text:
The present invention provides radiation-curable ink compositions comprising pigment and a photohardenable composition; the photohardenable composition comprises a free radical addition polymerizable or crosslinkable compound and an ionic dye-reactive counter ion compound which is capable of absorbing actinic radiation and producing free radicals which initiate free radical polymerization or crosslinking of the polymerizable or crosslinkable compound.
1. A radiation-curable composition comprising a colorant, a free radical addition polymerizable or crosslinkable compound, and an ionic dye-reactive counter ion compound, said ionic dye-reactive counter ion compound being capable of absorbing actinic radiation and producing free radicals which initiate free radical polymerization or crosslinking of said polymerizable or crosslinkable compound.
2. The composition of claim 1 wherein prior to exposure, said ionic dye-reactive counter ion compound is a stable, non-transient compound.
3. The composition of claim 2 wherein following exposure of said ionic dye-reactive counter ion compound to light, an electron is transferred from said dye to said counter ion or from said counter ion to said dye and the rate of said electron transfer is greater than a diffusion controlled rate.
4. The composition of claim 3 wherein said ionic dye-reactive counter ion compound is represented by the formula ##STR37## where D+ is a cationic dye; and R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic, and saturated or unsaturated heterocyclic groups.
5. The composition of claim 4 wherein said cationic dye is a cyanine dye.
6. The composition of claim 1 wherein said compound is an anionic dye compound.
7. The composition of claim 6 wherein said anionic dye is selected from the group consisting of xanthene and oxonol dyes.
8. The composition of claim 1 wherein said polymerizable or crosslinkable compound is an ethylenically unsaturated compound.
9. The composition of claim 6 wherein said ionic dye-reactive counter ion compound is an anionic dye-iodonium ion complex or an anionic dye-pyryllium ion complex.
10. The composition of claim 9 wherein said dye is a xanthene dye.
11. A method of coating or printing comprising the steps of:
coating or printing on a substrate with a radiation-curable ink composition comprising a colorant, a free radical addition polymerizable or crosslinkable compound, and an ionic dye-reactive counter ion compound, said ionic dye-reactive counter ion compound being capable of absorbing actinic radiation and producing free radicals which initiate free radical polymerization or crosslinking of said polymerizable or crosslinkable compound; and
exposing said coated or printed substrate to actinic radiation.
12. The method of claim 11 wherein prior to exposure, said ionic dye-reactive counter ion compound is a stable, non-transient compound.
13. The method of claim 12 wherein following exposure of said ionic dye-reactive counter ion compound to radiation, an electron is transferred from said dye to said counter ion or from said counter ion to said dye and the rate of said electron transfer is greater than a diffusion controlled rate.
14. The method of claim 13 wherein said ionic dye-reactive counter ion compound is represented by the formula ##STR38## where D+ is a cationic dye; and R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic, and saturated or unsaturated heterocyclic groups.
15. The method of claim 14 wherein said cationic dye is a cyanine dye.
16. The method of claim 11 wherein said ionic dye-reactive counter ion compound is an anionic dye complex.
17. The method of claim 16 wherein said anionic dye is a xanthene dye.
18. The method of claim 11 wherein said polymerizable or crosslinkable compound is an ethylenically unsaturated compound.
19. The method of claim 16 wherein said ionic dye-reactive counter ion compound is an anionic dye-iodonium ion compound or an anionic dye-pyryllium ion compound.
20. The method of claim 19 wherein said dye is a xanthene dye.
The present invention relates to novel radiation-curable ink and coating compositions, and more particularly, to radiation-curable ink and coating compositions containing an ionic dye-reactive counter ion complex as a photoinitiator.
Radiation-curable ink compositions are widely used. Compared to solvent-based ink compositions, radiation-curable ink compositions are advantageous because toxicological and environmental concerns are avoided. U.S. Pat. Nos. 3,661,614; 4,003,868; and 4,215,167, teach ultraviolet-curable ink compositions. These compositions comprise a polymerizable material such as a monomer, an initiator system, and a pigment or a dye.
While the most common examples of radiation curable inks are sensitive to ultraviolet radiation or blue light, compositions which are sensitive to longer wavelengths of visible light such as longer wavelength blue, red or green light would be desirable. Ultraviolet-sensitive photoinitiators often are suitable for cyan and magenta ink compositions because cyan and magenta pigments absorb little near ultraviolet or blue light. However, ultraviolet-sensitive photoinitiators are generally undesirable for yellow compositions because yellow pigments and dyes absorb strongly in the near ultraviolet-blue region. As such, yellow ultraviolet-curable ink compositions cure more slowly or require higher intensity radiation than cyan or magenta ultraviolet-curable ink compositions. Inks with a large yellow components, such as brown, black, green, or red also cure more slowly.
In addition to inks, there are other applications in which radiation curable compositions containing a colorant are useful. In particular, in coating paper, paperboard, and other sheet materials, such compositions are useful. They are also useful in printing simulated wood coatings.
The present invention provides a radiation-curable ink and coating composition comprising a pigment or a dye and a photohardenable composition. The photohardenable composition comprises a free radical addition polymerizable or crosslinkable compound and an ionic dye-reactive counter ion compound.
It has been found that ionic dye-reactive counter ion compounds, such as cationic dye-borate anion compounds, are useful photoinitiators of free radical addition reactions. Such compounds consist of a visible light absorber (the ionic dye) ionically bonded to a reactive counter ion. The counter ion is reactive in the sense that upon excitation of the dye, the counter ion donates an electron to or accepts an electron from the excited dye. This electron transfer process generates radicals capable of initiating polymerization of a monomer.
The mechanism whereby the compounds absorb energy and generate free radicals is not entirely clear. It is believed that upon exposure to actinic radiation, the dye ion is excited to a singlet state in which it accepts an electron from or donates an electron to the counter ion. For a cationic dye-borate anion compound, this can be illustrated by the following equation:
The lifetime of the dye singlet state is extremely short by comparison to the lifetime of the triplet state. The quenching rate constants which have been observed suggest that the ionic compounds experience a very efficient electron transfer via the singlet state. In solution in the polymerizable compound, tight ionic pairing of the counter ion and the dye is believed to provide favorable spacial distribution promoting electron transfer to such an extent that the transfer occurs even though the lifetime of the singlet state is very short. Of course, this does not mean that electron transfer is restricted to the singlet state. Ionic dyes which have significant populations of triplet state may undergo electron transfer through the singlet state, triplet state, or both singlet and triplet states.
Upon transfer of the electron, a radical is formed. Many of the ionic compounds used as initiators in the present invention do not appear to exhibit back electron transfer. It is believed that following electron transfer, the dye and counter ion become disassociated such that back electron transfer does not occur.
The ionic compounds used in the present invention are different than the collision generated species encountered in other photosensitive systems such as collision complexes which yield encounter complexes, exciplexes and/or contact ion pairs. See for example, Kavarnos et al., "Photosensitization by Reversible Electron Transfer", Chem. Rev. 401(1986).
In accordance with the present invention, the ionic dye and the counter ion are present in the photopolymerizable composition as a stable, non-transient compound, and not as a dissociated ion pair. Formation of the compound is not dependent upon diffusion and collision. As distinguished from photographic materials and compositions containing collision dependent complexes, essentially all of the sensitizing dye present in the photosensitive materials of the present invention prior to exposure is ionically bonded to the counter ion.
The ionic compounds used as initiators in the present invention can also be characterized in that they are soluble in nonpolar solvents such as trimethylolpropane triacrylate (TMPTA) and the like. They are soluble in an amount of at least about 0.1%, and preferably, at least about 0.3% by weight. While these amounts are not large, they are substantial considering the normally lower solubility of ionic materials in polar solvents. While the compounds are soluble, the dye and the counter ion do not dissociate in solution. They remain ionically bonded to each other.
In dye-sensitized photopolymerizable compositions, visible light is absorbed by a dye having a comparable absorption band, the dye is raised to its excited electronic state, the lifetime of which may be 10-9 to 10-3 second, depending upon the nature (singlet or triplet) of the excited state. During this time, absorbed energy in the form of an electron must be transferred to or from the dye molecule to produce the free radical. In prior initiator systems, this transfer is diffusion controlled. The excited dye must interact (collide) with another molecule in the composition which quenches the dye and generates a free radical. In the present invention, the transfer is not diffusion (collision) controlled. Electron transfer occurs at greater than diffusion controlled rates. In terms of Stern-Volmer kinetics, this means the quenching constant (Kq) of the excited dye is greater than 1010, and more particularly, greater than 1012. At these rates, electron transfer can occur through the singlet state.
As mentioned earlier, there is a tendency for yellow pigments and dyes to absorb strongly in the near ultraviolet-blue region. The present invention provides radiation-curable compositions which are sensitive at longer wavelengths in which the yellow pigment or dye does not absorb. The compositions of the present invention can contain any color pigment or dye including white, black, yellow, magenta, or cyan pigments or dyes but they are particularly useful as yellow compositions.
One of the particular advantages of using ionic dye-reactive counter ion compounds as initiators is the ability to select from a wide variety of dyes which absorb at substantially different wavelengths. The absorption characteristics of the compound are principally determined by the dye. Thus, by selecting a dye which absorbs at 400 nm or greater, the sensitivity of the compositions can be extended well into the visible range.
In accordance with the present invention, a radiation-curable ink or coating composition comprising a colorant, a free radical addition polymerizable or crosslinkable compound and an ionic dye-reactive counter ion compound is provided. The ionic dye-reactive counter ion compound is capable of absorbing actinic radiation and producing free radicals which initiate free radical polymerization or crosslinking of the polymerizable or crosslinkable compound.
In accordance with more particular embodiments of the invention, the ionic compound is a cationic dye-borate anion compound, and still more particularly, a cyanine dye-borate anion compound or an anionic dye compound such as ionic compounds of xanthene dyes with iodonium or pyryllium ions.
Another embodiment of the present invention resides in a method of coating or printing wherein a radiation-curable composition is coated or printed on a substrate and exposed to actinic radiation.
Other objects and advantages of the present invention will become apparent from the following description and appended claims.
The radiation-curable compositions of the present invention contain a colorant and a photohardenable composition wherein the photohardenable composition contains a free radical addition polymerizable or crosslinkable compound and an ionic dye-reactive counter ion compound.
Cationic dye-borate anion compounds are known in the art. Their preparation is described in U.S. Pat. Nos. 3,567,453; 4,307,182; 4,343,891; 4,447,521; and 4,450,227. The compounds used in the present invention can be represented by the general formula (I): ##STR1## where D+ is a cationic dye; and R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic, and saturated or unsaturated heterocyclic groups.
Useful dyes form photoreducible but dark stable complexes with borate anions and can be cationic methine, polymethine, triarylmethane, indoline, thiazine, xanthene, oxazine, and acridine dyes. More specifically, the dyes may be cationic cyanine, carbocyanine, hemicyanine, rhodamine, and azomethine dyes. In addition to being cationic, the dyes should not contain groups which would neutralize or desensitize the complex or render the complex poorly dark stable. Examples of groups which generally should not be present in the dye are acid groups such as free carboxylic or sulphonic acid groups.
Specific examples of useful cationic dyes are Methylene Blue, Safranine 0, Malachite Green, cyanine dyes of the general formula (II), and rhodamine dyes of the formula (III): ##STR2## n=0, 1, 2, 3, R=alkyl
Y=CH═CH, N--CH3, C(CH3)2, O, S, Se ##STR3## R', R=alkyl, aryl, and any combination thereof.
While they have not been tested, the cationic cyanine dyes disclosed in U.S. Pat. No. 3,495,987 should be useful in the present invention.
The borate anion is designed such that the borate radical generated upon exposure to light and after electron transfer to the dye (Eq. 1) readily dissociates with the formation of a radical as follows:
BR4.sup.. →BR3 +R.sup.. (Eq. 2)
For example, particularly preferred anions are 10 triphenylbutylborate and trianisylbutylborate anions because they readily dissociate to triphenylborane or trianisylborane and a butyl radical. On the other hand, tetrabutylborate anion does not work well presumably because the tetrabutylborate radical is not stable and it readily accepts an electron back from the dye in a back electron transfer and does not dissociate efficiently. Likewise, tetraphenylborate anion is very poor because the phenyl radical is not easily formed.
Preferably, at least one but not more than three of R1, R2, R3, and R4 is an alkyl group. Each of R1, R2, R3, and R4 can contain up to 20 carbon atoms, and they typically contain 1 to 7 carbon atoms. More preferably, R1 -R4 are a combination of alkyl group(s) and aryl group(s) or aralkyl group(s), and still more preferably, a combination of three aryl groups and one alkyl group.
Representative examples of alkyl groups represented by R1 -R4 are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, stearyl, etc. The alkyl groups may be substituted, for example, by one or more halogen, cyano, acyloxy, acyl, alkoxy, or hydroxy groups.
Representative examples of aryl groups represented by R1 -R4 include phenyl, naphthyl, and substituted aryl groups such as anisyl. Alkaryl groups include methylphenyl, dimethylphenyl, etc. Representative examples of aralkyl groups represented by R1 -R4 groups include benzyl. Representative alicyclic groups include cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of an alkynyl group are propynyl and ethynyl, and examples of alkenyl groups include a vinyl group.
As a general rule, useful ionic dye compounds must be identified empirically; however, potentially useful dye and counter ion combinations can be identified by reference to the Weller equation (Rehm, et al., Isr. J. Chem. 8, 259 (1970), which can be simplified as follows.
ΔG=Eox -Ered -Eh (Eq. 3)
where ΔG is the change in the Gibbs free energy, Eox is the oxidation potential of the borate anion BR4 -, Ered is the reduction potential of the cationic dye, and Ehν is the energy of light used to excite the dye. Useful compounds will have a negative free energy change. Similarly, the difference between the reduction potential of the dye and the oxidation potential of the borate must be negative for the compounds to be dark stable, i.e., Eox -Ered >O.
As indicated, Eq. 2 is a simplification and it does not absolutely predict whether a compound will be useful in the present invention or not. A number of other factors will influence this determination. One such factor is the effect of the monomer on the compound. Another factor is the radial distance between the ions. It is also known that if the Weller equation produces too negative a value, deviations from the equation are possible. Furthermore, the Weller equation only predicts electron transfer, and does not predict whether a particular compound is an efficient initiator of polymerization. The equation is a useful first approximation.
Specific examples of cationic dye-borate anion compounds useful in the present invention are shown in the following table with their λ max.
TABLE__________________________________________________________________________Compound No. Structure λ max__________________________________________________________________________ (TMPTA) ##STR4## 552 nm ##STR5## 568 nm ##STR6## 492 nm ##STR7## 428 nm ##STR8## 658 nm ##STR9## 528 nm__________________________________________________________________________ ##STR10## 450 nm__________________________________________________________________________No. R' Ar__________________________________________________________________________7A n-butyl phenyl7B n-hexyl phenyl7C n-butyl anisyl__________________________________________________________________________ ##STR11## 550 nm__________________________________________________________________________No. R' R Ar__________________________________________________________________________8A methyl n-butyl phenyl8B methyl n-hexyl phenyl8C n-butyl n-butyl phenyl8D n-butyl n-hexyl phenyl8E n-heptyl n-butyl phenyl8F n-heptyl n-hexyl phenyl8G ethyl n-butyl phenyl__________________________________________________________________________ ##STR12## 570 nm System ##STR13##10. ##STR14## 590 nm System ##STR15##__________________________________________________________________________ ##STR16## 640 nm__________________________________________________________________________No. R R' Ar__________________________________________________________________________11A methyl n-butyl phenyl11B methyl n-hexyl phenyl11C n-butyl n-butyl phenyl11D n-butyl n-hexyl phenyl11E n-pentyl n-butyl phenyl11F n-pentyl n-hexyl phenyl11G n-heptyl n-butyl phenyl11H n-heptyl n-hexyl phenyl11I methyl n-butyl anisyl__________________________________________________________________________ ##STR17## 740 nm System ##STR18##__________________________________________________________________________
The cationic dye-borate anion compounds can be prepared by reacting a borate salt with a dye in a counterion exchange in a known manner. See Hishiki, Y., Repts. Sci. Research Inst. 29, 72 (1953). Useful borate salts are sodium salts such as sodium tetraphenyl- borate, sodium triphenylbutylborate, sodium trianisylbutylborate, and ammonium salts such as tetraethylammonium tetraphenylborate.
Anionic dye compounds are also useful in the present invention. Anionic dye-iodonium ion compounds of the formula (IV):
[R5 --I--R.sup.≢ ]n D-n (IV)
where D- is an anionic dye and R5 and R6 are independently selected from the group consisting of aromatic nucleii such as phenyl or naphthyl and n is 1 or 2; and anionic dye-pyryllium compounds of the formula (V): ##STR19## where D- and n are as defined above are typical examples of anionic dye complexes.
Representative examples of anionic dyes include xanthene and oxonol dyes. For example, Rose Bengal, eosin, erythrosin, and fluorescein dyes are useful. In addition to iodonium and pyryllium ions, other compounds of anionic dyes and sulfonium and phosphonium cations are potentially useful.
As in the case of the cationic dye compoudns useful dye-cation combinations can be identified through the Weller equation as having a negative free energy.
Selected examples of anionic dye compounds are shown in Table 2 (λmax. ca. 570 nm in TMPTA). In Table 2, the symbol φ is used for a phenyl group and the structure ##STR20## is used for ##STR21##
TABLE 2______________________________________ (φ2 I+)1 ##STR22## ##STR23## ##STR24## ##STR25## ##STR26## ##STR27## ##STR28## ##STR29## ##STR30## φ2 I+ ##STR31## [φ3 +PCH 2 φ]2 ##STR32## φ3 +PCH 2 φ ##STR33## CH3 +SO 2 ##STR34## ##STR35## ##STR36## φ2 I+______________________________________
The most typical example of a free radical addition polymerizable or crosslinkable compound useful in the present invention is an ethylenically unsaturated compound, and more specifically, a polyethylenically unsaturated compound. These compounds include both monomers having one or more ethylenically unsaturated groups, such as vinyl or allyl groups, and polymers having terminal or pendant ethylenic unsaturation. Such compounds are well known in the art and include acrylic and methacrylic esters of polyhydric alcohols such as trimethylolpropane, pentaerythritol, and the like; and acrylate or methacrylate terminated epoxy resins, acrylate or methacrylate terminated polyesters, etc. Representative examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylol propane triacrylate (TMPTA), pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hydroxypentacrylate (DPHPA), hexanediol-1,6-dimethacrylate, and diethyleneglycol dimethacrylate. Another free radical addition polymerizable material is the reaction product of epoxidized soy bean oil and acrylic or methacrylic acid as described in U.S. Pat. No. 4,215,167 and the urethane and amine derivatives described therein.
The ionic dye compound is usually used in an amount up to about 1% by weight based on the weight of the photopolymerizable or crosslinkable species in the photohardenable composition. More typically, the compound is used in an amount of about 0.2% to 0.5% by weight.
While the compound can be used alone as the initiator, curing speeds tend to be quite low and oxygen inhibition is observed. It has been found that it is preferable to use the compound in combination with an autoxidizer. An autoxidizer is a compound which is capable of consuming oxygen in a free radical chain process. Alternatively, the composition can be cured in an oxygen-free environment.
Examples of useful autoxidizers are N,N-dialkylanilines. Examples of preferred N,N-dialkylanilines are dialkylanilines substituted in one or more of the ortho-, meta-, or para- position by the following groups: methyl, ethyl, isopropyl, t-butyl, 3,4-tetramethylene, phenyl, trifluoromethyl, acetyl, ethoxycarbonyl, carboxy, carboxylate, trimethylsilymethyl, trimethylsilyl, triethylsilyl, trimethylgermanyl, triethylgermanyl, trimethylstannyl, triethylstannyl, n-butoxy, n-pentyloxy, phenoxy, hydroxy, acetyl-oxy, methylthio, ethylthio, isopropylthio, thio-(mercapto-), acetylthio, fluoro, chloro, bromo, and iodo.
Representative examples of N,N-dialkylanilines useful in the present invention are 4-cyano-N,N-dimethylaniline; 4-acetyl-N,N-dimethylaniline; 4-bromo-N, N-dimethylaniline; ethyl 4-(N,N-dimethylamino) benzoate; 3-chloro-N,N-dimethylaniline; 4-chloro-N,N-dimethylaniline; 3-ethoxy-N,N-dimethylaniline; 4-fluoro-N,N-dimethylaniline; 4-methyl-N,N-dimethylaniline; 4-ethoxy-N,N-dimethylaniline; N,N-dimethylthioanicidine; 4-amino-N,N-dimethylaniline; 3-hydroxy-N,N-dimethylaniline; N,N,N',N'-tetramethyl-1,4-dianiline; 4-acetamido-N,N-dimethylaniline, etc.
Preferred N,N-dialkylanilines are substituted with an alkyl group in the ortho-position and include 2,6-diisopropyl-N,N-dimethylaniline; 2,6-diethyl-N,N-dimethylaniline; N,N,2,4,6-pentamethylaniline (PMA); and p-t-butyl-N,N-dimethylaniline.
The autoxidizers are preferably used in the present invention in concentrations of about 4-5% by weight.
Synthesis Examples 1 and 2 respectively illustrate the preparation of borates and dye-borate compounds.
Dissolve triphenylborane in 150 ml dry benzene (lM) under nitrogen atmosphere. Place flask in a cool water bath and, while stirring, add n-BuLi, (1.1 eg.) via syringe. A white precipitate soon formed after addition was started. Stirring is continued about 45-60 min. Dilute with 100 ml hexane and filter, washing with hexane. This resultant Li salt is slightly air unstable. Dissolve the white powder in about 200 ml distilled water and, with vigorous stirring, add aqueous solution of tetramethyl ammonium chloride (1.2 eg. of theoretical in 200 ml). A thick white precipitate forms. Stir this aqueous mixture about 30 min. at room temperature, then filter. Wash collected white solid with distilled water.
As an alternative synthesis, to a 1.0M solution of 2.0 equivalents of 1-butene in dry, oxygen-free dichloromethane, under inert atomosphere, was added slowly dropwise with stirring, 1.0 equivalents of a 1.0M solution of dibromethane-methylsulfide complex in dichloromethane. The reaction mixture stirred at reflux for 36 hours and the dichloromethane and excess 1-butene were removed by simple distillation. Vacuum distillation of the residue afforded 0.95 equivalents of a colorless mobile oil (Bp 66-7 0.35 mm Hg, "BNMR;bs (4.83PPM). Under inert atmosphere, this oil was dissolved in dry, oxygen-free tetrahydrofuran to give a 1.0M solution and 3.0 equivalents of a 2.0M solution of phenylmagnesium chloride in tetrahydrofuran were added dropwise with stirring. After stirring 16 hours, the resultant solution was added slowly with vigorous stirring to 2 equivalents of tetramethylammonium chloride, as a 0.2 M solution, in water. The resulting white flocculate solid was filtered and dried to afford a near quantitative amount of the desired product Mp 250�-2� C., " BNMR;bs (-3.70PPM).
Sonicate a suspension of a borate salt (1 g/10 ml) in MeOH, to make a very fine suspension. Protect flask from light by wrapping with aluminum foil then add 1 equivalent of dye. Stir this solution with low heat on a hot plate for about 30 min. Let cool to room temperature then dilute with 5-10 volumes of ice water. Filter the resultant solid and wash with water until washings are colorless. Suction filter to dryness. Completely dry initiator compound by low heat (about 50� C.) in a vacuum drying oven. Initiator is usually formed quantitatively. Analysis by H-NMR indicates 1:1 compound formation typically greater than 90%.
Conventional colorants can be used in conventional amounts in the radiation-curable ink compositions of the present invention. Suitable colorants include dyes and pigments such as carbon black, zinc oxide, titanium dioxide, benzidine yellow, hansa yellow, naphthol yellow lake, cadmium orange, cadmium yellow, chrome yellow, Prussian blue, bronze blue, chrome green, peacock blue lake, milori blue, ultramarine blue, red lake C, para red, toluidine red, sodium lithol red, barium lithol red, lithol rubine, molybdated scarlet chrome, ferric oxide, and aluminum hydrate. The colorant is used in amounts of about 5 to 80% by weight of the light-curable ink composition depending on the application.
It should be understood that the ionic dye-reactive counter ion compound selected will depend upon the colorant used. In other words, an ionic dye-reactive counter ion compound is selected which absorbs within a certain visible light wavelength region in which the particular colorant chosen preferably absorbs little, if any, visible light. Since the ionic dye compound absorbs at greater than 400 nm, it is colored, but the compound tends to be present in small amounts and it usually does not detract from the color of the colorant. There are applications, however, where the color of the ionic dye-reactive counter ion may be undesirable, for example, where the coating composition is white. In this case, it is desirable to select a photobleachable ionic dye compound. These ionic dye compounds are initially colored but are bleached upon exposure to radiation.
Known modifiers can be incorporated into the radiation-curable compositions of the present invention. Such modifiers include plasticizers; wetting agents for the pigment such as dichloromethylstearate and other chlorinated fatty acids; and leveling agents such as lanolin, paraffin waxes, and natural waxes such as cerise wax and carbauba wax. Such modifiers are generally used in amounts of about 1 to 3% by weight of the light-curable compositions. In order to improve the cure efficiency, a thiol could be added to the light-curable ink composition.
A three roll mill, a sand mill, a ball mill, a colloid mill, etc. may be used to mix the compositions. It should be understood that after preparation of the visible light-curable compositions of the present invention, the compositions are stored in light-tight containers or handled in a light-tight manner to prevent premature visible light exposure.
The light-curable compositions are used in a conventional manner. For example, the light-curable ink composition can be coated or printed on a substrate. The thickness of the composition can be varied as desired. Conventional coating techniques such as spray, curtain, dip, pad, roll-coating, and brushing can be used. Conventional printing techniques can be used.
The light-curable compositions can be applied by printing or coating to any conventional substrate. Examples of useful substrates include wood; metal, such as foils, cans, and bottle caps: glass; rubber; fabric, such as cotton, silk, and rayon; paper; newsprint; coated paper stock; corrugated board; fiber; plastic film: and molded plastic. They are useful in providing a variety of finishes including a simulated wood finish.
If the light-curable ink compositions are to be coated on a substrate, the substrate can be pretreated or primed as desired prior to the coating of the light-curable ink compositions thereon. Similarly, if the light-curable ink compositions are to be printed on a substrate, the substrate can be pretreated in any conventional manner prior to the printing of the light-curable ink compositions thereon.
The light-curable compositions are then exposed to visible light to cure the compositions. The actual exposure time required depends on a number of variables such as coating weight, coating thickness, the photohardenable composition, and the distance between the light source and the light-curable ink compositions.
The present invention is more fully illustrated by the following non-limiting Examples.
A yellow, light curable ink was produced by dissolving 3.0g of Disperse Yellow 42 (Aldrich) dye in 100g of trimethylolpropane triacrylate (Sartomer). This solution was divided into two equal portions. To portion A was added 1.0g of isopropylthioxanthone (Ward-Blenkinsop). To portion B was added 0.lg of N,N'-dibutylindocarbocyanine triphenylbutylborate. Both portions A and B were heated to 85� C. for 30 minutes and then cooled to room temperature. To each portion was added 1.0g of 2,6-diisopropyl-N,N-dimethylaniline. One drop of each was placed between two microscope slides and exposed to the light from one fluorescent tube at a distance of 12 centimeters. The times for first notable photopolymerization and for full slide immobilization were noted. Portion B exhibited polymerization at 26 seconds and slide immobilization at 32 seconds. Portion A exhibited no polymerization within 21/2 minutes. Thus, in 0 the presence of a visible light initiator (λmax approx. 550 nm), Portion B polymerized much more rapidly than Portion A, which contained a highly efficient UV (λmax=390 nm) initiator.
A yellow, light curable ink was produced by adding 12g of Quinoline Yellow pigment (Aldrich) to 100g of trimethylolpropane triacrylate (Sartomer). This mixture was divided into two equal portions. To portion A was added 1.0 g of isopropylthioxanthone (Ward-Blenkinsop). To portion B was added 0.1 g of N,N'-diheptylindocarbocyanine triphenylbutylborate. Both portions were heated to 85� C. for 30 minutes and then cooled to room temperature. To each portion was added 1.0 g of 2,6-diisopropyl-N,N-dimethylaniline. Several drops of each portion were placed on a 3 mil PET sheet and placed in a glass exposure frame. The samples were flushed with argon for ten minutes and then exposed for 15 seconds with two fluorescent tubes at a distance of 12cm with continuous flush. Portion B droplets, which contained the green sensitive initiator, fully polymerized. Portion A, which contained an efficient UV initiator (λmax=390 nm), polymerized only at the droplet surface, remaining liquid below that surface.
Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims
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Oven Baked Sweet & Sour Chicken
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Oven Baked Sweet & Sour Chicken
Using Gold's borscht is a creative and healthy way to make a quick Asian inspired sweet and sour sauce.
- Prep Time : 20 min
- Cook Time : 1 hour
- Ready Time : 1 hour, 20 min
- 1 cup Gold's duck sauce
- 1 1/4 cups Gold's borscht, divided into 1 and 1/4 cups
- 1 tablespoon corn starch dissolved in 2 tablespoons water
- 1 pound chicken cutlets, trimmed and thinned
- 1/3 cup soy sauce
- Panko crumbs
Combine the duck sauce, 1 cup borscht, and corn starch in a small saucepan. Cook on medium heat for about five minutes, until thickened.
Set aside.
Combine the remaining ¼ cup borscht and soy sauce and pour over chicken. Marinate chicken for at least 1 hour. Preheat oven to 350˚F. Line a shallow baking pan with parchment paper. Dredge chicken in panko crumbs and place on baking pan. Bake for twenty minutes. Pour reserved sauce on chicken.
As seen in Joy of Kosher with Jamie Geller Magazine (Summer 2013) – Subscribe Now.
About Shifra Klein
56 Responses to Oven Baked Sweet & Sour Chicken
This recipe was very easy to follow the only change I made was that I used a whole chicken 1/4 quarterd because two ppl only like bottoms also I used one cube of garlic because I felt it needed it other than that it was great. Oh I also sprayed the pieces of chicken with pam for a little extra crunch. I have a picture of it but don't know how to include or send it.
I froze one portion of this recipe want to see how it would be will let you know next week.
Made this chicken for supper tonight !!
Seemed odd to me but it was really good !!!
I used skinless boneless chicken thighs and they
were great !! Kids ate it without the sauce.
Put sauce on chicken for some and others just used as a dipping sauce. Everyone was happy !!
I made this tonight and what a surprise . I did not know how the borscht would work in this and it was wonderful I severed it over white rice .The chicken was very crisp and moist.We will definitely make this again.
I followed this recipe as directed, however, when I bought
the Gold's duck sauce, I did not notice that it said
"Hot and Spicy". Although we like a little heat, the flavor
was overpowering, even though I used the right measurements. Also, I think 20 minutes is not enough
time to cook chicken thoroughly, it needed at least 30-40
minutes. The idea was good and certainly easy. I may try
it again.
Made the recipe, using sweet and sour cabbage instead of borscht. There was plenty of sauce … a good thing because hubby and I enjoyed it immensely. I will make this again, but with less soy sauce (it was a tad salty).
The ease of this recipe is really appealing. Very simple to put together on weekday evening. My kids LOVED this chicken, and the sauce got a big WOW!
I made the chicken with gluten free soy sauce and gluten free Panko crumbs.
I made this dish for dinner tonight. Delicious – some changes – I didn't have cornstarch, so I used 1 tablespoon instead. I also didn't have boneless chicken, so I used thighs and pulled the skin. So, I baked it for about 1 hour.
Sorry – 1 tablespoon of flour instead of the cornstarch.
The chicken was so good. I did make some changes – I used thighs, but pulled the skin off first. I also did not have cornstarch, so I used 3 teaspoons of flour for thickener, instead. And lastly, I baked it for an hour. Big Hit!!!
The recipe looked interesting and although I'm also not a big borscht fan, the chicken was moist and the sauce great. It also looked really pretty. Like a previous commenter I also found it a bit salty, though, and would probably cut down on the soy sauce next time.
I was skeptical about the borscht but it worked really well! Nice tang and pretty blush color. I bought the borscht but forgot about duck sauce. Used a combo of apricot preserves, soy sauce, sesame oil. I used chicken tenders. Last few minutes I put on broil to brown.
The recipe was delicious. I used both boneless white and dark chicken to please all tastes in my house however I had to bake it longer than 20 minutes-more like 30. I was skeptical about the borsht but it gave it a good taste and the sauce was a beautiful color.
Very easy and tasty. Although I think I am going to have to make it again next week because I have no other use for borscht. I used chicken breast for ease, and regular bread crumbs. I needed 5 extra minutes of baking time.
Mmmmm Good and am I happy, I doubled the recipe expecting hearty eating gests only to learn that sickness would cause them to cancel. Guess you know what I'll be eating this week. Pleased to read that it stores well.
I will be pleased to serve this tasty moist dish to my guests in the future. By the way I made 50-50 with breasts and thighs.


text:
The first few puzzles are almost too easy, but as the difficulty increases you'll be thankful that you were able to practice the fundamentals of drawing track. As the game progresses, you'll have to use colour theory to combine trains of different colours, use timing to merge and split trains, and use every inch of your brain in your quest to beat the game.
9/10 "Simple yet awesome. Elegance in its simplicity." AppsZoom
Stuck on a puzzle? Visit http://trainyard.ca/solutions where there are over *1.5 million* player-submitted solutions.
What's New
Trainyard Express
"Devilishly addictive!" - Gizmodo
"You'll wrack your brains for hours!" - TapMagazine
"All aboard! Trainyard is a five star puzzle experience whose rails everyone should ride." - Gamezebo
"Trainyard is as fully featured as a puzzle fan could want." - Appspy
"It's a clever concept, simple to grasp but with a lot of variety." - 148Apps
Trainyard Express is a puzzle solving game unlike any that you've ever played. It's easy to learn but very tough to master. Your job is simple: get each train to a goal station. Red trains go to red stations, blue trains go to blue stations, etc. You control the trains by drawing track for them to follow. There isn't a time limit or even a score; the only thing you need to do is figure out a solution for each puzzle.
Trainyard Express Features:
+ Innovative and challenging puzzle mechanic
+ Smooth difficulty curve
+ Over 60 fantastic puzzles
+ Hundreds of ways to solve each puzzle
+ Solutions can be found on Trainyard.ca
+ Looks GREAT on tablets!
+ Engineered for low battery usage
+ Colour-blind mode
+ A year in the making
+ Developed in one person's spare time(support indie games!)
The first few puzzles are almost too easy, but as the difficulty increases you'll be thankful that you were able to practice the fundamentals of drawing track. As the game progresses, you'll have to use basic colour theory to combine trains of different colours, use timing to merge, and use every inch of your brain in your quest to beat the game.
What's the difference between Trainyard and Express? In the full game there are more than 100 more puzzles!
The full game also has splitter pieces, which are AWESOME.
Stuck on a puzzle? There are over 1.2 MILLION player submitted solutions at http://trainyard.ca/solutions
Find out more at http://www.trainyard.ca
Developed by Matt Rix (email@example.com)
Train Crisis Plus
***** This full version is 100% ads free and has unlimited tries for levels. *****
Would you like to travel through the history of the railroad?
This amazing game lets you play in four different railroad environments, where your goal is to overcome all the obstacles that appear on each level and guide each colored train toward its corresponding destination.
Download Train Crisis now! A puzzle and addictive strategy game with HD graphics where you have to prove your quick mind and reflexes in full 3D environment.
Train Crisis promises hours of challenging fun!
- 7 Eras of rail-road history (Industrial Era, Far West Era, Modern Era and Future Era).
- Spectacular High-definition 3D environments that recreate perfectly the three eras with many details as vegetation, animals, mountains, rocks, tunnels, banks, portals, etc.
- Train Crisis provides 168 challenging levels for players to conquer.
- In-game tool to help you solve puzzles more easily.
- Social features with Google Play Game Services: leaderboard, achievements, shared friends progress
- Cloud saving: share your progress across multiple devices and restore it upon reinstallation
- You must interact with several elements to get past the level: changing junctions; timed traffic lights; trap tunnels; transportation of money; ghost trains and parts of the track obstructed with rocks you must blow up.
- Spectacular colorful graphics effects with explosions of trains and rocks.
- Support for Android 4.4 (Kitkat) inmersive mode
Visit our Facebook site and twitter. Keep you informed on last news and announcements of Train Crisis HD: https://www.facebook.com/traincrisis
Puzzle Trains
Do not let your train get out of the way ...If you do, you will lose your precious cargo!
Puzzle Trains Puzzles Free is a fun and educational game for children of all ages, it will teach them ways to build and direct the vehicles to reach their destination. All in a colorful scene filled with animation and sounds appealing for the little children and not so little.
Enjoy this simulator rail maze, building your own railroad to subsequently add an infinity of trains as you can see in the series of drawings thomas friends. Enjoy your perspective train simulator in top view, easy and simple for kids of all ages view. Create a network of trains and simulates it a real large model trains, stations and train cars. Without doubt a great train sim for kids.
Puzzle Trains now Free!!
Web: http://www.codelabs-studio.com
Facebook: https://www.facebook.com/CodeLabsStudio
Twitter: https://twitter.com/CodeLabsStudio
Youtube: https://www.youtube.com/channel/UCPq4t0ZpieLDgzCO0HXvebw
Google+: https://plus.google.com/118096255293031533693/posts
Rail Maze : Train puzzler
* 100+ puzzles
* Tunnels
* Bombs
* PIRATE trains
* Super long trains
* 4 game modes:
LABYRINTH - Puzzle
BUILD RAILROAD - Action
SNAKE - Action
LONGEST RAILROAD - Puzzle Action
Get Rail Maze now!
"Rail Maze is an amazing puzzle game that will give you so many different options, youll be busy playing it for hours" – AppAdvice.com
"The biggest one is the change of art style, which – as you can see from the comparison screens below – is more honed and cowboy-like"- PocketGamer.com
"Rail Maze, with over 100 levels and thousands of downloads, certainly seems to be one of the hotter casual games out there at the moment."
- Gamezebo.com
"If puzzle games are your thing, you wont want to miss this one" – App Advice.com
LEGO® DUPLO® Train
Copying grownups and their activities is important to your 2-year-old toddler's development - and few things are quite as 'grownup' as driving a huge steam train around the the bright and friendly LEGO® countryside, horns tooting.
If your toddler is fascinated by trains, this simple game will provide new inspiration for hours of creative play - with or without a LEGO® DUPLO® train set.
*Bright, fun, and toddler-friendly animations and soundtrack
*Intuitive icons and navigation for easy game play
*Virtual building with LEGO® DUPLO® bricks
*No in-app purchases
*No third party advertising
*No links to websites
About LEGO® DUPLO®
A preschool building toy specifically designed for children ages 1 ½ - 5 – small hands and big imaginations! Preschoolers can learn about shapes and colors hands-on. When the chewing-the-bricks phase fades out, the building experience phase takes over, helping to stimulate and improve fine motor skills development. (Bricks-poured-onto-hard-surface noises stimulate other senses, too.)
Visit www.LEGO.com/duplo to find out more about LEGO® DUPLO®.
For app support contact LEGO Consumer Service.
For contact details refer to http://service.lego.com/contactus
Our privacy policy and terms of use for apps are accepted if you download this app.
Read more on http://aboutus.lego.com/legal-notice/Privacy-Policy and http://aboutus.lego.com/en-us/legal-notice/terms-of-use-for-apps
LEGO, the LEGO logo and DUPLO are trademarks of the LEGO Group. ©2013 The LEGO Group.
Train Tiles Express Puzzle
Travel from calm forests to dangerous volcanoes while battling increasingly fun and challenging brain teasers.
Rotate the tiles to guide the trains safely home… and make sure you don't crash!
- 120 puzzles to solve
- Twist and turn train tracks to lead your trains home
- 4 different worlds to conquer
- Fun brain teasers for the whole family!
TuTiTu Train
This game is one in a series of apps to accompany the series TuTiTu - "The toys come to life" which is a 3D animated YouTube wedisode targeting 2-3 year olds.
Through colorful shapes TuTiTu will stimulate the children's imagination and creativity. On each episode TuTiTu's shapes will transform into a new and exciting toy.
Track My Train
Track My Train is a addictive & fun puzzle game in which you have to quiz your mind and take your train out of crisis.
Put on Train Conductor Cap and quiz your mind! play with the railroads and take your pocket train out of crisis. You can adjust railroads to make a path for your train and make it reach its destination safely.
Total of 108 Levels!!
Quiz your mind and See if you can understand the game physics and complete all levels!
Lets see how good train conductor you are! Are you a man of crisis when it comes to helping trains out? Can you quiz your brain for all 108 levels??? Lets hope so! :)
Train Slide Puzzles iSlider
good for people who like train, locomotive, tracks, railroad, rail road, railway, jigsaw, jig saw, puzzle, puzzles, games, slider puzzles
Tiny Train
Paper Train Reloaded
Even the original version was awesome:
"Charmingly hand-drawn landscapes laid out on simulated graph paper" - Kotaku [http://bit.ly/eROvAd]
"Controlling chaos and preventing disaster is the name of this game." - Touch Reviews, 4/5 [http://bit.ly/h6Lkgg]
"Very addicting." - Flashfire5215 [iTunes review]
But with Paper Train Reloaded, you simply can't have more fun with trains:
Step into the shoes of a train dispatcher in this grand re-imagining of the critically acclaimed Paper Train game. Control railway traffic without crashing any trains. Direct and facilitate the movement of trains over exotic territories like rocky canyons, amusement parks, plane cemeteries, spacecraft crash sites, holiday resorts and much more. Complete the levels in time to collect stars and unlock new level packs, or just browse through the levels stress-free. Control the challenge and enjoy the beautiful hand-drawn graphics, which makes Paper Train Reloaded a truly remarkable experience. This is a train you must not miss!
- 300 challenging levels
- Fully animated hand-drawn graphics
- Incredibly simple controls
- Leaderboards via Scoreloop
Facebook: http://www.facebook.com/IstomGames
Trains Railroad Crossing
From the creators of Puzzle Trains, comes now Trains Railroad Crossing,Cross Road, a game that will test your mental and visual ability to anticipate the opening of the barrier. Do not let your train breaks down barriers and get the 3 stars and the "Perfect" in each of its 50 levels.
You can use multipliers to get more points, boosters, powerups, and power and you'll have new trains as a reward, and especially lots and lots of fun.
Ever wanted to be that person who handles press the button and raise the barrier to allow the train to pass over?
This is your chance. Do not miss Trains Railroad Crossing, Cross Road, Railroad Crossing, and download it now. Free game about trains, for you and your family.
Tap anywhere on the screen to open the next barrier. No need to press over the barrier, because you can not see the screen. The game tells you where is the next barrier because it is surrounded by a circle, and your mission is to guess when to open it, so the train can cross through it without breaking it.
The barrier, after a while, closes, so your visual and mental dexterity is essential.
A game that will test your mental capacity. A game that sometimes believe that tests your brain as Brain Trainer.
This game trains children and adults train set has been recognized by large and important industry sectors. It is also a free game trains.
Enjoy 50 increasingly difficult levels across 5 worlds, each world with colorful graphics adapted for high resolution tablets or smartphone.
Web: http://www.codelabs-studio.com
Facebook: https://www.facebook.com/CodeLabsStudio
Twitter: https://twitter.com/CodeLabsStudio
Youtube: https://www.youtube.com/channel/UCPq4t0ZpieLDgzCO0HXvebw
Google+: https://plus.google.com/118096255293031533693/posts
Train Memory
Circus Train
Use your shapes to build a bridge, road or tower for the train to travel across.
Can you help the minitrain to pass through all 50 levels?
Trains Planes Puzzle for Kids
When a puzzle is completed children are rewarded with a variety of fun celebrations and interactions such as balloon popping.
The fun matching activities help improve visual perception, knowledge of shapes & develop fine motor skills by dragging and dropping puzzle pieces to match their holes. Perfect for preschoolers.
• Kids Safe, please see our Privacy Policy
• Original high quality cartoon art drawn by professional children's book illustrator
• Three different vehicle groups: Trains, Air & Sea Vehicles
• Automatic advance to the next puzzle
• Three different puzzle styles with increasing difficulty levels
• Interface & touch controls designed for toddlers
• Press & hold button to limit menu access to parents
• Option to hide/show locked puzzles to prevent accidental purchases
The first 4 puzzles are free, all of the remaining ones can be unlocked easily via single in-app purchase. Once unlocked, there are no further in-app purchases or other dialogs.
We take privacy very seriously, this app:
Does not contain ads
Does not contain integration with social networks
Does not contain web links
Does not use analytics / data collection tools
Does contain a single in-app purchase to unlock full version
If you like our app, please take a minute to rate and review it.
If you have any questions or need help, please reach us at http://www.pixelenvision.com/support/ or by sending an e-mail to firstname.lastname@example.com
West Train
Noodlecake Studios Inc
Brickies is a fresh take on the classic breakout game, with fast paced levels that will leave you thirsty for more action.
Use the paddles to launch the ball and unleash a variety of power ups upon the brickies, but don't worry if you miss the ball!
In Brickies missing a shot doesn't mean the game is over, it deactivates the ball until you bounce it again and then you're back in action!
Explode, shoot and cut your way through over one hundred levels featuring, action, puzzles and tricky bosses. Unlock new exciting powers as you progress through the levels, beat the timer and collect three stars.
Earn achievements and compete for the highest score with your friends!
• Colourful and addictive breakout game
• Fast paced fun gameplay
• Over 100 levels to complete
• Combine power-ups for epic destruction
• Creative and challenging levels
• Endless mode for endless action
• Achievements
• Colourful and modern graphics
'A twist that least had us saying, "Huh, that's neat." ...Which doesn't happen often in the world of brick breakers' - Touch Arcade
The Blockheads
You haven't yet made shelter and your campfire has gone out.
All you have is a spade, some wood and a few sticks.
You have only minutes before exhaustion hits.
Do you create a bed, dig a cave or refuel your fire?
What will you do?
Explore, mine, craft and build in this giant and detailed sandbox game. Navigate huge simulated worlds thousands of blocks wide with a full temperature and climate system, seasons, an equator, and frozen poles. Explore complex cave systems and flowing water, and survive deserts and snowy mountain tops.
• Control your blockheads in a vast randomly generated world with oceans, mountains, forests, deserts and deep underground caves.
• Keep an eye on their needs - give them sleep, feed them, create clothing and shelter - and they'll be happier, quicker and more productive.
• Craft tools with the resources they find, and they'll be able to work even faster and find more resources.
• Upgrade workbenches and unlock more advanced items to craft.
• Discover precious stones and metals deep underground, or rare plants and animals on the surface.
• Craft a boat and navigate the oceans using the accurate night sky to guide you.
• Make fur clothing and venture to the North Pole.
• Pick coconuts at a tropical beach.
• Cook meat at a campfire.
• Build a marble palace.
• Paint the walls.
• Plant an orchard.
• Ride a donkey!
Zombie Road Trip
From the creators of the Tiki Totems saga comes a game that blends the boundaries of runner and racer trick games!
Race against the unrelenting Zombie Horde across the great wastelands in the never-ending game of survival. Shoot the zombies ahead with your impressive arsenal of weapons and witness true ragdoll-packed gore galore! Earn zombie coins to upgrade your ride and weapons to lay waste to the undead and show them just how much you hate them.
Perform and perfectly land tricks to earn boost and drive as far as you can, or else you might just die a horrible death!
Zombie road trip features :
- 5 landscapes each with its own distinct look
- fully randomised terrain (every play through will feel brand new)
- dynamic zombie demolition engine (every a zombie dies the collision will look awesome and new)
- 10 exciting weapons to dispatch your foes
- 34 unique cars
- 8 add ons that will change the way you play the game
- beautiful high def graphics
- buttons & tilt controls; you choose!
- spin bonus the wheel to earn more zombie coins
7/10 "Thrilling and Challenging with excellent graphics" - AppsZoom
Zombie Road Trip - coming from Spokko and Noodlecake.
Bitcoin Billionaire
Bitcoin Billionaire is an idle clicker that's all about raking in bitcoins and building up a massive fortune! You start with almost nothing: a run-down office, a rickety old desk, a crummy computer. By tapping the screen you can mine virtual bitcoins and slowly increase your wealth. Spend digital dough to upgrade that awful furniture into swanky things like entertainment centers and priceless works of art. If you're smart (which, you are!), you'll spend some of that money on investments to help you earn while you're away. And don't worry, investments aren't as boring as in real life. How could robot butlers, virtual reality and holographic dating be anything but awesome?
Tap your way from geeky bitcoin miner to geeky bitcoin miner who owns a private island with Bitcoin Billionaire!
- Supremely satisfying bitcoin tapping action!
- Upgrade investments to earn bitcoins while offline.
- Grab bonuses from special delivery drones.
- Customize your character to mine in style.
- Unlock achievements by being awesome.
- Adopt a kitty!
Zombie Road Trip Trials
Choose from an arsenal of guns to dispatch zombies roaming the wastelands. Watch them get dismembered thanks to our realistic rag-doll physics. Your garage is packed full of different vehicles that you can buy, upgrade and even repaint to your liking. Each vehicle is unique in both how it drives and looks.
Compete with your friends and thousands of players in the turn-based multiplayer mode for both money and fame. Race your Facebook friends and show them who is the boss! Not keen on using your Facebook ID? Well there is a guest mode awaiting as well.
ZRT: Trials lets you race, climb hills and shoot zombies across a variety of awesome post apocalyptic landscapes ranging from desolate deserts to destroyed cites and more.
Zombie Road Trip Trials features:
- 480 physics based missions
- 10+ hours of single player
- zombies with realistic rag doll physics
- cross platform multiplayer
- lots of upgradable cars and weapons
Happy Jump
Help our friendly dessert reach new heights in this action packed game. Bounce from platform to platform, dodge the mean flies, and grab everything you can to get the highest score.
Great fun to play with friends and family! Who can jump the highest in Happy Jump?
Brought to you by Retro Dreamer & Noodlecake Studios.
Ready Steady Bang
Progress through the game to unlock 31 unique cowboy deaths, then show them off in your Kill Gallery. Are you fast enough?
Super Stickman Golf 2
The sequel to the award winning and critically acclaimed, Super Stickman Golf is here!!!
Super Stickman Golf 2® out does the original in almost every way possible. With over 20 dynamic courses, new power-ups, customizable characters, 53 achievements, online multiplayer, Super Stickman Golf 2® will keep you on the fairway for a long time!
9/10 - AppsZoom - "Gameplay at its best"
5/5 - AppAddict.net - "Fantastic"
8.2/10 - IGN - "Polished to near perfection."
4.5/5 - Touch Arcade - "It is awesome!"
4.5/5 - Gamezebo - "Hugely entertaining"
4.5/5 - 148 Apps - "Sticktacular"
** Description **
20 Dynamic Courses. Never have the links been better looking or as unique as now. Moving obstacles, portals, magnets and more await you on the most creative courses to date.
Turn Based Multiplayer. Challenge golfers from all over the world to Turn Based multiplayer fun! Challenge random opponents or use the NEW Username Search to challenge your friends directly.
Customizable Characters. Stand out from the crowd with new unlock-able characters and even more valuable hats. Each hat contains a unique ability and some are more rare than others. Can you collect them all and become a certified Super Stickman Golf Legend?
** Features **
* Online Multiplayer
* 180 Challenging Holes
* 53 Achievements
* 28 Hats
* 10 Golfers
* NEW Powerups
* Dynamic Courses
At Noodlecake Studios we focus on making fun games. If you appreciate what we do and like our game, please give our game a positive review as we really do appreciate it.
Follow us on twitter: @noodlecakegames
Thank you!
Mmm Fingers
Mmm Fingers is a fun, single touch high score game oozing with charm from the creators of Small Fry and Flappy Golf. Touch and hold the screen as long as you can. Don't lift your finger or hit anything with teeth or else CHOMP, it is game over. Compete against your friends using in game leaderboards to see who can survive the longest.
- Leaderboards and Achievements
- One Touch Control Scheme
- No In App Purchases
Random Heroes
A group of unlikely heroes are set out to save the world. Monsters from another dimension are trying to take over Earth. Blast your way through these invaders in this action platformer! Collect coins and upgrade your weapons and characters to become stronger, faster and more lethal!
Choose your hero and save the world!
- Over 40 Levels
- 24 Characters
- 17 Weapons
- Google Play Game Services Achievements
Punch Quest
Jab, uppercut, slam, and otherwise pummel your way through dungeons full of monsters, branching path choices, rare events, and fragile pottery.
- Unlock and equip many special abilities and Supermoves.
- Ride a dinosaur that shoots lasers out of its mouth.
- Character customization.
- Punch an egg that turns you into a magical gnome.
- Do quests to earn really fancy hats.
- Combo system where you launch enemies into each other from across the map.
- Tablet support!
Punch Quest is a collaboration between Rocketcat Games (Hook Champ, Mage Gauntlet) and Madgarden (Saucelifter, Sword of Fargoal).
Brought to Android by Noodlecake Studios.
Flappy Golf
Flap your way to the hole with this unique spin on our famous golf game! Using the now famous "flap" mechanic you must get to the hole in the fewest flaps as possible!
Featuring the courses from Super Stickman Golf 2®, Flappy Golf is a fun little project we put together for the Flappy Jam game jam. Can you get gold stars on all the holes?
- Over 52 courses in total!
- Everyones favorite courses from Super Stickman Golf 2®
- Simple flap controls
- Race your Facebook friends in King of the Hole mode!
- Fun for the whole family!
- "This game is incredible. I've been playing it nonstop since I've downloaded"
- "This is by far one of the most fun and addicting games I've ever played!"
- "It seems like a joke, but somehow it turns into an amazing hybrid! Easy to learn and fun to master!"
Super Stickman Golf
"One of my favorite games of all-time!" -Toucharcade
"It's is a total winner. Once you play it you'll be hooked." -Slapapp
"A smash hit physics-based puzzle game with a golf mechanic" -Appadvice
The mobile gaming sensation is now available for android! Get it now while it's FREE!
Super Stickman Golf is no ordinary game.. it's actually an award winning physics puzzler! Swing your way through over 280 unique holes. Use all your special abilities to help you par the courses including sticky balls, ice balls, air brakes, and nitro balls! Have you ever wanted to stick your shots on walls and ceilings? Have you ever wanted to freeze those pesky water hazards? Ever wanted to stop your shot in mid-air? Well now you can..
- 7 unlockable super clubs!
- Over 280 unique holes!
- OpenFeint online leaderboards.
- Amazing HD graphics
- Integrated OpenFeint Achievements.
- New crazy obstacles. Conveyor belts anyone??
- 8-bit chiptune game soundtrack!
At Noodlecake Studios we focus on making fun games that actually don't suck. If you appreciate what we do and like our game, please give our game a positive review as we really do appreciate it.
Follow us on twitter: @noodlecakegames
Thank you!
Pumped BMX 2
Following the 2012 cult hit, Pumped BMX is back and packed full of more wild levels, more wild tricks, and over 500 challenges and achievements. Oh, and it's 3D too!
Ride your way through increasingly challenging levels while pulling off crazy trick combinations. 16 authentic BMX tricks can be combined with flips, spins, grinds and manuals for almost unlimited creativity. Includes a totally redesigned tutorial system so in just a few minutes anyone can be shredding like a pro.
Throw down your best moves to beat all 500 challenges or kick back and chill! It's up to you. Google Play leaderboards and achievements, featuring the best BMXers in the world, mean that you'll be sessioning Pumped BMX 2 long after the main game is complete.
Choose from 6 authentic rider styles and 10 unique bike colorways - look how you want to look, ride how you want to ride!
- 50 levels, 500 challenges - from the simple to the fiendishly difficult.
- Google Play Game Services leaderboards and achievements, featuring top BMX pros.
- 16 legit tricks from kickouts to cliffhangers, from icepicks to nose manuals.
- Super accurate physics - as close as you'll get to real BMX without picking up a bike.
- Amazing controls allow full creativity, from floaty 360s to frontflip bikeflips.
Wayward Souls
Procedurally generated random levels mean that every time you play the game, it's a different experience. Control one of six characters, all with their own unique playstyles, abilities, and equipment. Explore and fight for survival, in combat where your tactics, positioning, and timing matter.
More Features:
- Fancy control scheme with no virtual buttons or sticks to fumble over.
- Unlock new areas, for increasingly punishing difficulty.
- 13 area types, all with different monsters, potential traps, and rare encounters.
- Each character can find equipment combinations that change their gameplay.
- Victory is based on your increasing skill as a player, not solely on grinding.
- Hats.
- No IAP ever, even for the hats. All content updates will be free for our fans.
- Unprecedented scope and variety for an action-adventure game on Android, maybe anywhere.
Second Update Plans: MFI controller support, some sort of save sync, boss health bars, more character tweaks, Rogue buffs, and more! You can reach us on twitter or facebook to give requests or feedback on the game:
@NoodlecakeGames / facebook.com/noodlecakestudios
@rocketcatgames / facebook.com/rocketcatgames
Pumped: BMX Free
• Brand new gameplay - totally unique!
• Incredible controls - as close as you can get to real BMX!
• Over 100 challenges
• real tricks, 1000s of combos
• Outstanding physics simulation - true to life trails riding!
• Stunning HD artwork


text:
"[Simon and I] didn't really have our true voice, it was always off to the side," Sam confessed. "We never got to truly express ourselves, we didn't get to make the music that we really wanted to make. There's something that really eats at you inside when you're in a project and you don't feel like it's you."
"March 2010 we played Coachella," Sam explained. "10,000 people, it was insane. And then we were done 2 weeks later. We knew it was over."
"At the end of the day, it just didn't work out," Sam sighed. "The relationship between [Jarvis, Simon and myself] was toxic, and life's too short to spend time with people that make you feel bad. So Simon and I ultimately had to leave the situation, even though we had some success under our belt, it's was just not a way to live."
After a project that had taken up over five years of Sam Martin and Simon Katz's lives imploded, the two would have been forgiven if they took some time to recoup and recover. However, the pair did the exact opposite of that and, as the expression goes, simply got back on the horse. Two weeks after Iglu & Hartly called it a day, Sam and Simon started writing new tracks together. "Sam and I just locked ourselves in my studio —my 2nd bedroom studio— and just wrote and wrote and wrote as much as we possibly could," Simon explained. "Not really for any reason, but just to get stuff out."
"We poured out all these emotions that we had," Sam added. "It was really a cathartic experience, our major goal was just to get this sh*t off our chest. We had just gone through something that not a lot of people experience. There was a lot of anger, and fear, and regret. But there was also this feeling that we were on the right path. We can get somewhere, there's something happening here that's special. That really fueled us."
The two met up at noon and worked late into the night each and every day for months on end, penning nearly 200 songs while they tried to figure out the bedrock of what would eventually become the Youngblood Hawke sound, a few of which eventually became demo tracks. However, what they knew from the get go this time around was that as important as the music is, what would make or break this new endeavor were the people that they surrounded themselves with. "How do we make this thing like family?", Simon verbalized. "What we learned from past experiences is the importance of having those connections. One of the most important parts of being a band is having that connection with band members that will be long lasting. How many bands do you know that last for 10 years? Not many. And we want to be that. And it's very difficult to do that if you don't really get along with everyone in the band."


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Eqium 2.0 brings new interface, RTAS support
updated 07:45 am EST, Mon December 15, 2003
Equim 2.0: band DQ toolbox
Elemental Audio Systems today released version 2.0 of its unlimited band EQ tool box, Eqium. automation support, a completely redesigned user interface, and Digidesign Pro Tools RTAS compatibility for Mac OS X and Windows XP. In addition to RTAS format, Equim 2.0 supports Audio Unit and VST formats on Mac OS X and VST format on Windows. It presents a flexible mechanism for automating EQ changes through a host and users may choose which of their filters will be externally controlled. Elemental says that any of Eqium's 11 filter types, including its 4 and 8 Harmonic Parametric filters, may be automated. It is available for $130 through the end of December and runs on Mac OS X 10.2 or later.


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Maryland-Florida State Preview: Take a Look in the Mirror
by Steven Ruiz
When Maryland and Florida State take the floor Wednesday night, I implore you to pay close attention. If not, it may be difficult for you to tell the two teams apart... Read More »
N.C. State vs. Syracuse Basketball: Orange Defense Steps Up to Down Wolfpack
by Allen Lopp
The N.C. State Wolfpack traveled to the Carrier Dome in New York to take on the seventh-ranked Syracuse Orange. The Wolfpack looked destined to upset the Orange, but the Syracuse defense stepped up i... Read More »


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Football's over, March Madness hasn't yet begun and winter shows no signs of leaving. Time for a new hobby.
Fond du Lac author Karen Barouski has written a page-turning thriller set in Marinette, Wisconsin in the late 1990s.
Puccini's beloved opera La Boheme was a smash hit when it debuted in Italy in 1896. Today, it's one of the most-frequently performed operas in the world. Local aficionado the Rev. Jack Stubbs will host a lively discussion of the work at 6:30 p.m. Tuesday, March 5, at the Fond du Lac Public Library.
Sara Cujak hosted the Cujak's Wine Market Holiday Wine Tasting at the Fond du Lac Public Library in November.
The ins and outs of selling on eBay will be covered in free classes at the Fond du Lac Public Library. Three classes will be offered in February: 6 p.m. to 7:30 p.m. Tuesday, February 19; 1:30 p.m. to 3 p.m. and 6 p.m. to 7:30 p.m. Tuesday, February 26. The class will be repeated at 6 p.m. Tuesday, March 12.
It's easy to save money on glam accessories if you use the skills you learn in the Saturday, February 16, Crafternoon program at the Fond du Lac Public Library.
Prospective college students and their parents can get help with filling out the FAFSA (Free Application for Federal Student Aid) at the Fond du Lac Public Library. Lauren Lopez from Great Lakes Higher Education will hold a free open workshop from 5 p.m. to 8 p.m. on Monday, February 18, in the library's Mid-States Aluminum Training Room, in the lower level. Computers will be available, or students can bring their laptops, for applications to be filled out on site.
Thirty award-winning works of art by Wisconsin children and adults with disabilities will be featured in Creative Power: VSA Wisconsin's Traveling Exhibition February 1 through 25 in the Fond du Lac Public Library gallery.
Close Is Fine is a collection of 8 short stories featuring people who live and work on farms, at blue-collar jobs, and in the forests and taverns of Wisconsin, especially the area around Antigo and Shawano, and is a good choice for people who appreciate reflective, character-driven stories with a Wisconsin connection. These are not stories of dramatic redemption or tearful endings. The appeal of the stories is in the description of one particular event that happens to an ordinary individual at one point in time.
Are you smart? Do you have smart friends? Do you like to have a good time while helping a great cause? If you answered yes to one or more of these questions, the 13th Annual Team Trivia is the event for you.
Teams of four can sign up now for the March 5 and March 7 event at Whispering Springs Golf Club. Team members pay $25 for adults and $15 for teens (ages 13-18). The event includes a cash bar and a $12.50 per person Pulled Pork Sandwich dinner. Dinner is served at 5:30 p.m., accompanied by live music from Daryl Rogers, and the quizzing begins at 6:30 p.m.


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Product Information
Catch a Falling Star by Perry Como - Digital Sheet Music (Easy Piano)
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Catch a Falling Star digital sheet music. Contains printable sheet music plus an interactive, downloadable digital sheet music file.
* This arrangement does not contain lyrics
* This product is available worldwide
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Results 1 to 3 of 3
Thread: Shading
October 6th, 2002 #1
I need help with shading with a pencil. I just don't know how to make it look good. Any tutorials that give pointers?
- Similar Threads
- Shading help?
- Shading
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- Help with Shading Pls.
Hide this ad by registering as a memberOctober 8th, 2002 #2franz Guest
Be more specific, what are you having trouble with? Theory or technique? AFAIR there are some notes on pencil shading on http://www.portrait-artist.org - not all that helpful but it's a start.
How about you post some examples of pictures you're having trouble with? And you're not alone by the way, I'm having a hard time learning to shade properly as well.
October 9th, 2002 #3
That link seem to have a good tutorial.


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Originally written on hecmanhoops | Last updated 11/19/12
At 2-7 the Sacramento Kings needed to blame someone for their failures. Anyone! Psst, hey coach, let's blame Isaiah Thomas, everyone's doing it. He destroyed the Raptors, Pacers, Continental Basketball Association and the New York Knicks so it's ok, let's blame Isaiah, nobody will care. But wasn't that the other Isaiah Thomas? Yes, but they are both around the same height, black and play point guard, nobody will notice, just do it! Hurry! And with that amazing advice, Keith Smart benched his starting point guard who was only playing 23 mpg to begin with. Clearly it was all Isaiah's fault! So out goes Isaiah, in comes Aaron Brooks at point guard. Out goes James Johnson at small forward, in comes John Salmons. Nevermind the fact that John Salmons played and excelled only as a shooting guard while playing for Milwaukee and Chicago. Just ignore that, he's now the Kings new starting small forward! How did that work out last year for the Kings, Keith? In terms of fantasy, where does this ...
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