text:
A pre-adhesive composition is described comprising an acid-functional (meth)acrylate copolymer and a crosslinking system comprising an aziridine crosslinking agent and epoxy-functional (meth)acryloyl monomer, which when crosslinked, provides a pressure-sensitive adhesive and pressure-sensitive adhesive articles.
1. A crosslinkable composition comprising:
a) a first component acid-functional acrylic copolymer comprising:
i. 85 to 99 parts by weight of an (meth)acrylic acid ester of non-tertiary alcohol;
ii. 1 to 15 parts by weight of an acid functional monomer;
iii. 0 to 10 parts by weight of a second, non-acid functional, polar monomer;
iv. 0 to 5 parts vinyl monomer; and
b) a second component epoxy-functional (meth)acryloyl monomer; and
c) a third component aziridine crosslinking agent of the formula:
R1 is H or C1-C4 alkyl;
z is 0, 1 or 2
R2 is a H or C1-C4 alkyl;
R3 is a (hetero)hydrocarbyl group:
X1 is —O— or —NR1—;
Z is —H or a water-solubilizing group.
2. The crosslinkable composition of
3. The crosslinkable composition of
4. The crosslinkable composition of
5. The crosslinkable composition of
6. The crosslinkable composition of
7. The crosslinkable composition of
9. The crosslinkable composition of
10. The crosslinkable composition of
11. The crosslinkable composition of
13. The crosslinkable composition of
14. The crosslinkable composition of
15. The crosslinkable composition of
16. The crosslinkable composition of
(a) 30 to about 70 weight percent, based on the total weight of the emulsion, of the crosslinkable composition of
(b) 30 to 70 weight percent of an aqueous phase comprising a surfactant, based on the total weight of the emulsion.
17. The emulsion of
18. The crosslinkable composition of
a) a first component acid-functional acrylic copolymer comprising:
i. 85 to 99 parts by weight of an (meth)acrylic acid ester of non-tertiary alcohol;
ii. 1 to 15 parts by weight of an acid functional monomer;
iii. 0 to 10 parts by weight of a second, non-acid functional, polar monomer;
iv. 0 to 5 parts vinyl monomer;
b) a second component comprising at least one free-radically polymerizable solvent monomer,
c) a third component epoxy-functional (meth)acryloyl monomer; and
d) a fourth component aziridine crosslinking agent of the formula:
R1 is H or C1-C4 alkyl;
z is 0, 1 or 2
R2 is a H or C1-C4 alkyl;
R3 is a (hetero)hydrocarbyl group:
X1 is —O— or —NR1—;
Z is —H or a water-solubilizing group.
This application claims the benefit of U.S. Provisional Patent Application No. 61/263,422, filed Nov. 23, 2009, the disclosure of which is incorporated by reference herein in its entirety.
This invention relates to pressure sensitive adhesives and tape articles prepared therefrom. The tapes are characterized by exhibiting an overall balance of adhesive and cohesive characteristics and exceptional load bearing capabilities.
Pressure sensitive tapes are virtually ubiquitous in the home and workplace. In its simplest configuration, a pressure sensitive tape comprises an adhesive and a backing, and the overall construction is tacky at the use temperature and adheres to a variety of substrates using only moderate pressure to form the bond. In this fashion, pressure sensitive tapes constitute a complete, self-contained bonding system.
According to the Pressure-Sensitive Tape Council, pressure-sensitive adhesives (PSAs) are known to possess properties including the following: (1) aggressive and permanent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and (4) sufficient cohesive strength to be removed cleanly from the adherend. Materials that have been found to function well as PSAs include polymers designed and formulated to exhibit the requisite viscoelastic properties resulting in a desired balance of tack, peel adhesion, and shear holding power. PSAs are characterized by being normally tacky at room temperature (e.g., 20� C.). PSAs do not embrace compositions merely because they are sticky or adhere to a surface.
These requirements are assessed generally by means of tests which are designed to individually measure tack, adhesion (peel strength), and cohesion (shear holding power), as noted in A. V. Pocius in Adhesion and Adhesives Technology: An Introduction, 2nd Ed., Hanser Gardner Publication, Cincinnati, Ohio, 2002. These measurements taken together constitute the balance of properties often used to characterize a PSA.
With broadened use of pressure sensitive tapes over the years, performance requirements have become more demanding. Shear holding capability, for example, which originally was intended for applications supporting modest loads at room temperature, has now increased substantially for many applications in terms of operating temperature and load. So-called high performance pressure sensitive tapes are those capable of supporting loads at elevated temperatures for 10,000 minutes. Increased shear holding capability has generally been accomplished by crosslinking the PSA, although considerable care must be exercised so that high levels of tack and adhesion are retained in order to retain the aforementioned balance of properties.
There are two major crosslinking mechanisms for acrylic adhesives: free-radical copolymerization of multifunctional ethylenically unsaturated groups with the other monomers, and covalent or ionic crosslinking through the functional monomers, such as acrylic acid. Another method is the use of UV crosslinkers, such as copolymerizable benzophenones or post-added photocrosslinkers, such as multifunctional benzophenones and triazines. In the past, a variety of different materials have been used as crosslinking agents, e.g., polyfunctional acrylates, acetophenones, benzophenones, and triazines. The foregoing crosslinking agents, however, possess certain drawbacks which include one or more of the following: high volatility; incompatibility with certain polymer systems; generation of corrosive or toxic by-products; generation of undesirable color; requirement of a separate photoactive compound to initiate the crosslinking reaction; and high sensitivity to oxygen.
Briefly, the present disclosure provides a pre-adhesive composition comprising an acid-functional (meth)acrylate copolymer and a crosslinking system comprising a) an aziridine crosslinking agent and b) an epoxy-functional (meth)acryloyl monomer, which when crosslinked, provides a pressure sensitive adhesive composition.
The use of the novel crosslinking system affords a number of advantages as compared to the use of conventional crosslinking agents for (meth)acrylic adhesives. These advantages include, but are not limited to, decreased sensitivity of the crosslinkable composition to oxygen; the avoidance of evolution of any toxic or corrosive by-products or discoloration of the final product; and the capability to be used as a post-curing crosslinking additive. Furthermore, the crosslinking system, comprising an aziridine crosslinking agent and an epoxy-functional (meth)acryloyl monomer, have the following advantages over previously described agents: ease of synthesis, high solubility in the component monomers or organic solvents, and low cost starting materials. In addition, the cured adhesives exhibit high peel strength, and high cohesive strength, and high temperature shear strength.
In one aspect, the disclosure provides a novel pre-adhesive syrup polymer composition comprising a) an acid-functional (meth)acrylate solute copolymer, b) at least one free-radically polymerizable solvent monomer, c) an aziridine crosslinking agent and d) an epoxy-functional (meth)acryloyl monomer. The pre-adhesive syrup polymer composition may be polymerized and crosslinked to produce a pressure-sensitive adhesive.
In another embodiment the disclosure provides a pre-adhesive emulsion comprising an aqueous emulsion of the acid-functional (meth)acrylate copolymer, an aziridine crosslinking agent and an epoxy-functional (meth)acryloyl monomer, which may be coated and crosslinked to form a pressure sensitive adhesive. In a related embodiment, the present disclosure provides an adhesive emulsion comprising an aqueous emulsion of the reaction product of the acid-functional (meth)acrylate copolymer, the an aziridine crosslinking agent and an epoxy-functional (meth)acryloyl monomer, which may be coated and cured to form a pressure sensitive adhesive.
For environmental reasons, there is a desire to move away from the use of volatile organic solvents (VOC's) in coating processes, and towards more environmentally friendly water-based materials, so the present invention provides a waterborne adhesive comprising an aqueous emulsion supra. Waterborne systems are desirable for cost, environmental, safety, and regulatory reasons. The aqueous system may be readily coated, and provides a pressure-sensitive adhesive when cured.
The pressure-sensitive adhesives, the crosslinked compositions, of this disclosure provide the desired balance of tack, peel adhesion, and shear holding power, and further conform to the Dahlquist criteria; i.e. the modulus of the adhesive at the application temperature, typically room temperature, is less than 3�106 dynes/cm at a frequency of 1 Hz.
In some embodiments, this disclosure provides an adhesive composition derived from renewable resources. In particular, the present invention provides an adhesive composition derived, in part, from plant materials. In some embodiments, the present invention further provides an adhesive article, wherein the substrate or backing is also derived from renewable resources. The increase in the price of oil, and concomitant petroleum-derived products, has led to volatile prices and supply for many adhesive products. It is desirable to replace all or part of the petroleum-based feedstocks with those derived from renewable sources, such as plants, as such materials become relatively cheaper, and are therefore both economically and socially beneficial. Therefore, the need for such plant-derived materials has become increasingly significant.
In this application "pre-adhesive" refers to the solution, suspension, or emulsion comprising an acid-functional (meth)acrylate copolymer, and crosslinking system comprising an aziridine crosslinking agent and which may be crosslinked to form a pressure sensitive adhesive.
"Syrup polymer" refers to a solution of a solute polymer in one or more solvent monomers, the solution having a viscosity of from 500 to 10,000 cPs at 22� C. "Solution polymer" refers to a solution of a solute polymer in one or more organic solvents.
As used herein "(meth)acryloyl" is inclusive of (meth)acrylate and (meth)acrylamide.
In this application, (meth)acrylic is inclusive of both methacrylic and acrylic.
As used herein, "alkyl" includes straight-chained, branched, and cyclic alkyl groups and includes both unsubstituted and substituted alkyl groups. Unless otherwise indicated, the alkyl groups typically contain from 1 to 20 carbon atoms. Examples of "alkyl" as used herein include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and norbornyl, and the like. Unless otherwise noted, alkyl groups may be mono- or polyvalent.
As used herein, the term "heteroalkyl" includes both straight-chained, branched, and cyclic alkyl groups with one or more heteroatoms independently selected from S, O, and N with both unsubstituted and substituted alkyl groups. Unless otherwise indicated, the heteroalkyl groups typically contain from 1 to 20 carbon atoms. "Heteroalkyl" is a subset of "hydrocarbyl containing one or more S, N, O, P, or Si atoms" described below. Examples of "heteroalkyl" as used herein include, but are not limited to, methoxy, ethoxy, propoxy, 3,6-dioxaheptyl, 3-(trimethylsilyl)-propyl, 4-dimethylaminobutyl, and the like. Unless otherwise noted, heteroalkyl groups may be mono- or polyvalent.
As used herein, "aryl" is an aromatic group containing 6-18 ring atoms and can contain optional fused rings, which may be saturated, unsaturated, or aromatic. Examples of an aryl groups include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl. Heteroaryl is aryl containing 1-3 heteroatoms such as nitrogen, oxygen, or sulfur and can contain fused rings. Some examples of heteroaryl groups are pyridyl, furanyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl, benzofuranyl, and benzthiazolyl. Unless otherwise noted, aryl and heteroaryl groups may be mono- or polyvalent.
As used herein, "(hetero)hydrocarbyl" is inclusive of hydrocarbyl alkyl and aryl groups, and heterohydrocarbyl heteroalkyl and heteroaryl groups, the later comprising one or more catenary (in-chain) heteroatoms such as ether or amino groups. Heterohydrocarbyl may optionally contain one or more catenary (in-chain) functional groups including ester, amide, urea, urethane, and carbonate functional groups. Unless otherwise indicated, the non-polymeric (hetero)hydrocarbyl groups typically contain from 1 to 60 carbon atoms. Some examples of such heterohydrocarbyls as used herein include, but are not limited to, methoxy, ethoxy, propoxy, 4-diphenylaminobutyl, 2-(2′-phenoxyethoxy)ethyl, 3,6-dioxaheptyl, 3,6-dioxahexyl-6-phenyl, in addition to those described for "alkyl", "heteroalkyl", "aryl", and "heteroaryl" supra.
The present disclosure provides a pre-adhesive composition comprising an acid-functional (meth)acrylate copolymer and a crosslinking system comprising an aziridine crosslinking agent and epoxy-functional (meth)acryloyl monomer, which when crosslinked, provides a pressure-sensitive adhesive and pressure-sensitive adhesive articles.
The (meth)acrylate ester monomer useful in preparing the acid functional (meth)acrylate adhesive copolymer is a monomeric (meth)acrylic ester of a non-tertiary alcohol, which alcohol contains from 1 to 14 carbon atoms and preferably an average of from 4 to 12 carbon atoms.
Examples of monomers suitable for use as the (meth)acrylate ester monomer include the esters of either acrylic acid or methacrylic acid with non-tertiary alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-ethyl-1-butanol, 3,5,5-trimethyl-1-hexanol, 3-heptanol, 1-octanol, 2-octanol, isooctylalcohol, 2-ethyl-1-hexanol, 1-decanol, 2-propylheptanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, citronellol, dihydrocitronellol, and the like. In some embodiments, the preferred (meth)acrylate ester monomer is the ester of (meth)acrylic acid with butyl alcohol or isooctyl alcohol, or a combination thereof, although combinations of two or more different (meth)acrylate ester monomer are suitable. In some embodiments, the preferred (meth)acrylate ester monomer is the ester of (meth)acrylic acid with an alcohol derived from a renewable sources, such as 2-octanol, citronellol, dihydrocitronellol.
In some embodiments it is desirable for the (meth)acrylic acid ester monomer to include a high Tg monomer, have a Tg of at least 25� C., and preferably at least 50� C. Suitable high Tg monomers include Examples of suitable monomers useful in the present invention include, but are not limited to, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, stearyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, 3,3,5 trimethylcyclohexyl acrylate, cyclohexyl acrylate, N-octyl acrylamide, and propyl methacrylate or combinations.
The (meth)acrylate ester monomer is present in an amount of 85 to 99.5 parts by weight based on 100 parts total monomer content used to prepare the polymer. Preferably (meth)acrylate ester monomer is present in an amount of 90 to 95 parts by weight based on 100 parts total monomer content. When high Tg monomers are included, the copolymer may include up to 30 parts by weight, preferably up to 20 parts by weight of the 85 to 99.5 parts by weight of (meth)acrylate ester monomer component. In such embodiments, the copolymer may comprise:
The polymer further comprises an acid functional monomer, where the acid functional group may be an acid per se, such as a carboxylic acid, or a portion may be salt thereof, such as an alkali metal carboxylate. Useful acid functional monomers include, but are not limited to, those selected from ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids, and mixtures thereof. Examples of such compounds include those selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, oleic acid, β-carboxyethyl (meth)acrylate, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, and mixtures thereof.
Due to their availability, acid functional monomers of the acid functional copolymer are generally selected from ethylenically unsaturated carboxylic acids, i.e. (meth)acrylic acids. When even stronger acids are desired, acidic monomers include the ethylenically unsaturated sulfonic acids and ethylenically unsaturated phosphonic acids. The acid functional monomer is generally used in amounts of 0.5 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight total monomer.
The polar monomers useful in preparing the copolymer are both somewhat oil soluble and water soluble, resulting in a distribution of the polar monomer between the aqueous and oil phases in an emulsion polymerization. As used herein the term "polar monomers" are exclusive of acid functional monomers.
Representative examples of suitable polar monomers include but are not limited to 2-hydroxyethyl (meth)acrylate; N-vinylpyrrolidone; N-vinylcaprolactam; acrylamide; mono- or di-N-alkyl substituted acrylamide; t-butyl acrylamide; dimethylaminoethyl acrylamide; N-octyl acrylamide; poly(alkoxyalkyl) (meth)acrylates including 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, 2-methoxyethyl methacrylate, polyethylene glycol mono(meth)acrylates; alkyl vinyl ethers, including vinyl methyl ether; and mixtures thereof. Preferred polar monomers include those selected from the group consisting of 2-hydroxyethyl (meth)acrylate and N-vinylpyrrolidinone. The polar monomer may be present in amounts of 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight total monomer.
When used, vinyl monomers useful in the (meth)acrylate polymer include vinyl esters (e.g., vinyl acetate and vinyl propionate), styrene, substituted styrene (e.g., α-methyl styrene), vinyl halide, and mixtures thereof. As used herein vinyl monomers are exclusive of acid functional monomers, acrylate ester monomers and polar monomers. Such vinyl monomers are generally used at 0 to 5 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight total monomer.
In order to increase cohesive strength of the coated adhesive composition, a multifunctional (meth)acrylate may be incorporated into the blend of polymerizable monomers. Multifunctional acrylates are particularly useful for emulsion or syrup polymerization. Examples of useful multifunctional (meth)acrylate include, but are not limited to, di(meth)acrylates, tri(meth)acrylates, and tetra(meth)acrylates, such as 1,6-hexanediol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylates, polybutadiene di(meth)acrylate, polyurethane di(meth)acrylates, and propoxylated glycerin tri(meth)acrylate, and mixtures thereof. The amount and identity of multifunctional (meth)acrylate is tailored depending upon application of the adhesive composition. Typically, the multifunctional (meth)acrylate is present in amounts less than 5 parts based on total dry weight of adhesive composition. More specifically, the crosslinkers may be present in amounts from 0.01 to 5 parts, preferably 0.05 to 1 parts, based on 100 parts total monomers of the adhesive composition. In some embodiments the crosslinking compositions contains no multifunctional (meth)acrylates.
The adhesive composition further comprises an aziridine crosslinking agent, in addition to the (meth)acrylate copolymer. The aziridine crosslinking agent is generally added in amounts of 0.005 to 5.0 parts by weight of an aziridine crosslinking agent, relative to 100 parts of the copolymer.
The aziridine crosslinking agent is of the general formula:
In some embodiments, Z is a hydrogen and R3—Z represents a hydrocarbyl alkyl or aryl group.
In other embodiments, Z is a water-solubilizing group, and pre-adhesive compositions derived therefrom are particularly suited in emulsion adhesive polymer applications. The term "water solubilizing groups" are functional groups that help solubilizing or dispersing the crosslinking agent (and subsequently the adhesive copolymer) in water. By the term "water soluble" is meant that a concentration of at least 0.1% by weight, preferably 0.5% by weight, of the crosslinking agent can be dissolved in water at ambient temperature. By the term "water dispersible" is meant that a dispersion of at least 0.1% by weight of the crosslinking agent in water can be made that is stable for at least 1 hour, preferably for at least 4 hours, without additional emulsifier present.
In some embodiments the aziridine crosslinking agent contains Z; a water solubilizing group, or groups capable of forming water solubilizing groups, so as to obtain a reaction product that is self-emulsifying in water. Suitable water solubilizing groups include cationic, anionic and zwitterionic groups as well as non-ionic water solubilizing groups. Examples of groups capable of forming a water solubilizing group in water include groups that have the potential of being protonated in water such as amino groups, in particular tertiary amino groups.
The water solubilizing group Z may be a cationic, anionic or nonionic water solubilizing group. It will be understood that the ionic nature of any water-solubilizing groups will be affected by the pH of the emulsion, i.e. carboxylic acid groups may be nonionic at low pH and ionic at high pH.
In some embodiments of Formula II, Z may be Z1, where Z1 is an ionic water solubilizing groups selected from ammonium groups, phosphonium groups, sulfonium groups, carboxylates, sulfonates, phosphates, phosphonates or phosphinate groups. Such groups can be represented as —CO2M, —OSO3M, —SO3M, —OPO3M, —PO (OM)2, —NR2HX, —NR3X, —NRH2X, and —NH3X, wherein M is H or one equivalent of a monovalent or divalent soluble cation such as sodium, potassium, calcium, and NR3H+; X is a soluble anion such as those selected from the group consisting of halide, hydroxide, carboxylate, sulfonates, and the like; and R is selected from the group consisting of a phenyl group, a cycloaliphatic group, or a straight or branched aliphatic group having from about 1 to about 12 carbon atoms. Preferably, R is a lower alkyl group having from 1 to 4 carbon atoms.
Typical examples of a non-ionic water solubilizing group are hydroxyl groups and poly(oxyalkylene) groups. An oxyalkylene unit in the poly(oxyalkylene) group preferably has 2 or 3 carbon atoms, such as —OCH2CH2—, —OCH2CH2CH2—, and —OCH(CH3)CH2—, the oxyalkylene units in the poly(oxyalkylene) group can be the same, as in poly(oxyethylene), or present as a mixture, as in straight or branched chain or randomly distributed oxyethylene and oxypropylene units or as in a straight or branched chain of blocks of oxyethylene units and blocks of oxypropylene units, as long as the poly(oxyalkylene) group remains water soluble or water dispersible. Particularly preferred poly(oxyalkylene) groups are polyoxyethylene and alkoxypolyoxyethylenes that have a molecular weight up to about 1500. Preferably, the number of oxyalkylene units in a poly(oxyalkylene) is between 2 and 120 and more preferably between 2 and 48. With reference to Formula II, Z is Z2, where Z2 is a poly(oxyalkylene) group.
The aziridine crosslinking agents may be prepared by Michael addition of an aziridine compound with an acryloyl compound, using the general procedure described in U.S. Pat. No. 3,243,429 (Ham), and as illustrated in the following Scheme I:
Alternatively, compounds of Formula I may be prepared by Michael addition of an aziridine compound to an acryloyl compound, followed by transesterification or transamidation as illustrated in the following Scheme II:
The crosslinking system further comprises an epoxy-functional (meth)acryloyl monomer of the formula:
The epoxy-functional (meth)acryloyl monomer can be any suitable monomer as defined above and may be substituted as defined above. Preferably the R5 group is based on a straight-chain, branched, cyclic or polycyclic hydrocarbon of between 2-30 carbons having an oxirane (epoxy) group included. More preferably, the R5 group contains between 3-10 carbons, such as glycidylmethacrylate (GMA). Some embodiments contain an epoxycyclohexyl group such as 3,4-epoxycyclohexylmethyl (meth)acrylate and 3-(2,3-epoxypropoxy)phenyl acrylate, 2-[4-(2,3-epoxypropoxy)phenyl]-2-(4-acryloyloxy-phenyl)propane, 4-(2,3-epoxypropoxy)cyclohexyl acrylate, 2,3-epoxycyclohexyl acrylate, and the acrylic acid monoester of poly(Bisphenol-A diglycidyl ether), commercially available as Ebecryl™ 3605, from Rad-Cure Corp., Fairfield, N.J., and species having R5 according to the formula:
—[(CH2)5C(O)O]n—CH2-epoxycyclohexyl, wherein n is 0 to 10 and preferably 1-4. Epoxy-functional (meth)acrylate monomers useful in the invention include the acrylic acid monoester of poly(Bisphenol-A diglycidyl ether), commercially available as Ebecryl™ 3605, from Rad-Cure Corp., Fairfield, N.J., and the polyesters comprising (meth)acrylic acid, caprolactone or valerolactone or cyclooctanone lactone, and epoxidized cyclohexane derivatives such as 3,4-epoxycyclohexylmethanol, 3,4-epoxycyclohexane carboxylic acid, and 4,5-epoxycyclohexane-1,2-dicarboxylic acid.
Some preferred epoxy monomers are of the formula:
The epoxy-functional (meth)acryloyl monomer is generally used in amounts of up to a stoichiometric equivalent of the aziridine component. More generally the epoxy-functional (meth)acryloyl monomer is generally used in amounts of in amounts 0.005 to 5.0 parts by weight relative to 100 parts by weight of said first component acid-functional acrylic copolymer.
It is believed that the aziridine group reacts with the pendent acid functional groups of the acid functional (meth)acrylate copolymer to form a carboxyethyleneamino linkage as shown in Scheme III. In one embodiment, the intermediate may be of the following structure, with the optional monomer units and unreacted (free) acid functional monomer units not shown. It is further believed that the secondary nitrogen atom, derived from ring-opening of the aziridine, then adds to the epoxy group of the epoxy-functional (meth)acryloyl monomer. As can be seen, the reaction of the secondary nitrogen atom provides a pendent acryloyl group that may be subsequently crosslinked. It will be understood that the R1 group may be on the indicated carbon, or attached to the carbon adjacent to the ester oxygen atom, depending on the ring opening of the aziridine group.
The acid functional copolymers can be prepared by any conventional free radical polymerization method, including solution, radiation, bulk, dispersion, emulsion, and suspension processes. The (meth)acrylate polymers may be prepared via suspension polymerizations as disclosed in U.S. Pat. No. 3,691,140 (Silver); U.S. Pat. No. 4,166,152 (Baker et al.); U.S. Pat. No. 4,636,432 (Shibano et al); U.S. Pat. No. 4,656,218 (Kinoshita); and U.S. Pat. No. 5,045,569 (Delgado). Each describes adhesive compositions, and the descriptions of polymerization processes are incorporated herein by reference.
Water-soluble and oil-soluble initiators useful in preparing the acid functional copolymers are initiators that, on exposure to heat, generate free-radicals which initiate (co)polymerization of the monomer mixture. Water-soluble initiators are preferred for preparing the (meth)acrylate polymers by emulsion polymerization. When used, initiators may comprise from about 0.05 to about 1 part by weight, preferably about 0.1 to about 0.5 part by weight based on 100 parts by weight of monomer components in the acid functional copolymers.
Suitable water-soluble initiators include but are not limited to those selected from the group consisting of potassium persulfate, ammonium persulfate, sodium persulfate, and mixtures thereof; oxidation-reduction initiators such as the reaction product of the above-mentioned persulfates and reducing agents such as those selected from the group consisting of sodium metabisulfite and sodium bisulfite; and 4,4′-azobis(4-cyanopentanoic acid) and its soluble salts (e.g., sodium, potassium). The preferred water-soluble initiator is potassium persulfate. Suitable oil-soluble initiators include but are not limited to those selected from the group consisting of azo compounds such as VAZO™ 64 (2,2′-azobis(isobutyronitrile)), VAZO™ 67 (2,2′azobis (2-methylbutyronitrile)), and VAZO™ 52 (2,2′-azobis(2,4-dimethylpentanenitrile)), available from E.I. du Pont de Nemours Co., peroxides such as benzoyl peroxide and lauroyl peroxide, and mixtures thereof. The preferred oil-soluble thermal initiator is 2,2′-azobis-(2,4-dimethylpentanenitrile).
The copolymerizable emulsion mixture may optionally further comprise chain transfer agents to control the molecular weight of the resultant polymer. Examples of useful chain transfer agents include but are not limited to those selected from the group consisting of carbon tetrabromide, alcohols, mercaptans, and mixtures thereof. When present, the preferred chain transfer agents are isooctylthioglycolate and carbon tetrabromide. The emulsion mixture may further comprise up to about 0.5 parts by weight of a chain transfer agent, typically about 0.01 to about 0.5 parts by weight, if used, preferably about 0.05 parts by weight to about 0.2 parts by weight, based upon 100 parts by weight of the total monomer mixture.
Polymerization of the acid functional copolymers via emulsion techniques may require the presence of an emulsifier (which may also be called an emulsifying agent or a surfactant). Useful emulsifiers for the present invention include those selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, and mixtures thereof.
Preferably, emulsion polymerization is carried out in the presence of anionic surfactant(s). A useful range of emulsifier concentration is from about 0.5 to about 8 weight percent, preferably from about 1 to about 5 weight percent, based on the total weight of all monomers of the emulsion pressure sensitive adhesive.
The acid functional (meth)acrylate copolymers may be prepared by a batch, continuous or semi-continuous emulsion polymerization process. The polymerization generally comprises the steps of:
A neutralizing agent may be employed in the preparation of this copolymer. It may be employed at a level sufficient to neutralize all or a part of the acid groups of the polymer. Neutralization is achieved via the use of an alkali metal hydroxide or a combination of an alkali metal hydroxide with a minor amount of another neutralizing agent. A wide variety of other neutralizing agents may be used as will be understood by those skilled in the art. The selection of the other neutralizing agent, and the amount employed may be varied to achieve a desired result. However, the type and amount selected must not render the adhesive non-dispersible. Preferably ammonium, sodium and potassium hydroxide are used as neutralizing agents.
A alternate method of preparing acid functional (meth)acrylate copolymers comprises partially polymerizing monomers to produce a syrup polymer comprising the acid functional (meth)acrylate copolymer and unpolymerized monomers. The syrup polymer composition is polymerized to a useful coating viscosity, which may be coated onto a substrate (such as a tape backing) and further polymerized. Partial polymerization provides a coatable solution of the acid functional (meth)acrylate solute copolymer in one or more solvent monomers. Generally, the crosslinking system—comprising the aziridine and epoxy-functional (meth)acryloyl monomer—is added to the partially polymerized composition, then coated on a suitable substrate and further polymerized.
For syrup application processing, a preferred monomer mixture (second component) comprises 85 to 99.5 pbw of one or more (meth)acrylate ester monomers, 0.5 to 15 pbw of acid functional monomers, 0 to 10 pbw of one or more second, non-acid, polar monomers, and 0 to about 5 pbw of other vinyl monomers, based on 100 parts total monomer.
The polymerizations may be conducted in the presence of, or preferably in the absence of, suitable solvents such as ethyl acetate, toluene and tetrahydrofuran which are unreactive with the functional groups of the components of the syrup polymer.
Polymerization can be accomplished by exposing the syrup polymer composition to energy in the presence of a photoinitiator. Energy activated initiators may be unnecessary where, for example, ionizing radiation is used to initiate polymerization. These photoinitiators can be employed in concentrations ranging from about 0.0001 to about 3.0 pbw, preferably from about 0.001 to about 1.0 pbw, and more preferably from about 0.005 to about 0.5 pbw, per 100 pbw of the solvent monomer(s).
A preferred method of preparation of the syrup polymer is photoinitiated free radical polymerization. Advantages of the photopolymerization method are that 1) heating the monomer solution is unnecessary and 2) photoinitiation is stopped completely when the activating light source is turned off. Polymerization to achieve a coatable viscosity may be conducted such that the conversion of monomers to polymer is up to about 30%. Polymerization can be terminated when the desired conversion and viscosity have been achieved by removing the light source and by bubbling air (oxygen) into the solution to quench propagating free radicals. The solute polymer(s) may be prepared conventionally in a non-monomeric solvent and advanced to high conversion (degree of polymerization). When solvent (monomeric or non-monomeric) is used, the solvent may be removed (for example by vacuum distillation) either before or after formation of the syrup polymer. While an acceptable method, this procedure involving a highly converted functional polymer is not preferred because an additional solvent removal step is required, another material may be required (the non-monomeric solvent), and dissolution of the high molecular weight, highly converted solute polymer in the monomer mixture may require a significant period of time.
Useful photoinitiators include benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether; substituted acetophenones such as 2,2-dimethoxyacetophenone, available as Irgacure™ 651 photoinitiator (Ciba Specialty Chemicals), 2,2 dimethoxy-2-phenyl-1-phenylethanone, available as Esacure™ KB-1 photoinitiator (Sartomer Co.; West Chester, Pa.), and dimethoxyhydroxyacetophenone; substituted α-ketols such as 2-methyl-2-hydroxy propiophenone; aromatic sulfonyl chlorides such as 2-naphthalene-sulfonyl chloride; and photoactive oximes such as 1-phenyl-1,2-propanedione-2-(O-ethoxy-carbonyl)oxime. Particularly preferred among these are the substituted acetophenones.
Preferred photoinitiators are photoactive compounds that undergo a Norrish I cleavage to generate free radicals that can initiate by addition to the acrylic double bonds. The photoinitiator can be added to the mixture to be coated after the copolymer has been formed, i.e., photoinitiator can be added to the syrup polymer mixture. Such polymerizable photoinitiators are described, for example, in U.S. Pat. Nos. 5,902,836 and 5,506,279 (Babu et al.).
The syrup polymer composition and the photoinitiator may be irradiated with activating UV radiation to polymerize the monomer component(s). UV light sources can be of two types: 1) relatively low light intensity sources such as Blacklights which provide generally 10 mW/cm2 or less (as measured in accordance with procedures approved by the United States National Institute of Standards and Technology as, for example, with a UVIMAP™ UM 365 L-S radiometer manufactured by Electronic Instrumentation & Technology, Inc., in Sterling, Va.) over a wavelength range of 280 to 400 nanometers and 2) relatively high light intensity sources such as medium pressure mercury lamps which provide intensities generally greater than 10 mW/cm2, preferably between 15 and 450 mW/cm2. Where actinic radiation is used to fully or partially polymerize the syrup polymer composition, high intensities and short exposure times are preferred. For example, an intensity of 600 mW/cm2 and an exposure time of about 1 second may be used successfully. Intensities can range from about 0.1 to about 150 mW/cm2, preferably from about 0.5 to about 100 mW/cm2, and more preferably from about 0.5 to about 50 mW/cm2. Such photoinitiators preferably are present in an amount of from 0.1 to 1.0 pbw per 100 pbw of the syrup polymer composition.
Accordingly, relatively thick coatings (e.g., at least about 1 mil or 25.4 micrometers) can be achieved when the extinction coefficient of the photoinitiator is low.
The degree of conversion can be monitored during the irradiation by measuring the index of refraction of the polymerizing medium as previously described. Useful coating viscosities are achieved with conversions (i.e. the percentage of available monomer polymerized) in the range of up to 30%, preferably 2-20%, more preferably from 5-15%, and most preferably from 7-12%. The molecular weight (weight average) of the solute polymer(s) is at least 100,000, preferably at least 500,000.
When preparing acid functional (meth)acrylate copolymers, it is expedient for the photoinitiated polymerization reactions to proceed to virtual completion, i.e., depletion of the monomeric components, at temperatures less than about 70� C. (preferably at 50� C. or less) with reaction times less than 24 hours, preferably less than 12 hours, and more preferably less than 6 hours. These temperature ranges and reaction rates obviate the need for free radical polymerization inhibitors, which are often added to acrylic systems to stabilize against undesired, premature polymerization and gelation. Furthermore, the addition of inhibitors adds extraneous material that will remain with the system and inhibit the desired polymerization of the syrup polymer and formation of the crosslinked pressure sensitive adhesives. Free radical polymerization inhibitors are often required at processing temperatures of 70� C. and higher for reaction periods of more than about 6 to 10 hours.
In some embodiments, the acid functional (meth)acrylate copolymers may be prepared by solution methods. A typical solution polymerization method is carried out by adding the monomers, a suitable solvent, and an optional chain transfer agent to a reaction vessel, adding a free radical initiator, purging with nitrogen, and maintaining the reaction vessel at an elevated temperature, typically in the range of about 40 to 100� C. until the reaction is completed, typically in about 1 to 20 hours, depending upon the batch size and temperature. Examples of the solvent are methanol, tetrahydrofuran, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and an ethylene glycol alkyl ether. Those solvents can be used alone or as mixtures thereof.
It is preferable to coat the adhesive composition soon after preparation. The adhesive polymer composition, (containing the copolymer, monomers and crosslinking agent system), either as a syrup or solution are easily coated upon suitable substrates, such as flexible backing materials, by conventional coating techniques, then further polymerized, and cured or dried, to produce adhesive coated sheet materials. When emulsion polymerization techniques are used, an emulsion comprising the extant copolymer, and crosslinking agent system is coated and dried to produce adhesive coated sheet materials. The flexible backing material may be any material conventionally utilized as a tape backing, optical film or any other flexible material.
The pressure sensitive adhesives may also contain one or more conventional additives. Preferred additives include tackifiers, plasticizers, dyes, antioxidants, and UV stabilizers. Such additives can be used if they do not affect the superior properties of the emulsion pressure sensitive adhesives.
If tackifiers are used, then up to about 50% by weight, preferably less than 30% by weight, and more preferably less than 5% by weight based on the dry weight of the total adhesive polymer would be suitable. In some embodiments no tackifiers may be used. Suitable tackifiers for use with (meth)acrylate polymer dispersions include rosin acids, rosin esters, terpene phenolic resins, hydrocarbon resins, and cumarone indene resins. The type and amount of tackifier can affect properties such as contactability, bonding range, bond strength, heat resistance and specific adhesion.
Adhesive articles may be prepared by coating the adhesive or pre-adhesive composition of a suitable support, such as a flexible backing. Examples of materials that can be included in the flexible backing include polyolefins such as polyethylene, polypropylene (including isotactic polypropylene), polystyrene, polyester, polyvinyl alcohol, poly(ethylene terephthalate), poly(butylene terephthalate), poly(caprolactam), poly(vinylidene fluoride), polylactides, cellulose acetate, and ethyl cellulose and the like. Commercially available backing materials useful in the invention include kraft paper (available from Monadnock Paper, Inc.); cellophane (available from Flexel Corp.); spun-bond poly(ethylene) and poly(propylene), such as Tyvek™ and Typar™ (available from DuPont, Inc.); and porous films obtained from poly(ethylene) and poly(propylene), such as Teslin™ (available from PPG Industries, Inc.), and Cellguard™ (available from Hoechst-Celanese).
Backings may also be prepared of fabric such as woven fabric formed of threads of synthetic or natural materials such as cotton, nylon, rayon, glass, ceramic materials, and the like or nonwoven fabric such as air laid webs of natural or synthetic fibers or blends of these. The backing may also be formed of metal, metalized polymer films, or ceramic sheet materials may take the form of any article conventionally known to be utilized with pressure sensitive adhesive compositions such as labels, tapes, signs, covers, marking indicia, and the like.
The above-described compositions are coated on a substrate using conventional coating techniques modified as appropriate to the particular substrate. For example, these compositions can be applied to a variety of solid substrates by methods such as roller coating, flow coating, dip coating, spin coating, spray coating knife coating, and die coating. These various methods of coating allow the compositions to be placed on the substrate at variable thicknesses thus allowing a wider range of use of the compositions. Coating thicknesses may vary as previously described. The solutions may be of any desirable concentration, and degree of conversion, for subsequent coating, but is typically between 20 to 70 wt. % polymer solids, and more typically between 30 and 50 wt. % solids, in solvent. The emulsions also may be of any desirable concentration for subsequent coating, but is typically between 30 to 70 wt. % polymer solids, and generally contains less than 2% unreacted monomer. The syrup polymers may be of any desirable concentration for subsequent coating, but is typically between 5 to 20 wt. % polymer solids in monomer. The desired concentration may be achieved by further dilution of the coating composition, or by partial drying.
The flexible support may also comprise a release-coated substrate. Such substrates are typically employed when an adhesive transfer tape is provided. Examples of release-coated substrates are well known in the art and include, by way of example, silicone-coated kraft paper and the like. Tapes of the invention may also incorporate a low adhesion backing (LAB) which are known in the art.
Test Methods:
Peel Adhesion Test [ASTM D 3330/D 3330M-04]
Two 0.5 inch strips of tape were adhered to a glass plate by rolling a 4.5 lb roller onto the tape. The two tape samples were averaged. Force was measured in ounces per 0.5 inches with a platen speed of 90 and 12 inches per minute. Peel adhesion data was then normalized to Newtons per decimeter (N/dM) for the table below.
Shear Strength Test [ASTM D-3654/D 3654M 06, PSTC-7]
0.5 inch strips of tape were adhered by its adhesive to a stainless steel plate and cut down to leave 0.5 inch by 0.5 inch square for room temperature shears and a 1.0 inch by 0.5 inch square for 70� C. shears. A weight of 4.5 lbs was rolled over the adhered portion. A 1000 g load was attached to the room temperature shears and 500 g load for 70� C. shears. Each sample was suspended until failure and/or test terminated. Samples were run in triplicate and averaged for the tables below.
The aziridine crosslinking agents may be prepared by the Michael addition of the aziridine to an acryloyl compound. Generally, 1.1 to 4 equivalents of 2-methylaziridine are mixed with an (meth)acrylate or (meth)acrylamide, followed by standing at room temperature. The excess 2-methylaziridine is removed under reduced pressure to yield the Michael adduct, which may be used without further purification. Methacrylates and acrylamides generally require heating at about 70� C. with 1.1 to 4 equivalents of 2-methylaziridine for 1 to 7 days.
A sixteen-ounce (˜473 mL) jar was charged with 450 g of isooctyl acrylate (IOA, 90 parts), 50 g of acrylic acid (AA, 10 parts), and 0.2 g of 2,2-dimethoxy-2-phenylacetophenone photoinitiator (Irgacure 651, 0.04 phr). The monomer mixture was purged with nitrogen for 20 minutes then exposed to low intensity ultraviolet radiation until a coatable syrup copolymer was prepared, after which an additional 0.8 g (0.16 phr) of the photoinitiator was added.
The pre-adhesive polymer syrup was blended with various concentrations of the aziridine crosslinking agent and glycidyl methacrylate as shown in Table 1. The concentrations in Table 1 are based on the weight percent of pre-adhesive polymer syrup. The formulations were then coated on Mitsubishi Hostaphan™ primed polyester film at a 2-mil (˜50 micrometers) thickness for the syrup pre-adhesive formulations and cured at 500 mJ/cm2.
For comparative purposes, control examples using no crosslinking agent (Example C1), or using isooctyl aziridine (using 1.0 and 2.0 phr in Examples C2 and C3) or glycidyl methacrylate (using 0.2 phr in Example C4) as the crosslinking agents were also prepared and tested. Peel adhesion and shear strength were measured for tapes prepared from these adhesive as described in the test methods above and the data are shown in Table 1.
As can be seen by examination of the data in Table 1, functionalization of the IOA/AA polymer with either IO-Az or GMA alone (Examples C1-C4) does not provide excellent shear at both room temperature and 70� C., but functionalization of the polymer with both IO-Az and GMA (Examples 1-4) provides excellent shear properties while maintaining good peel characteristics.
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High5 Drink Bottle - 750ml
High5 Drink Bottle - 750mlKeeping hydrated whilst cycling is vital, the High5 Drink Bottle provides you with a 750ml professional quality bottle which is perfect to take with you on your journey. Also add or create your favourite sports drink using the measuring guide for specific quantities for maximum performance.
High5 Drink Bottle - 750ml Extra Info
- Professional quality drinks bottle
- Fast flow pull nipple for quick intake
- Created from food grade plastic
- Size: 750ml
- Colour: Clear
How can I get it?
Click & Collect
Delivery available
3 for the price of 2 on Cycle Accessories*
Mix & match and get the cheapest item free*
Must end Sunday 31st May
*excludes bike racks, cycle carriers, wearable tech, cycle computers & GPS, action & helmet cameras, discount applied in basket

subset: commoncrawl


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Private Tour: Giza Pyramids and Sphinx
Read what other Viator.com travelers think about the Private Tour: Giza Pyramids and Sphinx. What they loved, what they liked and what they think could be improved, it's all here to help you make the most of your next trip.
Click here for tour details, schedule and pricing
Julie T
The Pyramids and Sphinx were amazing. Our guide was very nice and knowledgeable. It was a private tour, which was great because we could go at our own pace.
Raymond P
They speak for themselves! Awesome! Timely comments, facts and history related by the guide made them all the more enjoyable.
I had a fantastic trip, and a very professional guide. A must for anyone going to Egypt!
Kieran B
United Kingdom
Friendly informative tour guide! A great tour and a brilliant experience!
Robert B
United Kingdom
Very good.
Angela H
United Kingdom
I had an excellent tour. My tour guide was very knowledgeable and friendly. She really seemed to enjoy her job. She was happy to take as long as I wanted at each stop and gave me the choice of shopping activities after we had seen the pyramids and sphinx. The perfume and oils shop was the most interesting and very Egyptian.
Victoria R
Excellent tour if you are just looking for the opportunity of seeing these major tourist attractions in a short space of time. Our guide spoke excellent English and was very knowledgeable and using our camera took some great photos of us in front of these awesome historical monuments. Highly recommended!
Robin G
Exceptional service. The tour was great and our guide was a wonderfully knowledgeable Egyptologist. She answered all our questions and was delightful with the kids. From meeting us at the gate to delivering us to the train it was a terrific experience. Thank you Viator!!!!
Our English speaking guide was great.
Kaspar F
We had a great guide, with a lot of good information. Pick up and drop off at the hotel, very good service.
Steve D
The guide we had was passionate and well informed about all aspects of the tour. The Papyrus and Perfume showrooms were average, but the drive between these gave us a view of Cairo we would not have normally seen.
Ellen H
Our guide was amazing and extremely knowledgeable!
Vas A
Great experience! Our Egyptian Guide was a very sympathetic lady who explained all about the Pyramids, and not only. Overall, a memorable tour!
Ruben J
South Africa
On time, friendly professional service.
Peggy O
Our guide was great, she helped us haggle for a camel ride, told us what we should and should not do and helped us do some shopping. She was knowledgeable and had a great sense of humor.
Cynthia S
The Egyptologist was fantastic he knew so much about ancient Egyptian culture and he answered all of our questions. He never rushed us and gave us plenty of time to explore on our own. He took the best pictures of us in front of the Pyramids. He also made sure we were not taken advantage of during our camel rides which he also helped arrange. A private tour and driver is the only way visit these amazing sites.It was truly an experience of a lifetime.
Every aspect of the tour was absolutely first class. Our contact for the week, was very helpful and friendly and arrived on time. Our minibus was clean, air conditioned and very well driven. Our tour guide, unfortunately I have forgotten her name, was really nice and treated us more like friends then tourists. She told the history of Egypt in a most interesting way and knew her stuff. We felt very good about everything. The pyramids and the sphinx were even better than we had expected. Splendid.
United Kingdom
The guide was absolutely amazing - her historical knowledge was great and she answered all of our questions. She was such a lovely person that nothing was too much hassle for her. She helped us negotiate good prices for camel rides and gifts. We had a fantastic day which we will remember for a very long time.
Amy A
The crew were AWESOME. A guide is needed to reach the pyramids, no taxis allowed. Our tour guide did great. Wish I could have had a bit more information from the tour guide, but one can not have it all. Also should use this company for transfer 'to' and 'from' airport, because inbound outbound flights are VERY confusing and taxis do not always know your hotel even though they say they do.
United Kingdom
The pick up on this trip was on time and the guide was very knowledgeable. We wondered before the trip how easy it is to get inside the pyramids it was surprisingly easy. There are plentiful tickets on sale for the second pyramid 25 Egyptian pounds, however it was more difficult to get tickets to the Great Pyramid as only 150 tickets are sold in the morning and 150 tickets for 1pm more expensive. We were told that advanced tickets were not available. These two pyramids are very similar in size. The photo opportunities are amazing, you can get close to the pyramids and the Sphinx. There are a number of locals that will try and get money for items or for taking photos however we did not find that a problem. We found it very hot inside the pyramid. It is made worse by having to crouch down and walk in a four, five foot high passage ways down and then up. We were only in the second pyramid for around 10 minutes and needed to drink lots of water after, take plenty of water with you. The only downside for us was the guide seemed to rush things along a bit and we needed to make efforts to slow things down and make a point of walking off on our own so we would have more time for photos etc. Also they do seem to try to tag on additional parts to the trip that involve buying items from factories, don't feel compelled to do these, just politely decline if they do not suit. Overall this is an awesome trip, a must do.
Stephen R
United Kingdom
This trip left me feeling in awe of the wonderous work put into the pyramids and also how the Kings son must have been a very intelligent man to have arranged the second pyramid in such a way that he looks more impressive than his father. An excellent trip well worth doing and would recommend this for anyone interested in ancient history.
David P
Excellent service, well worth the money.
Everything was perfect.
South Africa
Always on time - thanks! We will book through your company again!
James K
We had a great experience. We were picked up at our hotel on time. Our guide did an excellent job of explaining the various parts of the city as we drove to Giza. The pyramids were larger than expected, while the Sphinx was a bit smaller, but both were truly awesome. The driver was excellent and got us through the traffic in record time. He also managed to get us right up to nearest spot so we didn't walk much. The car was a clean, late-model and air conditioned vehicle. I would recommend the tour to all tourists, from any part of the world, as this is truly one of the 'Wonders of the World'.


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This updated and streamlined new edition of the pioneering Hyatt and French Community Association Law coursebook is an ideal vehicle for introducing students to this increasingly important subject. From housing just 2 million Americans in 1970, common interest communities had grown to house 57 million, or 19% of the American population, by 2006. Community associations, which manage these communities, bear similarities to not-for-profit corporations, municipal governments, and trusts, but are different. The evolving body of community association law draws from all these fields but reflects the unique character and needs of common interest communities. Reflecting the expertise of its authors, the book combines academic rigor and practical knowledge. Primary materials include important cases, statutes (including proposed revisions to UCIOA), the Restatement (Third) of Property, Servitudes, and references to the growing body of literature on gated communities, co-housing developments, private governments, and other property regimes used to avoid the tragedy of the commons in groups that hold common property.
Table of Cases
Ch. 1 Introduction to Common Interest Communities and Community Associations 3
Ch. 2 Creating Common Interest Communities 19
Ch. 3 Functions & Powers of a Common Interest Community 55
Ch. 4 Constitutional & Public Policy Constraints on Common Interest Communities 113
Ch. 5 Association Governance 171
Ch. 6 Financing the Community 271
Ch. 7 Design Standards and Control 345
Ch. 8 Enforcement in the Community 391
Ch. 9 Amending the Governing Documents 455
Ch. 10 Liability of Associations, Boards and Members 505
Ch. 11 Declarant Control of Association and Transition 607
Index 641


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RTS (C&C Generals C&C Generals::ZeroHour) // GTA::San Andreas // Car Race gaming (Need for Speed series) // enthousiast
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BMW Automaker to Invest $1 Billion in Mexico Factory
By Associated Press | July 3, 2014
Last Updated: July 3, 2014 4:11 pm
MEXICO CITY—Germany's BMW says it will invest $1 billion to build a new luxury car factory in northern Mexico.
BMW board member Harald Kruger says the plant in the northern state of San Luis Potosi and will have the capacity to make 150,000 cars per year.
Kruger made the announcement Thursday in Mexico City, accompanied by President Enrique Pena Nieto.
He says BMW has 28 factories in 13 countries.
The announcement comes a week after automakers Daimler and Renault-Nissan said they would invest $1.6 billion in a factory to make premium compact cars in Mexico.
Mexico has become a preferred spot for car makers because of low wages, its proximity to the United States and free trade agreements with 45 countries.


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Many long-term survivors of Inflammatory Breast Cancer (IBC) have contributed their inspiring stories to this website to provide hope to other victims of this deadly type of breast cancer.
The content on this site is for informational purposes only. It is not a substitute for professional medical advice. Do not use this information to diagnose or treat a health problem or disease without consulting with a qualified healthcare provider. Please consult your healthcare provider with any questions or concerns you may have regarding your condition. Use of this online service is subject to the disclaimer and the terms and conditions.
Copyright 2000-2015 © Cancer Survivors Network


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Samsung's first 4G LTE phone. This high-end phone sports a large 4.3-inch touch screen, 8-megapixel camera with HD video capture, video calling via front-facing camera, and 1 GHz Hummingbird processor. Other features include mobile Wi-Fi hotspot, HDMI TV-out, DLNA wireless media streaming, 3.5mm audio jack, and a memory card slot. With the support of lighting fast Android 2.2 platform, you can now enjoy all your favorite web content on the Samsung SCH Droid Charge phone. This Samsung smartphone supports the 4G LTE (Long Term Evolution) network, making it 10 times faster than the 3G networks. The 4.3-inch Super AMOLED Plus screen of this Samsung Verizon phone renders images with vibrant colors and stunning details. This Samsung smartphone, with ample multimedia features, gives options to keep you entertained all day long. Sporting a slim and sleek ergonomic design, this Samsung Verizon phone fits comfortably in your pocket.
Phone Specifications
Samsung Droid Charge
Samsung Droid Charge Android GPS 4G LTE PDA Phone Verizon
Only 0 left in stock--order soon.
30 day warranty
$124.99 New Available online


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While visting my sister in Astoria OR the walk along the river was always beautiful. Nikon D40, AF-S DX 18-70 Nikkor, f10, 1/250.
(2 votes)
River walk along Columbia River
By M Y Small Posted: May 13, 2014
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WRXtuners Member
Join Date: Apr 2008
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Struts and Srpings and Tophats
#1 Choice. Tokico D-Specs
#2 Choice KYB AGX
#3 Choice KYB GR-2
#1 gives an almost German ride quality with the ability to crank it up for track driving. #2 give you a good quality ride but there are 4 levels of adjustability vs the 32 for #1. #3 is not adjustable but are a good strut.
#1 Prodrive Springs. These are available through your local Cosworth Distributor (Suba, I believe). I've heard good things about RCE but I've never ridden in them so I'd go with the Prodrives
You don't need to do tophats but I've ridden in cars both with and without and I'd definitely spend the cash on them. Group N Tophats. Get them at Flatirons.
Chris is running Prodrive springs on AGX struts. I don't remember if he has tophats or not. My most favoritest strut/spring setup was D-Specs with Prodrive springs and Group N tophats. Budget setup would be GR-2's with Prodrive Springs on stock tophats.
These are your entry-level performance suspension packages.
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Tokyo, Japan
My Rating
We had a very good experience. We were always met by a representative and taken to where we wanted to go.Everyone was very pleasent
Tokyo, Japan
My Rating
Our experience was very good. Even though our flight was delayed we were met at the airport and taken to our .hotel
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Hockey News: Riding the Streak
Updated: March 21, 2007, 2:16 PM ETBy Darryl Dobbs | Special to ESPN.com
When a team is on a hot streak, it's always good to pick up several of the players for a week or two in your rotisserie league and ride the wave. When that team is also desperate and fighting for their playoff lives, this becomes an absolute no-brainer.
The Colorado Avalanche are riding an 8-0-1 wave and are now within striking distance of the Calgary Flames for the No. 8 spot in the Western Conference playoff picture. Anyone who is in second place in their fantasy leagues and needs a boost ...
Read full story
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8 Beautiful Baskets
Whether you're looking to corral laundry, store blankets, or have a picnic, these containers are sure to please.
West Elm Ikat Woven Collection—Small Storage Bin
Add some ethnic flair by using this basket for discarded newspapers or to contain lightweight throws beside the couch.
To buy: $39, westelm.com.


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Legal information is available in several languages on a variety of topics, including Housing, Family Law, Employment, Education, Consumer, Benefits, Health, Taxes, Veterans and Military, and Civil Rights. General court information is also offered, including fee waivers, small claims, and other court procedures.Maine Statutes
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Star Boxing's IBF# 2 rated welterweight, Delvin Rodriguez (24-2-2, 14KO) and his team left their camp today in the Catskill Mountains and are headed to the Mohegan Sun, where Rodriguez will take on South Africa's IBF #3 rated Isaac Hlatshwayo (28-1-1, 10KO) on Saturday night for the vacant IBF Welterweight Championship of the World. The card is being promoted by Joe DeGuardia's Star Boxing. Below are quotes from Rodriguez and his camp, as well as some photos from his last sparring session with middleweight Ossie Duran.
Delvin Rodriguez: I have had tremendous sparring and a tremendous training camp all together. I am as ready as I will ever be. This is the best work I have had in a long time, if not ever. I am very anxious and very excited..
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Should adults be taught like juniors?
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Join Date: Aug 2009
Location: Carolinas
Posts: 607
My thought would be to use the green ball exclusively until form is acceptable and points can be constructed. Since adults don't play on 36 or 60 foot courts, I wouldn't think the red or orange ball would be of much value. However, having said that, I'll do mini tennis with a foam ball sometimes for a good warm up. I see a lot of juniors that are hacking away in clinics and I wonder how or why they have graduated to the normal ball. Same for adults, but the flip side is that 3.0 tennis is alive and well. I realize that not every adult rec player can progress to 4.0 or 4.5, I just wonder what is the best method to get them to their maximum play ability in the shortest time?
Originally Posted by
Honestly, as I'm remaking my game, when in doubt, I pose the question, "what would a nationally top ranked U12 player do?"
He's obviously accomplishing more than me with a far weaker body, so he must be doing almost everything right.
Also, I think you're misinterpreting (or I am). The green ball is the standard ball. You mean "should they be using red and yellow balls until they are as good as these players?"
They should use them until they become solid. Being as good as those kids with an adult or adolescent body is quite a high level of play.
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The Group has set itself the aim of achieving +6% to +14% issue volume annual growth and over 10% growth in funds from operations per year.
In the framework of the strategy to "Conquer 2012" and "Invent 2016", the Group's Executive Committee, chaired by Jacques Stern , is being reorganized as follows:
Operational functions:
- Jean-Louis Claveau, Chief Operating Officer for Hispanic Latin America and North America
- Laurent Delmas, Chief Operating Officer for France
- Arnaud Erulin, Chief Operating Officer for Central Europe and Scandinavia
- Graziella Gavezotti, Chief Operating Officer for Southern Europe
- Oswaldo Melantonio Filho, Chief Operating Officer for Brazil
- Laurent Pellet, Chief Operating Officer for Asia-Pacific
- Bernard Rongvaux, Chief Operating Officer for Northern Europe, the Middle East and Africa
Support functions:
- Gilles Bonnin, Executive Vice President, Technology and Strategic Information Systems
- Gilles Coccoli, Executive Vice President, Strategy and Development
- Philippe Dufour, Executive Vice President for Alternative Investments
- Loïc Jenouvrier, Chief Financial Officer in charge of Legal Affairs
- Jeanne Renard, Executive Vice President, Human Resources
- Eliane Rouyer-Chevalier, Executive Vice President, Communications and Corporate Social Responsibility
- Gilles Bonnin , Executive Vice President in charge of Technology and Strategic Information Systems since 2011, is joining the Executive Committee. A digital transition pioneer, Edenred is therefore placing technology at the heart of its service quality and its ability to be different.
- Gilles Coccoli is joining the Executive Committee to take charge of the Strategy and Development department. The mission of this department is to support the development of new programs and services. Gilles Coccoli was previously Managing Director in charge of Edenred's authorization platform, PrePay Solutions. He will be replaced by Ray Brash , the former Deputy Managing Director of PrePay Solutions, who will report to Gilles Coccoli.
- Philippe Dufour , former Executive Vice President, Strategy and Development, is now Executive Vice President for Alternative Investments. In this capacity, he will coordinate an entity whose aim will be to accompany, through minority holdings, companies offering value-added services to Edenred's stakeholders (affiliates, beneficiaries, clients). This new initiative will supplement the internal approach to innovation and the external approach, which was recently initiated with the 15% investment in the Partech investment fund.
- Graziella Gavezotti, the former Chief Operating Officer of Edenred Italy, has taken on new responsibilities as the Chief Operating Officer for Southern Europe ( Spain, Greece, Italy, Portugal and Turkey). This region is strategically important for the Group, since it offers new opportunities for growth by developing new solutions.
- Laurent Pellet , the former Chief Operating Officer for Southern Europe, excluding Italy, is the new Chief Operating Officer of the Asia-Pacific zone ( China, South Korea, India, Singapore, Taiwan - with South Africa also included in this region), which is a source of high potential growth for Edenred, especially in terms of geographic expansion.
- Jeanne Renard, former Deputy Director reporting to the Chairman and Chief Executive Officer, has been appointed Executive Vice President for Human Resources. She remains in charge of the Group's in-house governance bodies.
- Employee benefits (Ticket Restaurant ® , Ticket Alimentación, Ticket CESU, Childcare Vouchers, etc.).
- The expense management process (Ticket Car, Ticket Clean Way, Ticket Frete, etc.).
- Incentive and rewards programs (Ticket Compliments, Ticket Kadéos, etc.).


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Implementation detailssection
As we reviewed in a previous blog with JSF 2 and RichFaces 4 you already have the Bean Validation support all the way to the browser with our client side validation. So you can effectively work with your server side object without any additional view level code related to validation.
This blog is going to review the last (but not least) validation feature which RichFaces 4 adds to JSF 2 . It's called Object Validation and provides a way to validate all your model Object fields considering even ones which were not used in the current view.
Why do you need that? The very first example which came to my mind as it appears frequently on various forums is dependent fields validation.
Password Validation Example
Let's check the password validation example:
<h:form> <rich:panel header="Change password" style="width:500px"> <h:panelGrid columns="3"> <h:outputText value="Enter new password:" /> <h:inputSecret value="#{userBean.password}" id="pass"/> <rich:message for="pass"/> <h:outputText value="Confirm the new password:" /> <h:inputSecret value="#{userBean.confirm}" id="conf"/> <rich:message for="conf"/> </h:panelGrid> <a4j:commandButton value="Store changes" action="#{userBean.storeNewPassword}" /> </rich:panel> </h:form>
And the simple managed bean source:
@ManagedBean @RequestScoped public class UserBean { @Size(min = 5, max = 15, message="Wrong size for password") private String password; @Size(min = 5, max = 15, message="Wrong size for confirmation") private String confirm; //... public void storeNewPassword(){ FacesContext.getCurrentInstance().addMessage("", new FacesMessage(FacesMessage.SEVERITY_INFO, "Succesfully changed!", "Succesfully changed!")); } //Getters and setters }
So we solved half of the problem:
We are seeing the error messages if the password fields do not satisfy the validation rules given. Nothing is checking if passwords are the same though, just that they are independently valid. So what is the easiest way to validate if the fields are equals? We could perform that in action but that is quite late in the JSF lifecycle for validation. We could use some solutions using f:attribute in order to pass dependent field id to the other input and find the component by that id in custom validate method. There are also some other ways which are pretty easy to find across different knowledge-bases'. But most of them are either invoked in an improper phase (like action at INVOKE_APPLICATION) or has possible maintenance problems(f:attribute solution requires us to be patient with id's changes in view as validation depends on them).
RichFaces 4 Object Validation for cross-field validation
This is where RichFaces 4 Object Validation feature come in play! Here is what we propose to use:
<h:form> <rich:graphValidator value="#{userBean}" id="gv"> <rich:panel header="Change password" style="width:500px"> <rich:messages globalOnly="true"/> <rich:messages for="gv"/> <h:panelGrid columns="3"> <h:outputText value="Enter new password:" /> <h:inputSecret value="#{userBean.password}" id="pass"/> <rich:message for="pass"/> <h:outputText value="Confirm the new password:" /> <h:inputSecret value="#{userBean.confirm}" id="conf"/> <rich:message for="conf"/> </h:panelGrid> <a4j:commandButton value="Store changes" action="#{userBean.storeNewPassword}" /> </rich:panel> </rich:graphValidator> </h:form>
And the Bean(Updated with implements Cloneable):
@ManagedBean @RequestScoped public class UserBean implements Cloneable{ @Size(min = 5, max = 15, message="Wrong size for password") private String password=""; @Size(min = 5, max = 15, message="Wrong size for confirmation") private String confirm=""; @AssertTrue(message = "Different passwords entered!") public boolean isPasswordsEquals() { return password.equals(confirm); } public void storeNewPassword(){ FacesContext.getCurrentInstance().addMessage(null, new FacesMessage(FacesMessage.SEVERITY_INFO, "Succesfully changed!", "Succesfully changed!")); }
So lets look through the sample details. rich:graphValidator tag should wrap the inputs bound to the object which we are interested in validating. The value attribute should be pointed to that bean name. Then at PROCESS_VALIDATION phase all the object fields will be validated according to constraints added. And in that particular case isPassWordEquals will be validated using AssertTrueValidator. That looks just like we expected!
Different passwords entered(but valid according to size):
Verification successful:
Implementation DetailsUPDATED(28.02) section below. Actually 3.3.x used the same way. Was written that it worked at model updates by mistake.
Just one question appears. Those who know the JSF life-cycle will ask immediately about how the bean could be validated before the model updates? Does RichFaces propose to use validation after process updates phase? No. We perform a clone() on your bean instance at validation phase and updating new instance with all the new values submitted(that's why we still need to wrap all the inputs related to rich:graphValidator). We then validate the cloned object firing validation messages if needed. Your model objects remains clean, lifecycle gets interrupted properly after Process Validations phase and messages encoded to client during Render Response.
NOTE: if cloneNotSupportedException thrown from the object – validation will be done at model updates. And that is the only exception to our architecture which really can't be workaround-ed.
Try it out!
Now having JSF 2 Bean Validation support standardized, RichFaces 4 Client Side Validation and Object Validation features we believe you will be able completely concentrate on your business tasks and will not spend time for any additional JSF development in the validation phase. Try our new features in RichFaces 4.0.0.M6 and let us know about any problems or questions appeared. That will help us greatly to provide those features stable and well documented prior to RichFaces 4 Final release!
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13 comments:
I like the @AssertTrue annotation and how it separates the validation from the action and doesn't require those extra JSF parameters (ie, FacesContext)
Does it create a deep clone of the UserBean? If not, I'm not sure I see the point since in the case of a sub property it will still ultimately 'dirty' the bean. If so, isn't it a potentially expensive operation?
My ignorance is going to shine here (and maybe this isn't the place to ask): What's wrong with doing some validation after updating the model? The user has to keep retrying until they get it right so the model will be correct, or they give up in which case the context dies anyways (if conversation) and the model goes away and no changes are applied (if entity in conversation). In cases the user alters, say a session or view scoped bean, would it be better to control if/how properties are updated manually through the action method instead of going through a cloning process (which might have one of the two issues mentioned above) before invoke application?
How to implement this pattern to CDI beans?
It works with CDI beans (I have just tested it). No special configuration :) You only have to change de annotations:
import javax.inject.Named; import javax.enterprise.context.RequestScoped; @Named @RequestScoped public class UserBean {
Thank you very much. What library implements bean validation? Weld-servlet?
You can go with HibernateValidation implementation. You will need validation-api-1.0.0.GA.jar (JSR-303) and hibernate-validator-4.1.0.Final.jar. It would be nice if you post your questions in the RF forun. Give it a try!
Weld-servlet is the library to enable CDI in Tomcat or Jetty container, it doesn´t have JSR-303 library.
Paul, sorry for the delay. Here is the comments to your question.
1) default clone() method doesn't make deep copies - it should be performed by developer.
2) having dirty values in scenario does the same thing: user creates temporary copy ( DTO ), updates it with new values and performs validation before persist() call. The only difference that richfaces creates temporary object and forget it on every request, so if user press 'back()' button, cancel conversation or performs some other action, data object doesn't keep dirty values.
First of all, this is a great feature. It also works in RichFaces 3.3.
Ilya, what I am struggling with:
Is there a way to display the message from AssertTrue (
Another example is a validation whether a value (email, username) already exists in the database. Implementing the same approach as above with AssertTrue (instead of writing a custom Hibernate validator) will display the message above / belove the fields. So how do I bind the message to the field (email or username).
Kind regards, Jernej
Hi everybody!
Im new to Richfaces, especially with Object Validation. So im trying to implement Object Validation in my project, just like Showcase dictates.
I have a problem with this: when I click the button
I have in my classpath the following libraries: richfaces-components-ui-4.2.2.Final.jar, javax.faces-2.1.7.jar, validation-api-1.0.0.GA.jar, hibernate-validator-4.2.0.Final.jar, hibernate-annotations-3.2.1.ga.jar. Im using IBM Integration Designer 7.5 built on Eclipse.
Any kind of help you can give me I would appreciate so much.
Thanks in advance!!! :)
Save Friends ..
there is some form of set the focu on <rich:autocomplete>
with "#{rich:element('id')}.focus();"
because I'm not getting
from already thank you very much
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Anderson was a Master Class winner at Le Monaco
The team from Goodwood Kartways kept its Eastern Canadian Karting Championship momentum rolling a week ago as the series hit Quebec for the first time this season.
Aug 12
May 29
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Sep 13
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Aug 06
Le Monaco de Trois-Rivieres
The Eastern Canadian Karting Championship made its return to Quebec over the weekend as teams and drivers headed to Le Monaco de Trois-Rivieres and the fabled grounds of Exhibition Place/GP3R.
Jul 22
Jul 12
Jul 06
IPK was on the Goodwood Kartways podium four times on Saturday
For the second straight event, IPK North America had a very strong showing in Eastern Canadian Karting Championship competition as it once again sent seven different drivers to the podium, this time in six different classes and in both two-cycle and four-cycle categories.
Jul 03
Jul 02
Goodwood Kartways report
The Eastern Canadian Karting Championship returned to action closing out the month of June with a doubleheader event at Goodwood Kartways.
Jun 13
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Jun 04
Ben Cooper finished a weekend sweep of DD2 with his second win on Sunday
The second race of the 2013 Eastern Canadian Karting Championship was held Sunday at Mosport International Karting and if not more, there was at least one thing consistent from a day earlier – weather that just couldn't decide what it wanted to be.
Jun 03
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For the winner of the DD2 class during the Monaco de Trois-Rivières!
It is with great pleasure that the organizing committee for the Monaco de Trois-Rivières, partnered with the GP3R (Grand Prix de Trois-Rivières) and Elitech Sprot Evasion, would like to announce that the winner of the final race in the ROTAX MAX DD2 category, part of the Eastern Canadian Karting Championship hold Sunday the August 4th, will have the privilege of racing in the Sportsman racing series which is presented as part of the GP3R, which will be held August 9-11, 2013.


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Latin America Topics
Democracy Now! stories, posts and pages that relate to Latin America
- On Thursday, armed men sabotaged an El Salvadoran nonprofit dedicated to finding children who went missing three decades ago during a time when the United States was backing Salvador's military government. The intruders broke into the Pro-Búsqueda Association for Missing Children, destroyed four of its offices, and set fire to its archives. They also stole computers, possibly containing sensitive information about children stolen by...November 15, 2013 | Story
- As Congress continues to shape an immigration reform bill that could provide a path to citizenship for some 11 million undocumented residents, we look at the overlooked plight of migrants from Central and South America who travel through Mexico en route to the United States. Many of them are fleeing violence and poverty in their countries only to face robberies, beatings and kidnappings by smugglers who hold them for ransom. Human rights...May 23, 2013 | Story
- Part two of our conversation with the celebrated Uruguayan writer Eduardo Galeano, author of the new book, "Children of the Days: A Calendar of Human History."May 08, 2013 | Web Exclusive
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- Millions are gathering in Caracas to mourn the late Venezuelan President Hugo Chávez on the day of his funeral. More than 30 world leaders are expected to attend today's ceremony as Venezuelans brave long lines to see Chávez lying in state. We go to Caracas to speak with Carol Delgado, Venezuelan consul general in New York, who has returned home for the funeral. Delgado responds to the torrent of U.S. corporate media criticism that has...March 08, 2013 | Story
Operation Condor Trial Tackles Coordinated Campaign by Latin American Dictatorships to Kill LeftistsA historic trial underway in Argentina is set to reveal new details about how Latin American countries coordinated with each other in the 1970s and '80s to eliminate political dissidents. The campaign known as "Operation Condor" involved military dictatorships in Argentina, Bolivia, Brazil, Chile, Paraguay, Peru and Uruguay. They worked together to track down, kidnap and kill people they labeled as terrorists: leftist activists,...March 07, 2013 | Story
- The new Spanish-language radio program "Radio Ambulante" gathers voices from around Latin America and the United States to showcase the untold human stories behind issues such as immigration and kidnappings. Using a network of journalists from around the Americas, the monthly program fills a gaping hole in the radio landscape for Spanish speakers. We're joined by Radio Ambulante executive producer Daniel Alarcón, the acclaimed...February 07, 2013 | Story
- Venezuela has postponed today's presidential inauguration as Hugo Chávez remains hospitalized in Cuba. The Venezuelan Supreme Court says Chávez is still president, but the opposition is calling for a caretaker government and new elections. We host a debate on Chávez's presidency and what is next for Venezuela with Michael Shifter, president of the Inter-American Dialogue and adjunct professor at Georgetown University, and Miguel...January 10, 2013 | Story
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