have even better colloidal stability towards liquid vehicles which comprise water and relatively high proportions of water-miscible organic liquids.
Inks preferably comprise at least one colorant such as a dye or a pigment. Preferably, in inks the particulate solid is a pigment. Preferably, no other colorant is present in the ink.
Preferably, the ink (especially an ink jet printing ink) comprises a dispersion according to the third aspect of the present invention.
According to a fourth aspect of the present invention there is provided an ink comprising a dispersion according to the third aspect of the present invention wherein the particulate solid is a pigment.
Preferably, the ink is an ink jet printing ink.
Preferably, the ink has a viscosity of less than 30 mPa·s, more preferably less than 20 mPa·s and especially less than 10 mPa·s. The viscosity is preferably at least 2 mPa·s. Preferably, the viscosity is Newtonian. Preferably, the viscosity is measured at 25° C. Preferably, the viscosity is measured using a shear rate of 100 s−1. The viscosity is preferably measured using a cone and plate geometry. A preferred apparatus for measuring the viscosity is a TA Instruments rheometer.
Preferably, the ink comprises:
i) 0.1 to 10 parts, more preferably from 1 to 10 parts of polymer according to the second aspect of the present invention;
ii) 0.1 to 10 parts, more preferably from 1 to 10 parts of a pigment;
iii) 80 to 99.8 parts, more preferably 80 to 98 parts of a liquid vehicle wherein all parts are by weight.
The ratio of polymer to pigment is as hereinbefore preferred. Preferably, the ink has a surface tension of 20 to 65 dynes/cm, more preferably 30 to 60 dynes/cm, when measured at a temperature of 25° C. The surface tension is preferably measured using a Kibron AquaPi.
The pH of the ink is preferably from 4 to 11, more preferably from 7 to 10.
When the ink is to be used as ink jet printing ink, the ink preferably has a concentration of halide ions of less than 500 parts per million, more preferably less than 100 parts per million. It is especially preferred that the ink has less than 100, more preferably less than 50 parts per million of divalent and trivalent metals. Parts per million as used above refers to parts by weight relative to the total weight of the ink. These low concentrations of ions in the resultant ink can be achieved by the abovementioned purification step.
The ink has preferably been treated so as to remove particles having a particle size of greater than 1 micron. This may be done by centrifugation or filtration.
The ink preferably comprises a liquid vehicle which is or comprises water. More preferably the liquid vehicle also comprises at least one water-miscible organic liquid. Preferably, the weight ratio of water to water-miscible organic liquid when both are present in the liquid medium may be from 99:1 to 5:95, more preferably 95:5 to 50:50, especially 95:5 to 70:30. Preferred water-miscible organic liquids are mentioned above. These inks are especially useful for ink jet as they assist in preventing any polymer from depositing on the ink jet printer nozzles. These water miscible organic liquids also help in the firing, substrate wetting, surface tension and substrate penetration characteristics of the ink.
The ink may optionally contain one of more ink additives. Preferably, the ink further comprises one or more additives selected from viscosity modifiers, pH buffers, metal chelating agents, surfactants, corrosion inhibitors, biocides, dyes, water miscible organic solvent(s) and/or kogation reducing additives.
Ink Jet Printer Cartridge
According to a fifth aspect of the present invention there is provided an ink jet printer cartridge comprising a chamber wherein an ink is present in the chamber and the ink is according to the fourth aspect of the present invention.
According to a sixth aspect of the present invention there is provided a substrate printed with an ink according to the fourth aspect of the present invention. The substrate may be of any kind including paper, glass, metal, material and plastic. We have found that the inks according to the fourth aspect of the present invention print onto substrates to provide prints having especially good optical density even on plain paper. The prints also demonstrate particularly good wet and dry rub-fastness.
Use of the Polymer for Dispersing
According to a seventh aspect of the present invention there is provided the_use of a polymer according to the second aspect of the present invention for dispersing (especially comminuting) a mixture comprising the polymer, the particulate solid and the liquid vehicle. The use of the polymer is especially good for dispersing and comminuting pigments. The particle size of the resulting particulate solid is preferably as mentioned above.
The present invention will now be illustrated by the following examples in which all parts are by weight unless stated to the contrary.
1. Preparation of Polymer Solution (1)
1.1 Preparation of the compound of Formula (1) [(Monomer (1)]
In step 1.1 the following compound of Formula (1a) may be prepared.
Cyanuric chloride (0.50 mol, 92.2 g) may be suspended in water (300 ml) and cooled to 0-5° C. in a reactor. A solution of ethanolamine (1.0 mol, 61.3 g) in water (50 ml) may be added dropwise to the reactor contents whilst maintaining the temperature at 0-5° C. to form a reaction mixture.
On completion of the addition the reaction mixture can be warmed to 40-45° C. and stirred at this temperature for 3 hours whilst slowly adding a solution of sodium hydroxide (1.0 mol, 40 g) in water (100 ml) to maintain the pH at 6-7.
40% Aqueous dimethylamine solution (0.50 mol, 56.3 g) may be added to the reaction mixture which can then stirred at a temperature of 70° C. and pH=9 (2M NaOH solution as required) for 8 hours and then allowed to cool to a temperature of 25° C. The product may be collected by filtration, washed with water (5×100 ml) and dried in a vacuum oven at 50° C. to give a white solid. This can be designated Monomer (1).
1.2. Preparation of Polymer Solution (1)
A mixture of the Monomer (1) as can be prepared above in step 1.1 (0.039 mol, 9.4 g), ethylene glycol (0.048 mol, 3.0 g), isophorone diisocyanate (0.273 mol, 60.7 g), 2,2 bis(hydroxymethyl) propionic acid (0.200 mol, 26.8 g) and N-methyl pyrrolidone (100 g) may be stirred and heated to 50° C. and 2 drops of tin ethylhexanoate may be added. This may form a reaction mixture. The reaction mixture can be stirred at a temperature of 95-100° C. for 18 hours.
The reaction mixture may be cooled, added to water (2000 ml) to give a solution and then can be acidified by the addition of concentrated hydrochloric acid until the pH was reduced to 3. The resultant precipitate may be collected by filtration and then suspended in water (2000 ml). The pH of the suspension may be adjusted to 9 by the addition of potassium hydroxide and then the suspension can be stirred for 1 hour.
Next the precipitate can be collected, suspended in water (500 ml) at pH=10 (KOH) and dialysed to a conductivity of less than 100 μS/cm. The dialysed solution may be concentrated under reduced pressure to give 325 g of a solution which contained the desired polymer at a concentration of 27% by weight. This can be designated Polymer Solution (1).
2. Inks
The polymers prepared in the present invention may be used to prepare dispersions of particulate solids (especially pigments) by means of comminution (e.g. milling). These dispersion may be added to ink vehicles so as to prepare a range of inks suitable for ink jet printing. Examples of preferred ink vehicles are as described in PCT patent publication WO2010/038071 at pages 28 to 30. Thus suitable ink jet printing inks can be prepared by substituting the mill-base in WO2010/038071 for analogous mill-bases using the polymer as prepared in the present invention.
1. A process for preparing a polymer comprising reacting at least the components i) to iii) in any order: i) a compound of the Formula (1): wherein: wherein: wherein: ii) a diisocyanate; iii) an isocyanate reactive compound having at least one ionic group.
Z is an HO— group or a group of the Formula (2) or (3); (*)-L-X Formula (2)
2. The process according to claim 1 where the ionic group is a carboxylic acid group, the isocyanate reactive compound has two groups selected from hydroxyl, thiol, amino and hydrazo groups and the ionic group is selected from phosphorus containing acid, sulfonic acid and carboxylic acid groups.
3. A process according to claim 1 wherein the ionic group is a carboxylic acid group, the isocyanate reactive compound having at least one ionic group is a dihdroxy alkanoic acid and the isocyanate reactive compound having at least one ionic group is 2,2-dimethylolpropionic acid.
4. The process according to claim 1 wherein T1 and T2 are HO—.
5. The process according to claim 1 wherein A1 and A2 are independently selected from —(CH2)1-20— groups.
6. The process according to claim 1 wherein the diisocyanate is selected from ethylene diisocyanate, 1,6-hexamethylene diisocyanate, tetramethylxylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenyl-methane diisocyanate and its hydrogenated derivative, 2,4′-diphenylmethane diisocyanate and its hydrogenated derivative, 1,5-naphthylene diisocyanate and isophorone diisocyanate.
7. The process according to claim 1 resulting in a polymer having a weight averaged molecular weight of from 1,000 to 500,000.
8. The process according to claim 1 wherein the resulting polymer has from 0.5 to 8 mmoles of ionic groups per g of polymer.
9. The process according to claim 1 wherein Z is of the Formulae (2) or (3).
10. A process according to claim 1 wherein the isocyanate reactive compound has two groups selected from hydroxyl, thiol, amino and hydrazo groups, the ionic group is selected from phosphorus containing acid, sulfonic acid and carboxylic acid groups, T1 and T2 are HO—, A1 and A2 are independently selected from —(CH2)1-20— groups, Z is of the Formula (2) or (3), the resulting polymer has a weight averaged molecular weight of from 1,000 to 500,000 and the resulting polymer has from 0.5 to 8 mmoles of ionic groups per g of polymer.
11. A polymer obtained by the process according to claim 1.
12. A dispersion comprising a polymer according to claim 11, a particulate solid and a liquid vehicle.
13. The dispersion according to claim 12 comprising: wherein the sum of the parts i) to iii) is 100 parts and all parts are by weight.
i) 0.1 to 40 parts of the polymer;
ii) 0.1 to 40 parts of the particulate solid;
iii) 50 to 99.8 parts of the liquid vehicle;
14. The dispersion according to claim 12 wherein the polymer has been cross-linked in the presence of the particulate solid and the liquid vehicle thereby encapsulating the solid particles.
15. An ink comprising a dispersion according to claim 12 wherein the particulate solid is a pigment.
16. An ink jet printer cartridge comprising a chamber wherein an ink is present in the chamber and the ink is according to claim 15.
17. A polymer obtained by the process according to claim 10.
19. The dispersion according to claim 18 comprising:
Referenced Cited
U.S. Patent Documents
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Patent History
Filed: Jul 2, 2012
Date of Patent: Jun 30, 2015
Patent Publication Number: 20140267513
Assignee: Fujifilm Imaging Colorants Limited
Inventor: Gavin Wright (Manchester)
Primary Examiner: Doris Lee
Application Number: 14/130,960
Current U.S. Class: Ink (347/100)
International Classification: C09D 11/30 (20140101); C08G 18/08 (20060101); C08G 18/32 (20060101); C08G 18/34 (20060101); C08G 18/38 (20060101); C08G 18/75 (20060101); C09D 11/102 (20140101); C09D 11/326 (20140101); B41J 2/175 (20060101);


text:
import React from 'react'
import Next from './scenes/Next'
import PastLaunches from './scenes/PastLaunches'

export default function App() {
  return (
    <React.Fragment>
      <Next />
      <PastLaunches />
    </React.Fragment>
  )
}

redpajama_set_name: RedPajamaGithub


The Pisteuo Real Estate Group is a boutique agency, assisting hundreds of buyers and sellers in the South Florida area purchase and sell their homes. We are Local Real Estate Specialists with a promise to "Find or Sell homes fast, for Top Dollar, and with the Least Amount of Stress."
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Assist clients in choosing mortgage options that meet their needs.
closing statements, deeds and leases.


After celebrating their twenty-five year anniversary in 2016 showcasing a majority of older material, Roadburn Live displays songs mainly from the "newer" and more progressive era of ENSLAVED's career, with songs from "In Times," "Riitiir," "Isa," "Below The Lights," and "Monumension." Featuring guest appearances of Einar Selvik (Wardruna), Aðalbjörn Tryggvason (Sólstafir), Per Wiberg (Opeth, Candlemass), and Menno Gootjes (Focus) on "Immigrant Song," the first cover song by ENSLAVED to appear on any record ever.
View the "Death In The Eyes Of Dawn" video by Costin Chioreanu on YouTube HERE on Vimeo HERE.
Grutle Kjellson comments on the album: "I'm generally not a huge fan of live albums. I like to be present at a show, to grasp the energy of the band, and to witness the sometimes magical symbiosis that occurs between the band and the audience. I am, however, a huge fan of the Roadburn Festival! I consider this to be my all-time favorite, both as a musician and as a guest. Therefore, if everENSLAVED were to release a live album, it had to be from a Roadburn show! I hope you will enjoy listening to this piece of wax as much as we did recording it!"


text:
Q: Table align RIGHT within VML textbox??? Does anyone know how to align a table right within a VML textbox? Left and center work fine but Right seems to get ignored....
Heres and example of the code

                         | This is test text |

A: Try setting your
 to width:100%;. If that doesn't fix it, put a 100% width table in there, nest and align the child (your desired content) within that.
Example:

                             | This is test text |

A: Sorry, late coming to the party...
you need an extra div with align="right" before you table & contents. VML textbox ignores align on tables for some reason.

                         | This is test text |

And here is the link

redpajama_set_name: RedPajamaStackExchange


text:
State History
Learn about the history of Massachusetts and find fun and interesting things to do and see all across Massachusetts. We've also found the best books, guides, websites, and other resources to make your study of Massachusetts fun and educational.
Things to See & Do in Massachusetts
Teaching Tips & Ideas
Frederick Law Olmsted National Historic Site
Frederick Law Olmsted (1822-1903) is recognized as the founder of American landscape architecture and the nation's foremost parkmaker. Olmsted moved his home to suburban Boston in 1883 and established at "Fairsted" the world's first full-scale professional office for the practice of landscape design. Over the course of the next century, his sons and successors expanded and perpetuated Olmsted's design ideals, philosophy, and influence. Visitors may tour the recently restored "Fairsted" historic landscape and a century-old design office that remains virtually unchanged from the days when the Olmsted firm's activity was at its height. Housed within the office complex are nearly 1,000,000 original design records detailing work on many of America's most treasured landscapes including the U. S. Capitol and White House Grounds; Great Smoky Mountains and Acadia National Parks; Yosemite Valley; New York's Central Park; and whole park systems in cities such as Seattle, Boston, and Louisville.
Boston Fire Museum
Located in an old firehouse, the Boston Fire Museum displays antique fire apparatus, fire alarms and artifacts, photos, and firefighting equiment.
Lowell National Historical Park
The history of America's Industrial Revolution is commemorated in Lowell, Massachusetts. The Boott Cotton Mills Museum with its operating weave room of 88 power looms, "mill girl" boardinghouses, the Suffolk Mill Turbine Exhibit and guided tours tell the story of the transition from farm to factory, chronicle immigrant and labor history and trace industrial technology. The park includes textile mills, worker housing, 5.6 miles of canals, and 19th-century commercial buildings.
Boston National Historical Park
Boston National Historical Park is an association of sites that together give the visitor a coherent view of the city's role in the nation's history. Each site brings to life the American ideals of freedom of speech, religion, government, and self-determination. Most of Boston National Historical Park's sites are connected by the Freedom Trail, a 3-mile walking tour of 16 sites and structures of historic importance in downtown Boston and Charlestown. In addition to the sites along the Freedom Trail, the National Park Service maintains an important part of the Charlestown Navy Yard, one of the nation's first naval shipyards, where the USS Constitution (also a stop on the Freedom Trail) is berthed. Located in South Boston and separate from the Freedom Trail, Dorchester Heights is significant for its role in the evacuation of the British from Boston during the Revolutionary War.
Saugus Iron Works National Historic Site
This is the site of the first integrated ironworks in North America, 1646-1668. It includes the reconstructed blast furnace, forge, rolling mill, and a restored 17th century house. With the archeological site of the 17th century iron-making plant, the museum collection, Iron Works House, and the reconstructed iron works complex, Saugus Iron Works National Historic Site illustrates the critical role of iron making to seventeenth-century settlement and its legacy in shaping the early history of the nation. The site's enclave setting on the Saugus River, featuring an open-air museum with working waterwheels, evokes a unique experience for park visitors. These resources demonstrate 17th century engineering and design methods, iron-making technology and operations, local and overseas trade, and life and work in the Massachusetts Bay Colony. The original manufacturing site served as a training ground for skilled iron workers for what would become America's iron and steel industry. Iron making provided the infrastructure for the rise of other colonial industries. Called, "the forerunner of America's industrial giants," the site served as a center for technology, innovation and invention. The site interprets early industrial manufacturing, with its enduring social, political and environmental ramifications.
Springfield Armory National Historic Site
Begun as a major arsenal under the authority of General George Washington early in the Revolutionary War, the first national armory, the Springfield Armory, began manufacturing muskets in 1794. Within decades, Springfield Armory had perfected pioneering manufacturing methods that were critical to American industrialization. The Armory represents nearly two centuries of continuous production of rifles and muskets used by America's armed forces in every war in the nation's history. Reopened in 1978 as the Springfield Armory National Historic Site, the original 1840's arsenal houses the world's largest collection of American military firearms. Year-round public programs, exhibits, and special events are hosted on the grounds of the National Historic Landmark.
Longfellow National Historic Site
Longfellow National Historic Site is an outstanding example of a historic site representing the themes of arts and literature. For almost half a century (1837-1882) this was the home of one of the world's foremost poets, scholars and educators, Henry Wadsworth Longfellow. Longfellow House is also significant in America's colonial history. General George Washington, Commander-in-Chief of the newly-formed Continental Army, headquartered and planned the Siege of Boston here between July, 1775 and April, 1776. Henry Wadsworth Longfellow enjoyed enormous popularity during his lifetime and continues to influence our cultural and historical perceptions. He and his immediate and extended family and friends played a central role in the intellectual and artistic life of nineteenth century America and are credited with shaping a distinctly American identity and culture. Longfellow House was a favorite gathering place for many prominent philosophers and artists including Ralph Waldo Emerson, Nathaniel Hawthorne, Julia Ward Howe, and Charles Sumner.
Essex National Heritage Area
The Essex National Heritage Area begins just 10 miles north of Boston and extends for 40 miles along the scenic coast of Massachusetts. The Area is characterized by white, sandy beaches interspersed with rugged granite outcroppings, and overlaid by 400 years of New England history and culture. From the Atlantic Ocean up the Merrimack River, this 550-square-mile region features historic seaports, white clapboard buildings, renown art and cultural museums, antique farms, wooden boat-building shops, early industrial mill complexes, and significant wildlife refuges - both on-shore and off-shore. The Area is instilled with authentic Yankee character. Three significant themes of American history can be easily experienced within its boundaries: early colonial settlement, maritime commerce and sailing, and New England's early Industrial Revolution. The Area contains two National Park sites and hundreds of historic structures, museums, and natural resources, and it is within an easy day trip of Boston by train or car.
Salem Maritime National Historic Site
Salem Maritime, the first National Historic Site in the National Park System, was established to preserve and interpret the maritime history of New England and the United States. The Site consists of about nine acres of land and twelve historic structures along the waterfront in Salem, Massachusetts, as well as a Visitor Center in downtown Salem. The Site documents the development of the Atlantic triangular trade during the colonial period, the role of privateering during the Revolutionary War, and the international maritime trade, especially with the Far East, which established American economic independence after the Revolution. The Site is also the focal point of the Essex National Heritage Area, designated in 1996, which links thousands of historic places in Essex County around three primary historic themes: colonial settlement, maritime trade, and early industrialization in the textile and shoe industries.
Boston African American National Historic Site
Located in the heart of Boston's Beacon Hill neighborhood, the site includes 15 pre-Civil War structures relating to the history of Boston's 19th century African-American community, including: the African Meeting House, the oldest standing African-American church in the United States. The sites are linked by the 1.6 mile (2.5 km) Black Heritage Trail®. Augustus Saint-Gaudens', memorial to Robert Gould Shaw and the African-American Massachusetts 54th Regiment, stands on the trail.
New Bedford Whaling National Historical Park
New Bedford Whaling National Historical Park commemorates the heritage of the world's preeminent whaling port during the 19th century. A variety of cultural landscapes, historic buildings, museum collections, and archives preserve this history and collectively recount the stories of a remarkable era. Whaling, a leading 19th century enterprise, contributed to America's economic and political vitality. New Bedford Whaling National Historical Park was created in 1996. The park encompasses 34 acres spread over 13 city blocks and includes a visitor center, the New Bedford Whaling Museum,the Seamen's Bethel, the schooner Ernestina, and the Rotch-Jones-Duff House and Garden Museum. The park's enabling legislation also established a legislative connection with the Inupiat Heritage Center in Barrow, Alaska, to commemorate the more than 2,000 whaling voyages from New Bedford to the Western Arctic.
Boston Harbor Islands national park area includes 34 islands situated within the Greater Boston shoreline. The islands are rich in natural and cultural resources. Imagine a place where you can explore tide pools, walk through a Civil War era fort, climb a lighthouse, hike lush trails and salt marshes, camp under the stars, or relax while fishing, picnicking or swimming...all within reach of downtown Boston. The 34 islands are managed by a unique, 13-member Partnership which includes the National Park Service and other public and private organizations. An advisory council provides a mechanism for public involvement.
Blackstone River Valley National Heritage Corridor
The Blackstone River Valley National Heritage Corridor is a region of nearly 400,000 acres located within Worcester County in central Massachusetts and Providence County in northern Rhode Island. It includes cities, towns, villages and almost one million people. The American Industrial Revolution began in the Blackstone River Valley. It changed the landscape of the Valley and transformed life in America. The Blackstone River provided the waterpower for the birth of industry in America with its 438-foot drop over a 46-mile length. Even today, the Valley retains its "wholeness" as a unique landscape with a concentration of historic, cultural and natural resources that represent 18th and 19th century industrial production in America.
John F. Kennedy National Historic Site
John Fitzgerald Kennedy National Historic Site preserves the birthplace in 1917 and boyhood home of the 35th President of the United States. The modest frame house at 83 Beals Street in Brookline was the first home shared by the president's father and mother, Joseph P. and Rose Fitzgerald Kennedy, and represents the social and political beginnings of one of America's most prominent families. Today the National Park Service presents guided tours of the house with its display of household furnishings, photographs, and significant mementos personally collected by Mrs. Kennedy. Many pieces in the museum collection are original to the 1914-1920 historic period, reflecting the lifestyle and various pursuits and interests of the Kennedys. A narrative tour produced by Mrs. Kennedy provides visitors with an evocative glimpse of family life in the early Brookline years. Park Rangers also occasionally offer tours of the nearby neighborhood that include stops by the second Kennedy home, schools where the children studied, and Saint Aidan's Roman Catholic Church where the family worshipped.
Adams National Historical Park
Adams National Historical Park is located in the City of Quincy, Norfolk County, Massachusetts, approximately ten miles south of Boston. The Park comprises 11 historic structures and a cultural landscape totaling almost 14 acres. The story encompasses five generations of the Adams family (from 1720 to 1927) including two Presidents and First Ladies, three U.S.Ministers, historians, writers and family members who supported and contributed to the success of these public figures. The site's main historic features include: John Adams Birthplace, where 2nd U.S. President John Adams was born on October 30, 1735, and less than 75 yards away the John Quincy Adams Birthplace, where his son, John Quincy Adams, 6th U.S. President was born on July 11, 1767; the "Old House," home to four generations of the Adams family; the Stone Library contains more than 14,000 historic volumes and includes the book collection of John Quincy Adams; no tour is complete without a visit to the United First Parish Church, where both Presidents and the First Ladies are entombed in the Adams family crypt. There is an off-site visitor center located within one mile of the historic structures.
Minute Man National Historical Park
At Minute Man National Historical Park, the Battles of Lexington and Concord are brought to life through the preservation, restoration and interpretation of significant sites from "that famous day and year" when Colonists took up arms in defense of liberty and touched off the American Revolution. At Concord's North Bridge, visitors can see the place where, on April 19, 1775, Colonial militia men fired the famous "shot heard 'round the world." Reflect on the meaning of freedom in a tranquil, commemorative landscape that includes Daniel Chester French's Minute Man Statue. Along our five-mile "Battle Road Trail" you can travel back in time through a restored colonial landscape and retrace the steps of the British Regulars as they made the long and deadly journey back to Boston under fire from thousands of Colonial militia men. Parts of this trail follow the original route of the old "Battle Road" of April 19, 1775. Along the way, stop in and visit the Hartwell Tavern, a restored 18th-century tavern on Battle Road. It is now a "living history" center staffed by costumed Park Rangers who can offer you a glimpse of life in Revolutionary times. At the Wayside: Home of Authors, learn about Concord's "second revolution" as you visit the home of Nathaniel Hawthorne, one of America's most famous authors of the 19th century who helped define our American identity.
Knowledge Quest offers historical outline maps and timelines designed for the interactive study of world history and geography.
How I Teach a Large Family in a Relaxed, Classical Way: History
A look at teaching history across several grades using the classical method of education and a rotation of history every four years.
Ancient History Old Testament History Ancient Egypt Ancient Greece Ancient Rome Vikings Ancient Indo-Asia Middle Ages Renaissance Exploration & Discovery U.S. History World History Biographies Historical Fiction Historical Documents State History
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