text:
That's my gay follower. He likes to follow me and use my name to get the rise out of people. He works nights at the Rainbow Club doing dances for the men there. He was fired once because he got a little too friendly with a couple that was there one night. I guess he really makes the men happy there because they kept requesting for him. That kind of forced the Club to hire him back. He means no harm he just needs more consoling. He also needs to move out of his mothers basement.<quoted text>And people called me a racist on here before, yet they say nothing about your comments.
Car buyers standing by GM
General Motors Corporation stock hit its lowest point in more than 75 years on Friday, falling to just $1.27 per share at one point. Read more
7,061 - 7,080 of 7,213 Comments Last updated Jan 24, 2014
United States
#7295 Dec 27, 2012
#7296 Dec 27, 2012
As you may recall, I'm not a big union fan but the trade unions have excellent apprenticeship programs. They turn out some of the most skilled people.
Since: Oct 12
Location hidden
#7297 Dec 27, 2012
But, once a shop or factory has become completely union, do they have any choice?
#7298 Dec 27, 2012
I agree with you on that point Frank. I'm just saying that a merit pay increase is better than an across the board negotiated pay increase to everyone regardless of their job performance. Employers get more bang for their buck that way and they have more, motivated employees. There is an incentive to do above average work because they know they will be rewarded for it. If everyone gets the same pay raise, there is no incentive for workers to improve. They are satisfied with the status quo. For companies to grow, they can never be satisfied with their short term successes. They must always be looking for ways to improve.
#7299 Dec 27, 2012
I am glad you understand that but there are many people out there and on here that do not know that and just say all unions are bad.
#7300 Dec 27, 2012
Yes they have choices. I have seen some big companies and small companies that told unions if they don't accept what the company wants they will close the doors and move the work to another facility or just close down or sell the company. If a company treats their workers good and with respect they will be willing to give up raises or benefits if the company is really hurting.
#7301 Dec 27, 2012
I understand what you are saying but I think the company I work for is a good example. The other plants in our company have not got raises for 4 years and the company stopped there contributions to the workers 401k 4 years ago. Out of all the plants in the company our plant has the oldest and most experienced workers because we have something to work for. The other workers don't care because they don't have anything to work for. Another good point is if we didn't have a union we would be working some kind of a 12 hour continuous shift that is definite because our plant president pushes that every negitiation. We work 8 hour days 5 days a week, time and a half saturdays and double time sundays.
#7302 Dec 27, 2012
Another thing is we tried to get some kind of incentive program but they didn't want anything to do with that. The one in place is a joke and it's funny because the only time we get it is when a contract is up. We got a check for that program for the month before we went on strike. Its a joke, we even tried to give it back to them in a negotiation and they didn't want it. That just goes to show how good it is.
Since: Mar 09
#7303 Dec 27, 2012
I Do understand Frank.
I hope you didnt take what I said wrong,.. I did not mean to come off as being "anti-union".
It's been a long time, but I used to work for a unionized company.
But ever since then, I've been fortunate to work for a smaller company, which is kind of nice. If I want to, at any time I can talk to the owner if I want to, and it's much different where I am now. I know how it is at some big companies. I think I'm very lucky, and get to work in an environment like I do.
On a totally different note,......how do you like your new truck?
I'm on the fence right now, I've been looking a little bit at new ones. But mine only has 60K miles on it, and I dont really need a new one, but it's 8 years old, and sometimes, I just think I'd like something different.
I hope you like your new truck, I'm leaning towards just keeping mine for right now (main reason its paid for) which is kinda nice.
But then,..... a new one would be nice too.
The issue I have, is back about three years ago, the local Chevy dealer, and the GMC dealership were closed down, and it's now a 20 mile drive to one of those.
There is a Dodge dealership by me, and the Ford dealership where I bought mine at about 5 miles away, but no Chevy or GMC dealers near by.
#7304 Dec 27, 2012
Understand//////Toyota is worlds ahead of GM=Govt Motors. Nobody believed for a second that the same company that was bailed out with taxpayers money was #1/////Its laughable!!!!!!News sells....not GM autos of course. Detroit news talked about the Space Shuttle Endeavor.They left out the part where thw Toyota Tundra pulled it .....the rest of the world told the whole story....not Derot!Toyota Envy Lives!!!!!!!!!!
United States
#7305 Dec 27, 2012
so it looks like Frank and Jim have been doing pole dancers at the rainbow club. Both of you show your ignorance everytime you post. You guys are there to the biggest push back to sender or at least at the nothing else you were both a couple of real sure if you're down with pizza and I said that because that because of American car is always going to be better that you played great day after day and with slanted eyes and order your skin to touch with your interview rice.
#7306 Dec 28, 2012
If that's the case, then the company is not a forward thinking company.
#7307 Dec 28, 2012
I love my new truck. I was in the same situation but mine had 150,000 miles I couldn't pass up the deal. Old truck still ran great though. I love having a new truck but I do miss the old one.
United States
#7308 Dec 28, 2012
I got my new toy I love my new toy It's big and black It's a nice toy with spots turd burglars on pizza in the back door with screws on the cars short weewee in the air on the fish last night when the rainbow club Saturday morning slept poverty in Obama back end angry black lady big butt! Lol! In the door second constitutions suck fruit with what angle black nefarious negro poor rainbows and elephants
Since: Oct 12
Location hidden
#7309 Dec 28, 2012
You do know, the ranking in this regard, is totally subject to sales numbers? It isn't about quality or innovation or fuel mileage....it isn't even about government subsidy, and by the way, the japanese have helped out their own corporations as well.....That is why it is a positive corporate step, when GM builds a plant in China or Toyota builds a truck plant in Thailand or California....It isn't necessarily about who is ahead of who....if it was, Mercedes Benz would likely be number one.....
#7310 Dec 28, 2012
I have talked to people that worked at other plants and done other research and all they do is take from their workers except for us because we are the only union shop and thats why we have a union. they told their other workers when they took 5% off of their pay and stopped 401k contributions they were looking toward the future. A good way to explain the way this company is, they started in the 80's as a small shop down south and the way they grew was to buy other plants, close the plants and add on to the plant down south. They still do that to this day. The other plants that are still open were bought because they specialize in something others don't and because of their location. There was a plant in our area they bought in the 90's that had about 500 workers and was one of the biggest plants in the industry at the time. As soon as they bought it they locked the gates and told the people working they had to leave because they were closing and the next shift coming in was locked out and told to go home. They had tractor trailers with flat beds lined up over a mile down the road, brought in security guards and the people that were taking machines out killed the power and air, took a sawzall to the air lines and electric lines and took out the machines. This was all done because a customer they got at their plant down south. The local plant had the big machines they needed for their new customer. They really made out they got a new customer, the machines they needed and extra work to go with it. On the other end almost 500 people are out of a job. I hope this helps you understand what the people are like I work for.
London, UK
#7311 Dec 28, 2012
When ever I see a war torn nation on the news, there's always a bunch of militia, with AK47s, sitting in the back of a Toyota pick up truck, I think its the universal vehicle choice for insurgent guerrillas LOL
London, UK
#7312 Dec 28, 2012
What are you talking about, "miles ahead", the Japanese car industry has taken massive blows recently, from performance, design and mechanical faults, European cars are the worlds best right now, and have been for a long time, Japan has fallen behind
London, UK
#7313 Dec 28, 2012
Gm have a division in britain and europe called vauxhall, and it is one of the best selling cars in europe and especially in britain, ford are also big sellers in europe, but the other american car companies are rarely seen here, Chevrolet, Buick, cadilacs, etc, they dont seem to sell in Europe and you hardly ever see them, allthoe there are a lot of massive humvees in Britain
Since: Oct 12
Location hidden
#7314 Dec 28, 2012
Good on gas and takes a 50cal. like a man.....
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The "unitary patent package" consists of three elements:
The two Regulations implement enhanced cooperation in the area of the creation of unitary patent protection. 25 Member States participate in this enhanced cooperation. All these Member States and Italy which signalled in December 2011 its intention to join will conclude the international agreement on the Unified Patent Court.
The unitary patent package will have four major advantages:
It will create a unitary patent with uniform protection within the territory of the participating 25 Member States;
The unitary patent will be available on a one-stop shop basis at affordable costs, as it will be centrally granted by the European Patent Office and no further validation requirements need to be fulfilled and applications can be filed in any language;
It will create a unified and specialised jurisdiction in patent matters for the participating Member States, and thus avoid an unnecessary duplication of litigation cases before the various courts of the various Member States concerned, and enhance legal certainty; and
It will ensure the dissemination of patent information in all languages of the European Union through high-quality machine translation services which will be available online and free of charge.
The single unitary patent option will offer those who wish to protect their invention in Europe huge cost advantages and reduce the administrative burden.
The single jurisdiction for patent matters will have the major advantage compared to today's situation that, in the future, legal certainty will be enhanced. The risk of multiple parallel court proceedings leading possibly to divergent outcomes will disappear.
A patent can be granted for any inventions having a technical character provided that they are new, involve an inventive step and are susceptible of industrial application. A patent can cover how things work, what they do, what they are made of, and how they are made. Anybody - an individual or a company or an institution - can apply for a patent.
Aesthetic creations, mathematical methods, computer games etc. are not regarded as inventions as they lack a technical character. To qualify as new, it is important that the invention has not been in the public domain (state of the art) before the date on which the patent application is filed.
Patents encourage companies to make the necessary investment for innovation. There would be little incentive otherwise for individuals and companies to devote the necessary resources to research and development.
A patent gives the owner the right to prevent others from making, using or selling the invention without permission. However, it is not automatically implied that the patent owner may make use of it. Quite often, permits from national authorities governed by laws other than patent law, have to be obtained before commercialising a product covered by a patent.
In general, the exclusive rights of a patent owner to exploit the invention commercially last for a maximum of 20 years from the filing date, subject to the payment of regular renewal fees. Anyone else wishing to use the invention while it is still patented must request authorisation from the patent holder and may have to pay a licence fee. In return for this exclusive right, the details of how it works are published 18 months after filing the patent application. In this way, the scientific or technical know-how - the technical teaching of the invention - is made public allowing others to further their own research. As a general rule the patent renewal fees increase over time. This means that only the most commercially viable patents are maintained for the full period. At the end of the 20-year term, the patent lapses.
As a hypothetical example, a company may get a patent for a new chemical that acts as better lubricant than existing products on the market. The patent could include claims about the molecule or composition of the lubricant, how it can be made, and examples of where the lubricant can be applied, for example, in the engine of a car. Anyone wanting to produce the chemical would have to ask the company for a licence, normally in return for payment. However, researchers in the field would benefit from the technological knowledge disclosed, for example the process involved to make the chemical protected by the patent. This could bring about further research leading to more advanced lubricants which themselves could be patented.
Today, (technical) inventions can be protected in Europe either by national patents granted by the competent national authorities or by European patents granted centrally by the European Patent Office (EPO).
Member States have their own patent authorities which deal with applications for national patents. The protection conferred by a national patent is limited to the territory of the State concerned.
If the applicant chooses to apply for a European patent, the application will be dealt with by the EPO, having its headquarters in Munich and a branch in The Hague. The EPO is a body of the European Patent Organisation, an international organisation comprising 38 members (27 EU Member States + 11 other European countries). The Organisation was established in 1973 following the signature of the European Patent Convention (EPC).
The EPC provides a single procedure for granting patents in Europe. On the basis of one single patent application processed in one of the three official languages of the EPO (English, French and German), inventors and businesses can obtain a European patent. When the EPO grants a European patent, the full text of the patent, known as the specification, is published in the official language of the EPO chosen by the applicant as the language of the proceedings. At the grant stage, the applicant must also provide a translation of the part of the patent that defines the scope of protection - the claims – into the other two official EPO languages.
However, the grant of the European patent is not enough for it to take effect in most Contracting States to the EPC. The patent proprietor must choose the countries in which he/she wishes to have protection and validate the European patent in these states within a short time limit after grant. A number of different validation requirements may apply. For example, the patent proprietor may have to pay a fee to the national patent office, comply with various formal requirements and provide a translation of the patent to the official language of the State.
In order to obtain unitary effect, patent holders need to request the unitary effect at the European Patent Office (EPO) no later than one month after the grant of their European patent has become effective. The unitary effect which is entered by the EPO into its Register transforms the European patent into one single patent for the 25 Member States. Anybody, regardless of the country of origin, can opt for a unitary patent.
The unitary patent will be centrally administered by the EPO throughout its whole life, i.e. until the end of the patent term (20 years from the filing date of the patent application at the latest).
For the two Member States which, up until now, do not participate in this project, inventors will of course be able to obtain patent protection via their 'classical' European patents. The European patent will need to be separately validated in these two countries.
As the unitary patent is a further option, it is at the moment not clear how frequently the new alternative will be used. We are however confident that the system will stand the test which however can only be demonstrated once the system is in place.
The unitary patent – which is the object of today's EU regulations - will be a third option for companies or inventors seeking patent protection in Europe. It will be a further tool in the inventor's toolbox in addition to national patents and 'classical' European patents (i.e. without unitary effect). For more details on the latter see point 6.
A unitary patent is a European patent with unitary effect. The procedure up to the grant of the patent will be the same as for ('classical') European patents without unitary effect. After grant, European patents will fall into one of the two categories.
A 'classical' European patent needs to be validated in each State for which it has been granted. It has the same effect as a national patent granted in the respective territory and its fate in these States may be different, depending e.g. on any court proceedings which take place in these States. The 'classical' patent is therefore often compared with a bundle of national patents which is centrally granted.
In contrast, the unitary patent will ensure uniform protection for an invention in 25 Member States (all Member States except Italy and Spain) on a one-stop shop basis.
In 2011, 142 810 patent applications were filed with the EPO, of which 71 904 came from EPC countries and 70 906 from other parts of the world.
Germany filed the most applications to the EPO (26 234), followed by France (9 633), the Netherlands (5 611), the UK (4 765) and Italy (3 982). For the full list, please consult the EPO's 2011 annual report at
In 2011, 62 112 European patents were granted by the EPO.
Efforts to create a common patent applicable across all European countries have been made since the 1960s but for a number of reasons have never been successful.
In 2000 the European Commission made a proposal to create a Community Patent through a Regulation [now 'EU patent' under the Lisbon Treaty]. The aim was to provide for a single patent title applicable in all Member States. In 2003 Member States agreed a common political approach but failed to reach a final agreement, including over the details of the translation regime. Following a wide-scale consultation in 2006, the Commission produced a Communication in April 2007 which confirmed the commitment to the Community patent and re-launched negotiations in Member States.
In December 2009 Member States unanimously agreed on Conclusions for an enhanced patent system, including the main features of the EU patent, except for the translation arrangements. Instead, they affirmed the need for a new Regulation to cover the latter matter. The Commission proposed a regulation on the translation arrangements for the EU patent in July 2010. But despite all the efforts of the Belgian Presidency, the Council could not reach a unanimous agreement on the applicable translation arrangements. In December 2010 the Competitiveness Council confirmed that there were insurmountable difficulties that made the establishment of such a regime impossible to attain within a reasonable period by applying the relevant provisions of the Treaties.
At the request of 12 Member States, the Commission proposed to launch enhanced cooperation in the area of unitary patent protection on 14 December 2010. Following the Commission's decision, another 13 Member States submitted their request to join the enhanced cooperation. The European Parliament gave its consent on 15 February and on 10 March 2011, the Competitiveness Council authorised the launch of enhanced cooperation with the participation of 25 Member States.
On 13 April 2011, the Commission adopted the proposals for the two implementing regulations. Both implementing regulations were finally adopted at the end of 2012. They entered into force in the beginning of 2013 but will only apply from 1 January 2014 or the date of entry into force of the Agreement on a Unified Patent Court (the 'Agreement'), whichever is the later.
One aspect of the reform package is the creation of unitary patent protection via the European patent with unitary effect ('unitary patent'). This will make it possible for inventors (individuals, companies or institutions) to protect their inventions in 25 Member States by filing a single patent application with the European Patent Office. After the patent is granted, there will be no need to validate it one by one in each country. This will make the existing system much simpler, much less burdensome and less expensive for inventors. It will end the complex validation requirements, and in particular limit the very expensive translation requirements in the participating Member States. Today, obtaining patent protection in the territory of the 27 Member States by means of a European patent costs about 36 000 euro (the majority of which goes on translation and other costs linked to validation, such as fees of local patent offices and costs for local patent agents). After full implementation of the unitary patent project, the costs will go down to about 5 000 euro (i.e. the fees up until the grant of the patent including the translation of the claims into the two other official languages of the EPO).
Unitary patent protection will also protect inventions better than the current system. Due to the prohibitive costs involved in the national validation of European patents, today many inventors only patent their inventions in a handful of countries. This makes inventions less valuable as the lack of protection in other countries allows them to be copied more easily.
The second aspect is the setting up of the Unified Patent Court (UPC). This court will have exclusive competence for European patents with unitary effect and, after a transitional period, for all 'classical' European (bundle) patents. Undertakings will thus have legal certainty (once the UPC has decided) and will no longer need to defend, or respectively challenge, the patents in various national courts. The risk of parallel court proceedings with different outcomes in the participating Member States will therefore disappear.
The new system will consequently stimulate research, development and investment in innovation helping to boost growth in the EU. It will be advantageous for all inventors, in particular those which are most affected by the deficiencies of the current system, including SMEs.
For other major markets such as the United States of America and China, one single patent with a single jurisdiction is in place. The implementation of the unitary patent package will do the same for Europe.
No. The European patent with unitary effect will be based on two regulations which will be adopted in the framework of enhanced cooperation of 25 Member States (all Member States but Italy and Spain). This was necessary because an agreement between all 27 Member States could not be found. Eventually, 25 Member States have decided to proceed with enhanced cooperation in order to create a system of unitary patent protection in Europe. Member States not participating now can join later.
Enhanced cooperation is a possibility ensured by the Treaties that can only be adopted by the Council as a last resort, when it has established that the objectives of such cooperation cannot be attained within a reasonable period by the Union as a whole, and that at least nine Member States participate in it.
Applicants will have to file an application for a European patent with the EPO the same way as they do today. The new element is that, no later than one month from the date on which the grant of the European patent has become effective, the patentee can request the EPO to register the unitary effect in the European Patent Register. In the case of such a request made after the grant, the patent will take effect retroactively (from the mention of the grant) in the 25 participating Member States without any additional validation requirement. It will provide equal protection through the territories of these countries. The patent owner will have the choice of whether or not to request unitary effect for their European patents.
Inventors may therefore choose between unitary patents, the 'classical' European patents (to be validated in the Member States) or national patents (to be filed in all the Member States). The new reform package just provides an additional tool in the toolbox.
After the transitional period (in which certain additional translations will be required), the cost to obtain a European Patent with unitary effect will be around 5 000 euro. This covers the procedural fees of the EPO as well as the cost of the translation of the claims to the two other procedural languages of the EPO.
During the transitional period of maximum 12 years, the cost will be slightly higher, about 6 500 euro. This includes the cost of the additional translation required during the transitional period: in order to facilitate the access to patent information until high-quality machine translations become available, European patents with unitary effect that were granted in French or German will need to be translated to English and the ones granted in English will need to be translated to another official language of the EU.
Obtaining patent protection in the territory of the 27 Member States by means of a European patent costs today about 36 000 euro (the majority of which goes on translation and other costs linked to validation, such as fees of local patent offices and costs for local patent agents).
By comparison, in the US, a patent costs about 2 000 euros, in China about 600 euros.
Applications for European patents can be filed in any language. Yet applicants have to provide a translation of the application into English, French or German which are the official languages of the EPO (if the application was not filed in one of the official languages).
Under the new translation regime applicable to the creation of the unitary patent protection, SMEs, natural persons, non-profit organisations, universities and public research organisations having their residence or principal place of business within any of the 27 EU Member States will get a compensation of all translation costs up to a ceiling if the application was filed in one of the official languages of the European Union that is not an official language of the EPO.
The European patent is granted in one of the three EPO languages. Before the grant, the applicant is required to provide a translation of the claims (which define the scope of the subject-matter for which patent protection is sought) into the other two official EPO languages.
Moreover, for a transitional period of maximum 12 years, European patents with unitary effect that were granted in French or German will need to be translated into English and the ones granted in English will need into be translated to another official language of the EU. These translations will be required until high-quality machine translations into all the official languages of the Union are made available to ensure the availability of patent information.
High-quality machine translations – on-line and free of charge - will soon be available in all languages. The European Patent Office (EPO) is already providing a machine translation service for 13 languages (between English and Danish, Dutch, German, Finnish, French, Greek, Hungarian, Italian, Norwegian, Polish, Portuguese, Spanish and Swedish). By the end of 2014 the service is expected to cover 32 languages, including all languages of the European Union, plus important non-European languages such as Chinese, Japanese, Korean and Russian.
The machine translation service "Patent Translate" can be accessed via the following website: http://www.epo.org/searching/free/patent-translate.html
The information on patents will be available in all EU languages due to high-quality machine translations. The European Patent Office (EPO) is already providing a machine translation service for 13 languages (between English and Danish, Dutch, German, Finnish, French, Greek, Hungarian, Italian, Norwegian, Polish, Portuguese, Spanish and Swedish). By the end of 2014 the service is expected to cover 32 languages, including all languages of the European Union. This will ensure that everyone can obtain information on all European patents – and not only on those validated in the respective country - in his own language and free of charge.
The machine translation service "Patent Translate" can be accessed via the following website: http://www.epo.org/searching/free/patent-translate.html
To ensure that the information is available before the quality of the machine translations has been established, the regulation provides that, for a transitional period of maximum 12 years, a manual translation into English will in any case have to be provided.
The Unified Patent Court (UPC) will be the future centralised patent jurisdiction of the participating Member States. It will be a court common to the participating Member States and thus subject to the same obligations under Union law as any national court of the participating Member States, in particular refer, where necessary, questions on the interpretation of European Union law to the Court of Justice of the European Union.
The UPC will have exclusive jurisdiction especially in respect of civil litigation related to infringement and validity for both the "classical" European patents and the European patents with unitary effect. It will also have competence in respect of supplementary protection certificates issued for a product protected by a European patent with or without unitary effect.note
During a transitional period of 7 years, actions for infringement or for revocation concerning "classical" European patents without unitary effect can still be brought before national courts. A proprietor of or an applicant for a European patent granted or applied for prior to the end of the transitional period will also have the possibility to opt out from the exclusive competence of the Court (unless an action has already been brought before the Court). To this end they shall notify their opt-out to the Registry by the latest one month before expiry of the transitional period. The transitional period may be prolonged up to a further 7 years by the Administrative Committee (decision making body within the court system composed of one representative per Contracting Member State).
The UPC will consist of a Court of First Instance, a Court of Appeal and a Registry. The Court of First Instance will comprise local and regional divisions as well as a central division. The Court of Appeal will be located in Luxembourg while the seat of the central division of the Court of First Instance will be in Paris. Specialised sections of the central division will be set up in London and in Munich. All panels of the new jurisdiction will have a multinational composition. In addition, they will be composed of legally qualified judges and, depending on the cases, they will also include technically qualified judges. All judges will ensure the highest standards of competence and shall have proven experience in the field of patent litigation.
The Court fees will be fixed by the Administrative Committee, once the Unified Patent Court has been set up. Member States are politically committed that the level be such as to ensure a right balance between the principle of fair access to justice and the objective of a self-financing Court with balanced finances. The fee system will provide specific tools to ensure proper access for e.g. SMEs to the Unified Patent Court. In addition, natural persons may be eligible for legal aid, if they do not have sufficient financial resources.
In principle, cases will be brought either before the local division hosted by the Member State where the actual or threatened infringement has occurred or may occur (or the regional division in which this Member State participates); or the local division hosted by the Member State where the defendant has his residence or place of business (or the regional division in which this Member State participates).
However, in some instances, cases have to be brought before the central division, e.g. (direct) revocation actions, infringement actions if the Member State does not host a local division nor participates in a regional division, actions for declaration of non-infringement and actions concerning administrative decisions of the EPO.
In other cases, the case may be brought or referred by a local/regional division to the central division, e.g. in cases in which the defendant has his residence in a third country, in cases in which both parties agree, in cases of counterclaims for revocation of patents or in cases in which a (direct) action for revocation is already pending before the central division.
The unitary patent package will reduce fragmentation.
25 Members States take part in the creation of the unitary patent protection (all except IT and ES) and potentially 26 Member States in the creation of the uniform patent jurisdiction (in December 2011 Italy signalled its intention to join; ES does not participate). It is evident that we would have preferred to have all Member States on board, but this was unfortunately not possible in the light of divergent views amongst the Member States.
However the situation of today is that, in order to get Europe-wide protection, it is necessary to validate the European patent in all 27 Member States. Patent litigation may theoretically occur in all those 27 Member States in parallel, even if the patent, the parties and the cause for the dispute (e.g. the allegedly infringing product or a prior art which was not yet taken into consideration) were the same.
Under the forthcoming unitary patent system, only one 'validation' (the request of the unitary effect with the EPO) will be necessary for obtaining patent protection in the 25 Member States. The system is of course available for all applicants, regardless of their nationality or domicile.
Furthermore, instead of a multiplication of potentially parallel patent litigation, only one court case will have to take place. This case will be centrally decided by the Unified Patent Court which is a court common to the participating Member States. This is a major step towards reducing fragmentation.
The Court of Justice of the European Union interprets the law of the European Union as highest instance. This remains unchanged.
The Unified Patent Court is a court common to the Contracting Member States and will ensure the correct application and uniform interpretation of Union law, as any national court, in particular in accordance with Article 267 TFEU. Decisions of the Court of Justice of the European Union shall be binding on the UPC.
This means that the UPC is obliged to refer questions to the Court of Justice of the European Union on the interpretation of, in particular, the two new Regulations creating the unitary protection and the Directive on the legal protection of biotechnological inventions.
The patentability requirements for European patents with unitary effect are identical to those of 'classical' European patents. The envisaged regulation on unitary patent protection does not change these patentability conditions.
The Directive on the legal protection of biotechnological inventions (Directive 98/44/EC of the European Parliament and of the Council of 6 July 1998, 'Biotechnology-Directive') harmonises the national laws of the Member States notably in the area of patenting biotechnological inventions. The Biotechnology-Directive has been fully integrated in the legal framework of the European Patent Organisation ("EPO") in 1999, before the expiry of the transposition period. This means that, as of that time, the European Patent Office which is the central authority responsible for the examination and, if the legal requirements are fulfilled, the granting of European patents follows the standard as laid down in the Biotechnology-Directive.
The Biotechnology-Directive, in particular, clarifies that biotechnological inventions are, as a general rule, patentable, provided that they meet the patentability criteria of novelty, inventive step and industrial applicability. However, the Directive clearly provides that plant and animal varieties and essentially biological processes for the production of plants or animals (i.e. conventional breeding methods based on crossing and selection) are not patentable.
The patentability requirements for European patents with unitary effect are identical to those of 'classical' European patents. The envisaged regulation on unitary patent protection does not change these patentability conditions.
The Biotechnology-Directive which has been fully integrated in the legal framework of the European Patent Organisation, also confirms the principle that inventions whose commercial exploitation offends against ordre public (eg. a process for cloning human beings) or morality cannot be patented. In particular, it provides an illustrative list of inventions which are excluded from patentability for these reasons. The non-exhaustive list comprises (1) processes for cloning human beings, (2) processes for modifying the germ line genetic identity of human beings, (3) the use of human embryos for industrial or commercial purposes and (4) processes for modifying the genetic identity of animals which are likely to cause them suffering without any substantial medical benefit to man or animals, and also animals resulting from such processes.
Up until now, the Court of Justice of the European Union was asked to interpret one of these categories, namely the use of human embryos for industrial and commercial purposes. The case is known as Brüstle-judgement (C-34/10). The judgement is binding on the courts of the Member States, and, of course also to the future Unified Patent Court. The CJEU-ruling has also been implemented in the practice of the European Patent Office.
The patentability requirements for European patents with unitary effect are identical to those of "classical" European patents. The envisaged regulation on unitary patent protection does not contain any particular disposition or derogation on the patentability conditions for inventions.
As to the patentability of software, Article 52(2) of the European Patent Convention provides that programs for computers do not constitute a patentable invention. However, patentability is only excluded for programs for computers 'as such'.
An invention which involves the use of a computer, a computer network or other programmable apparatus, where one or more features are realised wholly or partly by means of a computer program (so called computer-implemented inventions, "CII") can be patented if it fulfils the strict patentability requirements, in particular, it must have a technical character, be new and make an inventive technical contribution to the knowledge available at the date on which the application was first filed.


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Location and easy access to transport facilities. - Anthony
We always opt to stay at B&B's while travelling Europe to remain budget friendly and we were absolutely thrilled with our stay here (definitely our best stay of the trip). The rooms were very large, clean and breakfast delivered to our room every morning was fantastic. Our room had a great sitting area, large VERY comfortable bed, two pillows and a massive bathroom. The B&B is on a busy street however the bathroom is closest to the road, so we couldn't hear a thing throughout the night - Anonymous
Great location. Very friendly staff.
Excellent security. Breakfast was good, not great. A microwave would be nice - Anonymous
lots of space in the appartments - quiet position within a busy city - very convenient for sight seeing, especially via hope on buses - wonderful big windows which openned!! - Caroline
Hotel com boa localização (centro histórico), confortável, limpo e muito sossegado. - Isabel
Nice room, friendly personel,breakfast exactly for me. Very good
localisation. Walking time with not to big luggage from Circo Massimo,
which is easy available from the airport by train Leonardo express and
metro b line is only up to 7-10 minutes. For those people who likes walk
most interesting places in the city center are available by walking
including Vaticano - Anonymous


text: Here is the procedure for installing a 9/32 brass tube with teflon liner for a .187 flex cable. First I purchased a new battery tray. Then I found a brass tube with teflon liner from Rocket City Racing that was perfect for this application. Their tube has a step down to .250 on one end so it will fit the stock grommet on the Spartan. I cut the tube the same length as the stock tube leaving the teflon liner stick out a little at the motor end. I then took the battery tray and bolted the the plastic u clamp together. Starting with a 1/4 inch drill bit I drilled out the clamp. I kept the bit straight by centering it in the motor hole. This first bit will remove a small amount of material and keeps the hole alignment perfect. Next use a 17/64 bit to remove the next small amount of material keeping the bit aligned to the motor hole. The final bit is the 9/32 which will remove the final amount of material. The clamp is now the correct size to grip the brass tube. On the other end of the tray you will need to open up the plastic guide. Some slight grinding with a dremmel or a rat tail file and the tube will seat all the way down in the u shaped guide. Bolt the brass tube in and test fit in the boat. Mine fit perfect. After installing put the .187 flex cable in and make sure the rear of the strut is aligned with the brass tube. Your flex cable should be centered in the brass tube and not rubbing on the tube. Whenever you adjust the strut height make sure the flex cable is centered. This was a fairly easy mod and now you can run a .187 flex cable with the teflon liner.


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Ariadne Beach
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Day 169
... deep gorges, by the middle of the afternoon we turned off the main road and dropped down the side if a gorge, at one point it was so tight you could have touched both sides, however you would have got wet feet in the river. It's amazing how the roads are cut into the hillsides. Passing through a very narrow road in a village the overhanging balconies had their height painted on them, luckily the lowest was 3.5 metres.
At the coast we found a place to park at a small harbour in ...
Day 168
... clouds on the mountains and on the way back to camp the sun disappeared, however it didn't rain. The whole of Crete seems to be picking olives at the moment, as we have been driving around we have noticed groups of migrant workers standing in strategic places in villages, outside the church seems to be a favourite. They must hang about waiting to get hired. Every so often there are ...
The wind has dropped quite considerably overnight, but the noisy sea has kept us awake, I am craving some peace and quiet! We are heading for Zakros gorge today, an easy 7 kilometre walk, if the river isn't too full! It's well signposted and we parked up at car park A, next to another camper from Austria. The owners were inside and waved to us. We made a packed lunch, got out our rucksacks and set off. The oath ...
Day 165
... if the cove there us a house tucked back from the sea. We parked in front of the small lake where we could hear a loud animal sound, it sounded like a very loud cricket, after some research we decided that it was a Cretan marsh toad. We walked went for a walk through the olive groves, for an hour or so. When we got back we could hear several of the toads all making a loud noise, it sounded as if they were competing with each other. We thought they would keep us awake all ...
Day 164
... a few smaller speed boats and yachts and some children just back from sailing were washing off a their of toppers, We walk back around to the harbour and decided it would be a nice place to stay for the night. Tomorrow the town will be open and we can explore further. I forgot to mention in yesterday's blog, we will need to find somewhere secure to park Dream Catcher whilst were in Nepal and Namibia, if any one has any ideas or suggestion, please let us ...


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Discover a selection of top forums creatures runes on the internet. Come to share your passion on forums creatures runes and meet other fans of creatures runes. Then, why don't you create your own forum of creatures runes ?
A forum based fantasy RPG, with similarities to Dungeons and Dragons, and many other fantasy based games, along with ideas from other forum based games.
kings, queens, #runes, fantasy, based, similarities, dungeons, dragons, games, game, medieval, vampire, werewolf, magic, sword, armor, fighting, warrior, wizard, story, role, play, role-play, playing, role-playi
In 2015 the creatures realm of Romania has become utter turmoil. Some creatures are worried about humans finding out about them, thinking it would be best to nip it in the bud and wipe out all of the humans before they can attack and destroy them, wh
luna, vermiculus, university, darkness, vampires, supernatural, family, #creatures, fantasy, fiction
Free forum : Souls of the Unknown is a melting pot of species varying from the common human to mythical creatures like werewolves, vampires, demons etc. set in the present time.
free, forum, souls, unknown, werewolves, vampires, shape, shifters, supernatural, #creatures, role, play, roleplay, mythical, fantasy
This roleplay is set 100 years back in the small village of Aslad. The humans no nothing of the existence of the creatures that prowl the night. The vampires and werewolves are currently at a truce. But there is no telling how long that will last. So
blood, clans, have, vampires, side, werewolves, humans, role-play
A University full of Vampires, Hybrids, Wizards, Wolves and then some. Fighting against the Human race in order to survive.
fantasy, shadows, university, magic, vampires, magical, #creatures, wolves, hybrids
A place where writers go to make their visions come alive.
stories, fiction, fantasy, writing, online, community, illusion, vale, #creatures, original


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"Loved how I asked for them to review the product and send me a proof before they went to be printed! Great quality and quick to be shipped!"
"The print and card quality surpassed that of similar companies, but the real standout was the individual customer service given. An adviser called me to discuss my question and when asked to leave a message, they left an actual phone number so that I could call them back! So nice to hear from a person that the design works or that something needs to change instead of trusting the coloring on the computer screen."
"These ended up being much smaller than i thought but maybe i didnt read the description well enough...super cute though!! I bought these as thank you notes for my son to give, i am obsessed with little boys & mustaches so they are a perfect design! :)"
"This card is amazing. The paper felt very firm and had an 'expensive' feel to it. Its smaller than I thought it would be, but for a thank-you card its perfect. I opted for the envelope personalization which really looked classy. I'd definitely recommend this layout!"
"Although the card is gorgeous and the quality is outstanding when I ordered the card even though I checked for a designer review I received my card and noticed a misspelled word. Granted, I missed it, but so did they. I won't check the designer box anymore because it really doesn't do any good. Disappointed in the customer service/designer review."


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Found this on Youtube yesterday and love it!!
Found this on Youtube yesterday and love it!!
Just received it this weekend and I love the idea!
Handheld-SIZZA.. brilliant!!
This version was done by Marshall Alexander, check out his other Papertoys on his website! To get his version of SIZZA just click on the pic to download the PDF-File!
Just found that one on Sneaker Freaker:
"Kidrobot and Lacoste have teamed up to create a 'capsule' of sneakers due for release in November 2007. Production is capped to 500 pairs and each model comes with its very own customized 'PEECOL' toy created by eBoy and Kidrobot."
(for more info on that go here)
Made a new one!
This time I used only CDs, it was like the second time mixing with CDs, usually I am hooked on Vinyl!
Plus, I didn't know the tunes, I just used, what my good friend, the one and only Till West layed out in front of me.
So please don't be too hard on me.. ;)
Just found this on TOYSREVIL,
a first glimpse at the figures of the Series 4 "in action".. ;)
Lovin' it big time!
created by ReBo Labs = check the hi-res QT-video here
Can't wait for them to hit the shelves here in Germany..
Kidrobot has this to say about the new series:
Dunny Series 4 is rockin' the block with it's greatest assortment of artists yet. That isn't to say the first three series weren't great, it's just that this one is going to blow your minds!
The artist for this round include Mist, Jon Burgerman, MAD, Frank Kozik and Gary Baseman.
Dunny Series 4 will be available on Thursday, September 27th at 11am EST, here in Germany probably during the first week of October. If you live anywhere near Düsseldorf, you will find your Dunny along other cool stuff here at Jues!
Got a new custom joining the SIZZA-Army!
This time the incredible New York City-based Graff Artist and Spaceship Designer MIKE DIE came up with RoboSIZZA!
If you should be interested in doing a custom version of SIZZA yourself, just let me know – just drop a comment and I'll hook you up! ;)
The first tokidoki store opened in Milan, Italy on September 12, 2007.
If you plan on visiting Milan make sure to stop by this shop, it's got all the goods created by Simone Legno.
You can find the store here:
c.so di Porta Ticinese 62
20123 Milano
Keep looking out for his stuff, because future collaborations for 2008 will include Hello Kitty and Onitsuka Tiger..
quite busy, the man! ;)
One of the best Graffiti Artists of our time DAIM has done it again. For Gelaskins he has done two Designs for the iPod, iPhone and Apple Notebooks.. simply Breath-Taking I think!
(I have to come up with something like this someday, too!)
Join the SIZZA-Army!
Here is a brand new custom of SIZZA, done by Ly, the digitalbanana!
Now you can build your own S-Troopz Army, just click on the pic below!
SIZZA F-74 by digitalBanana 1221
If you should be interested in doing a custom version of SIZZA yourself, just let me know – just drop a comment and I'll hook you up! ;)
Again some people asked for the Tracklisting for this mix, so I put it together..
Here it is:
I collected my personal works and posted them on a page here, so you can see, what else I am doing with my time..
I will also put the stuff I did for other people up there..so you can get an impression of my work thus far..


text:
St James Plaza / ASPECT Studios
Architects: ASPECT Studios
Location: Melbourne, Victoria, Australia
Year: 2013
Photographs: Andrew Lloyd
The Flinders Street Station Winning Proposal / HASSELL + Herzog & de Meuron
The winning proposal for the Flinders Street Station competition comes from HASSELL + Herzog & de Meuron. The design integrates the station with the surrounding urban context, which has evolved and changed significantly since the building was designed 100 years ago. The station concept draws from many aspects – the site's historic fabric, location, and linear nature; the original 19th century design and existing heritage fabric; the river and city edge, rail, public and river-based operations as well as the station's place within the city fabric and public realm. More images and architects' description after the break.
The Flinders Street Station Shortlisted Proposal / John Wardle Architects + Grimshaw
As part of the People's Choice Award launch by Major Projects Victoria, this design by John Wardle Architects + Grimshawwas selected as one of the shortlisted competition proposals for the rejuvenation of Flinders Street Station in Melbourne. Their design conceives the station as an ensemble, each part precisely considerate of its place in the city. The theatrical nature of the station is amplified by the stitching of city to river. Landscape, bridges and vaults from the threads. More images and architects' description after the break.
The Flinders Street Station Shortlisted Proposal / Ashton Raggatt McDougall
Designed by Ashton Raggatt McDougall (ARM), their proposal for the Flinders Street Station, which was recently shortlisted in the design competition part of the People's Choice Award launch by Major Projects Victoria. Their proposal aims to create a seamless interface with the city, its streets and lanes, its intermodal transportation, and its future dreams. On the river this seamlessness is not so much a measurement of ease or just intentionality, but rather instead a sudden sense of spectacle, a special realization of the river that's always been there, even a sense of history and time. More images and architects' description after the break.
Six Flinders Street Station Proposals Battle It Out for "People's Choice Award"
UPDATE: Public voting is now closed. Feel free to review the concepts and share your thoughts in the comment section below.
The Victorian Coalition Government's design competition to re-imagine Melbourne's beloved Flinders Street Station has entered its final phase as the public submits their last minute votes for the "People's Choice Award" today, August 5. Though each proposal is dramatically different, ranging from Zaha Hadid Architects' carefully calculated, sinuous curves to Herzog & de Meuron's extrusion of vaulted canopies, all promise to elevate the station's status to the 21st century whilst respecting its historic context.
Form your own opintion and vote for your favorite after the break…
Sunday Apartments / Woods Bagot
Architects: Woods Bagot
Location: Coventry Street, Southbank, Melbourne, Australia
Development And Project Managers: Premier Capital Developments
Branding: Cornwall Design
Photographs: Trevor Mein
Fitzroy North Residence / Chan Architecture
Architects: Chan Architecture
Location: Melbourne, Australia
Project Team: Anthony Chan, Miriam Harris, Mei Yang, Michelle Ng
Builder: Whelan Master Builders
Structural Engineer: Jonicha Consulting Engineers
Building Surveyor: Wilsmore Nelson Group
Energy Rater: Green Doors
Land Surveyor: Aline Surveying
Geotechnical Engineer: Apex Geotechnical
Year: 2013
Photographs: Brendan Finn, Mark Fergus
Dolls House / Edwards Moore
Architects: Edwards Moore
Location: Melbourne, Australia
Year: 2013
Photographs: Frasen Marsden
Little Brick Studio / MAKE Architecture
Architects: MAKE Architecture
Location: Melbourne, Australia
Design Team: Melissa Bright, Bruce Rowe, Gillian Hatch, Shelley Freeman
Builder: 4AD Construction
Year: 2012
Photographs: Peter Bennetts
Ross Street / BE Architecture
Architects: BE Architecture
Location: Melbourne, Australia
Builder: Good Constructions
Area: 470 sqm
Photographs: Peter Clarke
Shortlist Revealed for Melbourne's Flinders Street Station Competition
The Victorian Coalition Government's design competition to re-imagine Flinders Street Station in Melbourne has entered its final phase with the six shortlisted competitors submitting their final designs. Selected from 117 entries, the shortlist includes the following Australian and international firms:
Eleven Inch Pizza / Zwei
Architects: Zwei
Location: Docklands, Victoria, Australia
Builder: Four Seasons Commercial Interiors
Lighting: Satelight / Volker Haug
Logo: Salmon Design
Area: 93 sqm
Year: 2013
Photographs: Michael Kai
Captain Melville / Breathe Architecture
Architects: Breathe Architecture
Location: Melbourne, Australia
Design Team: Linda Valentic, Jeremy McLeod
Construction Team: Ficus Constructions, Exzibit Design
Area: 286.0 sqm
Year: 2012
Photographs: Andrew Wuttke
The Nicholson / DesignInc
Architects: DesignInc
Location: Coburg, Victoria, Australia
Year: 2011
Photographs: Tony Miller, Dianna Snape
National Tennis Centre / Jackson Architecture
Architects: Jackson Architecture
Location: Melbourne, Australia
Design Team: Daryl Jackson, Matt Drysdale, Stewart Lock, Peter Cole, Aaron Paris, Kon Iakovidis, Elaine Quek
Structural Engineers: Winward Structures
Year: 2012
Photographs: John Gollings
CH2 Melbourne City Council House 2 / DesignInc
Architects: DesignInc
Location: Melbourne, Australia
Project Team: Rob Adams (Project Director -City of Melbourne), Mick Pearce (Design Director), Stephen Webb (Design Architect), Chris Thorne (Design Architect), Jean-Claude Bertoni (Project Architect), Vi Vuong (Architect), Aldona Pajdak (Interior Designer)
Area: 12,500 sqm
Photographs: Dianna Snape, David Hannah
Stonnington Pound Development / Architecture Matters
Architects: Architecture Matters
Location: Malvern, Melbourne, Australia
Project Director: Anthony Gionfriddo
Project Architect: Rebecca Dodd
Area: 179.53 sqm
Year: 2012
Photographs: Christopher Alexander
Bluff House / Inarc Architects
Architects: Inarc Architects
Location: Mornington Peninsula, Victoria, Australia
Directors: Reno Rizzo & Christopher Hansson
Project Architect: Wilson Tang
Year: 2012
Photographs: Peter Clarke


text:
The present invention is a blend of a thermoplastic engineering resin and an interpolymer of, on one embodiment, a C4 to C7 isomonoolefin, a para-methylstyrene and a para-(halomethylstyrene), the interpolymer having been pre-mixed with an exfoliated-clay, the entire blend forming a nanocomposite. The resin may or may not have a clay present prior to blending with the interpolymer. The interpolymer/clay mixture forms a distinct phase in the nanocomposite blend of the invention. The blend of the invention has improved air barrier properties and is suitable as an air barrier.
1. A nanocomposite comprising at least a first and second phase prepared by a method comprising forming the first and second phases, and blending the first and second phases, the first phase comprising a mixture of an interpolymer comprising C4 to C7 isomonoolefin derived units, para-methylstyrene derived units and para-(halomethylstyrene) derived units with an alkylamine-exfoliated or an alkylammonium-exfoliated clay; the second phase comprising at least one thermoplastic engineering resin containing an alkylamine-exfoliated or an alkylammonium-exfoliated clay.
2. The nanocomposite of
3. The nanocomposite of
4. The nanocomposite of
5. The nanocomposite of
6. The nanocomposite of
7. The nanocomposite of
8. The nanocomposite of
9. The nanocomposite of
10. The nanocomposite of
11. The nanocomposite of
12. A tire innerliner comprising the nanocomposite of
13. The nanocomposite of
14. The nanocomposite of
15. The nanocomposite of
16. A nanocomposite comprising at least two phases, wherein:
a) one phase comprises an alkylamine-exfoliated or an alkylammonium-exfoliated clay and at least one thermoplastic engineering resin; and
b) another phase comprises a blend of an alkylamine-exfoliated or an alkylammonium-exfoliated clay and an interpolymer of a C4 to C7 isomonoolefin containing up to 20 mole % of the following aromatic monomer units randomly spaced along the polymer chain:
wherein R and R1 are independently hydrogen, C1 to C4 alkyl or primary or secondary alkyl halides and X is hydrogen, or a functional group selected from the group consisting of halogens; carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide; cyanate; amino and mixtures thereof;
wherein the nanocomposite is made by a method comprising blending the alkylamine-exfoliated or alkylammonium-exfoliated clay-containing thermoplastic resin phase with the alkylamine-exfoliated or alkylammonium-exfoliated clay-containing interpolymer phase.
17. The nanocomposite of
18. The nanocomposite of
19. The nanocomposite of
20. The nanocomposite of
21. The nanocomposite of
22. The nanocomposite of
23. The nanocomposite of
24. The nanocomposite of
25. The nanocomposite of
26. The nanocomposite of
27. A tire innerliner comprising the nanocomposite of
28. The nanocomposite of
29. The nanocomposite of
30. The nanocomposite of
31. A method of forming a nanocomposite comprising forming a first phase of an alkylamine-exfoliated or an alkylammonium-exfoliated clay and an interpolymer of C4 to C7 isomonoolefin derived units, para-methylstyrene derived units and para-(halomethylstyrene) derived units; and blending the first phase with at least a second phase comprising a thermoplastic engineering resin also including an alkylamine-exfoliated or an alkylammonium-exfoliated clay.
32. The method of
33. The method of
34. The method of
35. The method of
36. The method of
37. The method of
38. The method of
39. The method of
40. A tire innerliner comprising the nanocomposite obtained by curing the composition obtained from the method of
41. The method of
42. The method of
43. The method of
This application is a National Stage Application of International Application No. PCT/US02/16794, filed May 29, 2002, which claims the benefit of Provisional Application Ser. No. 60/296,873, filed Jun. 8, 2001.
The present invention provides low-permeability nanocomposites which are blends of thermoplastics and elastomers, vulcanized or unvulcanized, in which the elastomer component contains nano-fillers such as clays.
Nanocomposites are polymer systems containing inorganic particles with at least one dimension in the nanometer range. Some examples of these are disclosed in U.S. Pat. Nos. 6,060,549, 6,103,817, 6,034,164, 5,973,053, 5,936,023, 5,883,173, 5,807,629, 5,665,183, 5,576,373, and 5,576,372. A common type of inorganic particle used in nanocomposites are phyllosilicates, an inorganic substance from the general class of so called �nano-clays� or �clays�. Ideally, intercalation should take place in the nanocomposite, wherein the polymer inserts into the space or gallery between the clay surfaces. Ultimately, it is desirable to have exfoliation, wherein the polymer is fully dispersed with the individual nanometer-size clay platelets. Due to the general enhancement in air barrier qualities of various polymer blends when clays are present, there is a desire to have a nanocomposite with low air permeability; especially a dynamically vulcanized thermoplastic nanocomposite such as used in the manufacture of tires.
Dynamically vulcanized thermoplastic compositions comprising a polyamide and various types of elastomers are known. See, for example, U.S. Pat. No. 4,173,556; U.S. Pat. No. 4,197,379; U.S. Pat. No. 4,207,404; U.S. Pat. No. 4,297,453; U.S. Pat. No. 4,338,413; U. 4,348,502; U.S. Pat. No. 4,419,499, and U.S. Pat. No. 6,028,147. The term �dynamic vulcanization� is used herein to mean a vulcanization process in which the components of the blend are vulcanized under conditions of high shear. As a result, the vulcanizable elastomer is simultaneously crosslinked and dispersed as fine particles of a �micro gel� within the resin matrix.
Dynamic vulcanization is effected by mixing, for example, an elastomer and a thermoplastic, at a temperature which is at or above the curing temperature of the polymer in equipment to provide high shear such as roll mills, Banbury� mixers, continuous mixers, kneaders or mixing extruders, extruders. One unique characteristic of the dynamically cured compositions is that, notwithstanding the fact that the polymer component may be fully cured, the compositions can be processed and reprocessed by conventional rubber processing techniques such as extrusion, injection molding, compression molding, etc. Scrap or flashing can be salvaged and reprocessed.
It is known to utilize exfoliated-clay filled nylon as a high impact plastic matrix, such as disclosed in U.S. Pat. No. 6,060,549 to Li et al. In particular, Li et al. disclose a blend of a thermoplastic resin such as nylon and a copolymer of a C4 to C7 isomonoolefin and a para-methylstyrene and a para-(halomethylstyrene), the blend also including nylon containing exfoliated-clays that are used as a high impact material. Further, Japanese Unexamined Application P2000-160024 to Yuichi et al. discloses a thermoplastic elastomer composition which can be used as an air barrier. The nanocomposite in Yuichi et al. includes is blend similar to that disclosed in Li et al. Other disclosures include U.S. Pat. No. 6,036,765 and EP 1 055 706 A.
There is still a problem of achieving a nanocomposite suitable for an air barrier, in particular, an air barrier incorporating the copolymer of a C4 to C7 isomonoolefin and a para-methylstyrene and a para-(halomethylstyrene). While enhancing the impact properties and abrasion resistance of plastics such as polyamides, this copolymer tends to be a poor air barrier as compared with that of polyamide alone or other low-permeability plastic matrices. What is needed is a blend of a thermoplastic resin such as nylon with the copolymer to form a nanocomposite suitable as an air barrier.
An embodiment of the present invention includes a blend of a thermoplastic engineering resin and an interpolymer of a C4 to C7 isomonoolefin, a para-methylstyrene and a para-(halomethylstyrene) that has been pre-mixed with a clay, the blend forming a nanocomposite. The resin may or may not have a clay present prior to blending with the interpolymer. In another embodiment, the interpolymer is not pre-mixed with the clay. The interpolymer/clay mixture form a distinct phase in the nanocomposite blend of the invention. The blend of the invention has improved air barrier properties.
One embodiment of the invention is a nanocomposite comprising having at least two phases, wherein:
The thermoplastic engineering resins suitable for practice of the present invention may be used singly or in combination and are resins containing nitrogen, oxygen, halogen, sulfur or other groups capable of interacting with an aromatic functional groups such as halogen or acidic groups. The resins are present in the nanocomposite from 30 to 90 wt % of the nanocomposite in one embodiment, and from 40 to 80 wt % in another embodiment, and from 50 to 70 wt % in yet another embodiment. In yet another embodiment, the resin is present at a level of greater than 40 wt % of the nanocomposite, and greater than 60 wt % in another embodiment.
Suitable engineering resins include resins selected from polyolefins (polypropylene, polyethylene, etc.), polyamides, polyimides, polycarbonates, polyesters, polysulfones, polylactones, polyacetals, acrylonitrile-butadiene-styrene resins (ABS), polyphenyleneoxide (PPO), polyphenylene sulfide. (PPS), polystyrene, styrene-acrylonitrile resins (SAN), styrene maleic anhydride resins (SMA), aromatic polyketones (PEEK, PED, and PEKK) and mixtures thereof. In another embodiment, suitable engineering resins include resins selected from polyamides, polyimides, polycarbonates, polyesters, polysulfones, polylactones, polyacetals, acrylonitrile-butadiene-styrene resins (ABS), polyphenyleneoxide (PPO), polyphenylene sulfide (PPS), polystyrene, styrene-acrylonitrile resins (SAN), styrene maleic anhydride resins (SMA), aromatic polyketones (PEEK, PED, and PEKK) and mixtures thereof.
Suitable thermoplastic polyamides (nylons) comprise crystalline or resinous, high molecular weight solid polymers including copolymers and terpolymers having recurring amide units within the polymer chain. Polyamides may be prepared by polymerization of one or more epsilon lactams such as caprolactam, pyrrolidione, lauryllactam and aminoundecanoic lactam, or amino acid, or by condensation of dibasic acids and diamines. Both fiber-forming and molding grade nylons are suitable. Examples of such polyamides are polycaprolactam (nylon-6), polylauryllactam (nylon-12), polyhexamethyleneadipamide (nylon-6,6) polyhexamethyleneazelamide (nylon-6,9), polyhexamethylenesebacamide (nylon-6,10), polyhexamethyleneisophthalamide (nylon-6, IP) and the condensation product of 11-amino-undecanoic acid (nylon-11). Additional examples of satisfactory polyamides (especially those having a softening point below 275� C.) are described in 16 ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY 1-105 (John Wiley & Sons 1968), CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 748-761 (John Wiley & Sons, 1990), and 10 ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY 392-414 (John Wiley & Sons 1969). Commercially available thermoplastic polyamides may be advantageously used in the practice of this invention, with linear crystalline polyamides having a softening point or melting point between 160 and 260� C. being preferred.
Suitable thermoplastic polyesters which may be employed include the polymer reaction products of one or a mixture of aliphatic or aromatic polycarboxylic acids esters of anhydrides and one or a mixture of diols. Examples of satisfactory polyesters include poly(trans-1,4-cyclohexylene), C2-6 alkane dicarboxylates such as poly(trans-1,4-cyclohexylene succinate) and poly (trans-1,4-cyclohexylene adipate); poly(cis or trans-1,4-cyclohexanedimethylene) alkanedicarboxylates such as poly(cis-1,4-cyclohexane-di-methylene) oxlate and poly-(cis-1,4-cyclohexane-di-methylene) succinate, poly (C2-4 alkylene terephthalates) such as polyethyleneterephthalate and polytetramethylene-terephthalate, poly(C2-4 alkylene isophthalates such as polyethyleneisophthalate and polytetramethylene-isophthalate and like materials. Preferred polyesters are derived from aromatic dicarboxylic acids such as naphthalenic or phthalic acids and C2 to C4 diols, such as polyethylene terephthalate and polybutylene terephthalate. Preferred polyesters will have a melting point in the range of 160� C. to 260� C.
Poly(phenylene ether) (PPE) thermoplastic engineering resins which may be used in accordance with this invention are well known, commercially available materials produced by the oxidative coupling polymerization of alkyl substituted phenols. They are generally linear, amorphous polymers having a glass transition temperature in the range of 190� C. to 235� C. These polymers, their method of preparation and blends with polystyrene are further described in U.S. Pat. No. 3,383,435.
Other thermoplastic resins which may be used include the polycarbonate analogs of the polyesters described above such as segmented poly (ether co-phthalates); polycaprolactone polymers; styrene resins such as copolymers of styrene with less than 50 mole % of acrylonitrile (SAN) and resinous copolymers of styrene, acrylonitrile and butadiene (ABS); sulfone polymers such as polyphenyl sulfone; copolymers and homopolymers of ethylene and C2 to C8 α-olefins, in one embodiment a homopolymer of propylene derived units, and in another embodiment a random copolymer or block copolymer of ethylene derived units and propylene derived units, and like engineering resins as are known in the art.
The interpolymers suitable for compositions of the present invention in one embodiment of the invention are random elastomeric copolymers of a C4 to C7 isomonoolefin, such as isobutylene and a para-alkylstyrene comonomer, preferably para-methylstyrene containing at least 80%, more preferably at least 90% by weight of the para-isomer and also include functionalized interpolymers wherein at least some of the alkyl substituents groups present in the styrene monomer units contain benzylic halogen or some other functional group. In another embodiment of the invention, the interpolymer is a random elastomeric copolymer of ethylene or a C3 to C6 α-olefin and a para-alkylstyrene comonomer, preferably para-methylstyrene containing at least 80%, more preferably at least 90% by weight of the para-isomer and also include functionalized interpolymers wherein at least some of the alkyl substituents groups present in the styrene monomer units contain benzylic halogen or some other functional group. Preferred materials may be characterized as interpolymers containing the following monomer units randomly spaced along the polymer chain:
The functional group X may be halogen or some other functional group which may be incorporated by nucleophilic substitution of benzylic halogen with other groups such as carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide; cyanate; amino and mixtures thereof. These functionalized isomonoolefin copolymers, their method of preparation, methods of functionalization, and cure are more particularly disclosed in U.S. Pat. No. 5,162,445.
Most useful of such functionalized materials are elastomeric random interpolymers of isobutylene and para-methylstyrene containing from 0.5 to 20 mole % para-methylstyrene wherein up to 60 mole % of the methyl substituent groups present on the benzyl ring contain a bromine or chlorine atom, preferably a bromine atom (para-(bromomethylstyrene)), as well as acid or ester functionalized versions.
In a preferred embodiment, the functionality is selected such that it can react or form polar bonds with functional groups present in the matrix polymer, for example, acid, amino or hydroxyl functional groups, when the polymer components are mixed at high temperatures.
These functionalized interpolymers have a substantially homogeneous compositional distribution such that at least 95% by weight of the polymer has a para-alkylstyrene content within 10% of the average para-alkylstyrene content of the polymer. Desirable interpolymers are also characterized by a narrow molecular weight distribution (Mw/Mn) of less than 5, more preferably less than 2.5, a preferred viscosity average molecular weight in the range of from 200,000 up to 2,000,000 and a preferred number average molecular weight in the range of from 25,000 to 750,000 as determined by gel permeation chromatography.
The interpolymers may be prepared by a slurry polymerization of the monomer mixture using a Lewis acid catalyst, followed by halogenation, preferably bromination, in solution in the presence of halogen and a radical initiator such as heat and/or light and/or a chemical initiator and, optionally, followed by electrophilic substitution of bromine with a different functional moiety.
Preferred BIMS polymers are brominated polymers that generally contain from 0.1 to 5% mole of bromomethylstyrene groups relative to the total amount of monomer derived units in the polymer. In another embodiment, the amount of bromomethyl groups is from 0.2 to 3.0 mol %, and from 0.3 to 2.8 mol % in yet another embodiment, and from 0.4 to 2.5 mol % in yet another embodiment, and from 0.3 to 2.0 in yet another embodiment, wherein a desirable range may be any combination of any upper limit with any lower limit. Expressed another way, preferred copolymers contain from 0.2 to 10 wt % of bromine, based on the weight of the polymer, from 0.4 to 6 wt % bromine in another embodiment, and from 0.6 to 5.6 wt % in another embodiment, are substantially free of ring halogen or halogen in the polymer backbone chain. In one embodiment of the invention, the interpolymer is a copolymer of C4 to C7 isoolefin derived units (or isomonoolefin), para-methylstyrene derived units and para-(halomethylstyrene) derived units, wherein the para-(halomethylstyrene) units are present in the interpolymer from 0.4 to 3.0 mol % based on the total number of para-methylstyrene, and wherein the para-methylstyrene derived units are present from 3 wt % to 15 wt % based on the total weight of the polymer in one embodiment, and from 4 wt % to 10 wt % in another embodiment. In another embodiment, the para-(halomethylstyrene) is para-(bromomethylstyrene).
The elastomeric functionalized interpolymer is incorporated into the nanocomposite at a level sufficient to enhance the impact properties of the plastic matrix, such as, for example, generally at a level of from 0.5 to less than 60 wt % in one embodiment, from 5 to 50 wt % in another embodiment, and from 10 to 40 wt % in yet another embodiment, based on the total polymer content of the composition, or at a level sufficient to render the nanocomposite as a thermoplastic elastomer, that is, generally at a level of from 35 to 99.5 wt % in one embodiment, or from 40 to 80 wt % in another embodiment, and from 45 to 75 wt % in yet another embodiment.
Swellable layered clay materials suitable for the purposes of this invention include natural or synthetic phyllosilicates, particularly smectic clays such as montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, stevensite and the like, as well as vermiculite, halloysite, aluminate oxides, hydrotalcite and the like. These layered clays generally comprise particles containing a plurality of silicate platelets having a thickness of 8-12 Å tightly bound together at interlayer spacings of 4 Å or less, and contain exchangeable cations such as Na+, Ca+2, K+ or Mg+2 present at the interlayer surfaces.
The layered clay may be intercalated by treatment with organic molecules (variously, swelling agents, or exfoliating �agents� or �additives�) capable of undergoing ion exchange reactions with the cations present at the interlayer surfaces of the layered silicate. This treatment is alternately referred to as �exfoliation�. Suitable exfoliating agents include cationic surfactants such as ammonium, alkylamines or alkylammonium (primary, secondary, tertiary and quaternary), phosphonium or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides.
Desirable amine additives (or the corresponding ammonium ion) useful for blending or �exfoliating� with clays as swelling agents useful in the invention are those with the structure R2R3R4N, wherein R2, R3, and R4 are C1 to C20 alkyls or alkenes which may be the same or different. In one embodiment, the exfoliating agent is a so called long chain tertiary amine, wherein at least R2 is a C14 to C20 alkyl or alkene.
Another class of exfoliating additives include those which can be covalently bonded to the interlayer surfaces. These include polysilanes of the structure �Si(R5)2R6 where R5 is the same or different at each occurrence and is selected from alkyl, alkoxy or oxysilane and R6 is an organic radical compatible with the matrix polymer of the composite.
Other suitable exfoliating additives include protonated amino acids and salts thereof containing 2-30 carbon atoms such as 12-aminododecanoic acid, epsilon-caprolactam and like materials. Suitable swelling agents and processes for intercalating layered silicates are disclosed in U.S. Pat. Nos. 4,472,538, 4,810,734, 4,889,885 as well as WO92/02582.
The exfoliating additive such as described herein is present in the composition in an amount to achieve the desired properties. For example, the additive may be blended with the terpolymer and other additives such as curatives from 0.1 to 30 phr in one embodiment, and from 0.2 to 20 phr in yet another embodiment, and from 0.3 to 15 phr in yet another embodiment. Stated another way, the amount of exfoliated clay incorporated in the nanocomposites in accordance with this invention is sufficient to develop an improvement in the mechanical properties of the nanocomposite, for example, flexural modulus and tensile strength. Preferred amounts generally will range from 0.5 to 10 wt % in one embodiment, and from 1 to 5 wt % in another embodiment, based on the polymer content of the nanocomposite. In one embodiment, the exfoliated clay is an alkylamine-exfoliated clay.
The exfoliating additive may be added to the composition at any stage; for example, the additive may be added to the interpolymer, followed by addition of the clay, or may be added to the interpolymer and clay mixture; or the additive may be first blended with the clay, followed by blending with the interpolymer in yet another embodiment. Desirably, the clay is pre-treated with the exfoliating additive prior to addition to the terpolymer and thermoplastic.
Treatment with the swelling additives described above results in intercalation of the layered platelets as a consequence of a reduction of the ionic forces holding the layers together and introduction of molecules between layers which serve to space the layers at distances of greater than 4 Å, preferably greater than 9 Å. This separation allows the layered silicate to more readily sorb polymerizable monomer material and polymeric material between the layers and facilitates further delamination of the layers when the intercalate is shear mixed with matrix polymer material to provide a uniform dispersion of the exfoliated layers within the polymer matrix.
The composition of this invention may optionally include curative systems which are capable of curing the functionalized elastomeric copolymer component of the blend to provide vulcanizable compositions. Suitable curative systems for the elastomeric copolymer component of the present invention include organic peroxides, zinc oxide in combination with zinc stearate or stearic acid and, optionally, one or more of the following accelerators or vulcanizing agents: Permalux (di-ortho-tolylguanidine salt of dicatechol borate), HVA-2 (m-phenylene bis maleimide), Zisnet (2,4,6-trimercapto-5 triazine), ZDEDC (zinc diethyl dithiocarbamate) and other dithiocarbamates, Tetrone A (dipenta-methylene thiuram hexasulfide), Vultac-5 (alkylated phenol disulfide), SP1045 (phenol formaldehyde resin), SP1056 (brominated alkyl phenol formaldehyde resin), DPPD. (diphenyl phenylene diamine), salicyclic acid (o-hydroxy benzoic acid), wood rosin (abietic acid), and TMTDS (tetramethyl thiuram disulfide) in combination with sulfur. The composition may also be cured using ultraviolet light or electron irradiation.
The compositions of the invention may also contain other conventional additives such as dyes, pigments, antioxidants, heat and light stabilizers, plasticizers, oils and other ingredients as known in the art. The compositions of the invention may also include secondary rubbers or �general purpose rubbers� such as, for example, natural rubber, polybutadiene rubber, nitrile rubber, silicon rubber, polyisoprene rubber, poly(styrene-co-butadiene) rubber, poly(isoprene-co-butadiene) rubber, styrene-isoprene-butadiene rubber, ethylene-propylene rubber, brominated butyl rubber, chlorinated butyl rubber, halogenated isoprene, halogenated isobutylene copolymers, polychloroprene, star-branched polyisobutylene rubber, star-branched brominated butyl rubber, poly(isobutylene-co-isoprene) rubber; halogenated poly(isobutylene-co-p-methylstyrene) and mixtures thereof.
Blending of the components may be carried out by combining the polymer components and the clay in the form of an intercalate in any suitable mixing device such as a Banbury� mixer, Brabender� mixer or preferably a mixer/extruder and mixing at temperatures in the range of 120� C. up to 300� C. under conditions of shear sufficient to allow the clay intercalate to exfoliate and become uniformly dispersed within the polymer to form the nanocomposite. Alternatively, the clay may be separately combined with the engineering resin or elastomer by melt mixing, followed by extrusion of the blend or nanocomposite. If the mixture is to be dynamically vulcanized, before or after the resin and the elastomeric copolymer have been intimately mixed, the curative or curatives are added. Heating and masticating at vulcanization temperatures of 180� C. to 300� C. are generally adequate to complete vulcanization in 0.10 to 10 minutes.
A more complete description of the preparation of dynamically vulcanized compositions is found in WO 92/02582, the disclosure of which is incorporated herein by reference.
The composition of this invention may be extruded, compression molded, blow molded or injection molded into various shaped articles including fibers, films, industrial parts such as automotive parts, appliance housings, consumer products, packaging and the like. The resulting articles exhibit both high impact strength and low vapor permeability.
Thus, the present invention is a nanocomposite comprising at least a first and second phase, the first phase a mixture of an interpolymer comprising C4 to C7 isomonoolefin derived units, a para-methylstyrene derived units and a para-(halomethylstyrene) derived units with an alkylamine-exfoliated clay; and the second phase a thermoplastic engineering resin. The phases form a dispersion of �particles� having a measurable size based on such techniques as AFM. The invention is not herein limited to the shape of the particles. The composition is useful for such applications as listed above, and is particularly useful in air barriers such as pneumatic tire components, for example, innerliners, innertubes, and other air barriers such as bladders, etc.
In one embodiment of the composition, the second phase also includes an alkylamine-exfoliated clay. Desirable alkylamine compounds (or the corresponding ammonium ion) useful for blending or �exfoliating� with clays as swelling agents useful in the invention are those with the structure R2R3R4N, wherein R2, R3, and R4 are C1 to C20 alkyls or alkenes which may be the same or different. In one embodiment, the exfoliating agent is a so called long chain tertiary amine, wherein at least R2 is a C14 to C20 alkyl or alkene.
In a desirable embodiment, the alkylamine-exfoliated clay is a di-methyl tallowalkyl octyl ammonia methyl sulfate-exfoliated clay, and a di-methyl di-hydrogenated tallow alkyl ammonia chloride-exfoliated clay in another embodiment; and wherein the alkylamine-exfoliated clay is present in the nanocomposite from 0.5 to 10 wt % in yet another embodiment.
In one embodiment, the thermoplastic resin is selected from polyolefins, polyamides, polyimides, polyesters, polycarbonates, polysulfones, polylactones, polyacetals, acrylonitrile/butadiene/styrene copolymer resins, polyphenylene oxides, polyphenylene sulfides, polystyrene, styrene/acrylonitrile copolymer resins, styrenelmaleic anhydride copolymer resins, aromatic polyketones and mixtures thereof.
In one embodiment, the interpolymer is present in the nanocomposite from 10 to 40 wt %.
In another embodiment, the thermoplastic engineering resin is present in the nanocomposite from 30 to 90 wt %.
In another embodiment, the composition includes one or more curing agents selected from metals, metal oxides, and metal-carboxylic acid (fatty acid) compounds such as zinc, zinc stearate, stearic acid, sulfur, and mixtures thereof.
In another embodiment, the nanocomposite can be described as having at least two phases, wherein one phase includes at least one thermoplastic engineering resin; and another phase includes a blend of an alkylamine-exfoliated clay and an interpolymer of a C4 to C7 isomonoolefin containing up to 20 mole % of the following aromatic monomer units randomly spaced along the polymer chain:
The compositions of the invention can be characterized in one embodiment in that the blend is a dispersion of particles, wherein the number average size of the particles in the blend as measured by AFM is from 0.30 to 0.65 microns in one embodiment, and from 0.35 to 0.60 microns in another embodiment.
The nanocomposites may be further characterized in having improved air barrier qualities when measure by the test method above, wherein the oxygen permeability of the elastomer/thermoplastic blend ranges from less than 3.0�10−8 cc-mil/m2-day-mmHg in one embodiment (at 60� C.), and less than 2.0�10−8 cc-mil/m2-day-mmHg in another embodiment, and between 3.0�10−8 cc-mil/m2-day-mmHg and 0.5�10−8 cc-mil/m2-day-mmHg in yet another embodiment.
The invention also includes a method of forming a nanocomposite comprising forming a first phase of an alkylamine-exfoliated clay and an interpolymer of C4 to C7 isomonoolefin derived units, a para-methylstyrene derived units and a para-(halomethylstyrene) derived units; then blending the first phase with at least a second phase comprising a thermoplastic engineering resin. The first phase may be formed by any suitable means such as blending in a Brabender� or Banbury� or other suitable blender such as a dispersion of materials is achieved. The first and second phases are blended by any suitable means as described herein.
The following examples are illustrative of the invention.
Materials used in the blends in the examples are shown in Table 1. A series of formulations were prepared by compounding polyamide resin and brominated isobutylene/para-methylstyrene elastomer (BIMS) present at various levels as shown in Table 2 (phr), then blended with the nylon in various amounts shown in Table 3 (wt %). The values in Table 2 in phr (parts per hundred rubber) can be converted to wt % by dividing each value by the total amount of components, in the present case 124. Thus, in Table 2, the equivalent value of BIMS expressed as a weight percent is 100/124, or 0.806 (80.6 wt %) of the BIMS/clay phase.
Permeability Testing. All specimens were compression molded with slow cooling to provide defect free pads. A compression and curing press was used for rubber samples. Typical thickness of a compression molded pad is around 15 mil. using an Arbor press, 2″ diameter disks were then punched out from molded pads for permeability testing. These disks were conditioned in a vacuum oven at 60� C. overnight prior to the measurement. The oxygen permeation measurements were done using a Mocon OX-TRAN 2/61 permeability tester at 60� C. under the principle of R. A. Pasternak et. al. in 8 JOURNAL OF POLYMER SCIENCE: PART A-2 467 (1970). Disks thus prepared were mounted on a template and sealed with a vacuum grease. 10 psi nitrogen was kept on one side of the disk, whereas the other side is 10 psi oxygen. Using the oxygen sensor on the nitrogen side, increase in oxygen concentration on the nitrogen side with time could be monitored. The time required for oxygen to permeate through the disk, or for oxygen concentration on the nitrogen side to reach a constant value, is recorded and used to determine the oxygen permeability. Permeability values are multiplied by 108 as expressed in the tables unless stated otherwise noted.
Tapping Phase Atomic Force Microscopy. All specimens were analyzed within 8 hours after cryofacing to prevent specimen relaxation. During cryofacing, the specimens were cooled to −150� C. and cut with diamond knives in a Reichert cryogenic microtome. They were then stored in a dissector under flowing dry nitrogen gas to warm up to ambient temperatures without condensation being formed. Finally, the faced specimens were mounted in a miniature steel vice for AFM analysis. The AFM measurements were performed in air on a NanoScope Dimension 3000 scanning probe microscope (Digital Instrument) using a rectangular Si cantilever. AFM phase images of all specimens were converted into a TIFF format and processed using PHOTOSHOP� (Adobe Systems, Inc.). The image processing tool kit (Reindeer Games, Inc.) was applied for image measurements. Results of image measurements were written into a text file for subsequent data processing using EXCEL�.
Mixing BIMS with Cloisite clays to form a first phase of the final nanocomposite, and curatives, was performed using a Banbury� mixer. It is understood that any number of curatives or additives can be used, and the invention is not limited as such. Compositions of these mixes are listed in Table 2. All BIMS blends were cured to prepare pads for permeability measurement using a Mocon permeability tester. Oxygen permeability values at 60� C. were measured for these cured pads. The permeability value (in cc-mil/m2-day-mmHg) for the BIMS sample is 20.5, while the values for the BIMS-1 through BIMS-3 samples range from 23 to 14, showing some reduction. The values of the BIMS-4 through BIMS-6 samples ranged from 17.3 to 18.6, thus showing generally more reduction in air permeability for the blends in Table 2. Adding 20 phr of clays would lower the permeability of BIMS rubber by 10 to 30%. TEM images of these clay containing BIMS rubbers revealed that a mixture of clay dispersion states is present, including undispersed clays, intercalated clays, and few exfoliated clays.
Further reduction in permeability was achieved by blending BIMS with low-permeability Nylon 6/66 with or without clays, the nylon forming another or second phase of the final nanocomposite. BIMS rubbers with or without clays as described in Table 2 were cut into strips to be fed into a Brabender� mixer at 220� C. Due to the presence of curatives in BIMS, dynamic vulcanization occurred during blending in the Brabender� mixer at 60 RPM for 5 minutes. Fine BIMS dispersions were observed by AFM and image processing. Number average sizes of BIMS dispersions in equivalent diameter range from 0.37 to 0.57 microns. The AFM confirms the presence of two phases in the nanocomposite resulting from the mixture of the BIMS/clay phase and the nylon phase. The dynamic vulcanized blend compositions are listed in Table 3 and their permeability values are tabulated in Table 4. As indicated in Table 4, mixing BIMS with Nylon in 30/70 ratio without clays could provide 92% reduction in permeability. It is also desirable to add clays to the nylon phase in another embodiment of the invention. By adding clays in both Nylon and BIMS, 97% reduction in permeability could be realized.
Embodiments of the final nanocomposite of the present invention are useful as air barriers, such as used in producing innerliners for motor vehicles. In particular, the nanocomposites are useful in innerliners in articles such as truck tires, bus tires, passenger automobile, motorcycle tires, off the road tires, and the like. The improved heat aging resistance of the present innerliner composition makes it particularly suited for use in truck tires to increase the retreading capability of the tire.
While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to many different variations not illustrated herein. For these reasons, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.
All priority documents are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted. Further, all documents cited herein, including testing procedures, are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted.
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