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Description
As to try to keep up to date on character colors, we as the MLP-VectorClub are trying to keep a better handle on the colors of new or recurring characters as they come up. As such, this is a preliminary color guide to all characters we've determined important to pick from. We will probably recheck some of these when we append to our more common guide (here i4.minus.com/iurGZ8Q9WHQVp.png ) but these should be good to use for now for your vectors. I will keep this deviation up to date as reasonably soon after a new episode comes out and iTunes uploads the HD version, with obvious things that need color keys.

Important Note: Prior to adding in the S5E10 "Princess Spike" colors, we've discovered that the way I have been taking screenshots through VLC to get the color keys produces colors in some ranges that are are a notch desaturated (between 3-6 RGB values lower on each channel) than what other methods that, we come to determine, are more direct sampling approaches. The difference is visually difficult to catch unless you overlap sections, but for exactness I'll need to go back through sections to get them up to spec. I will try to note when those have been changed on the sheet. In terms of submitting vectors, as long as it uses or other sets of colors (to avoid the normal saturation/desaturation that other video sources have), we'll be fine.

Note that all colors are sampled off the US iTunes release (our default "proper" color set).

The full color guide in PNG form can be found here:

Link to current AI CS6 file:
AI No Preview

Current version: Through E04, includes:
E01/E02 - Starlight Glimmer, Double Diamond, Party Favor, Sugar Belle, and Night Glider (equalized and normal), and the equalized Mane 6
E03 - Davenport (first best chance to color key)
E04 - Babs Seed's (apparent) cutie mark, Apple Bloom's 3 False Cutie Marks, Pest Control Pony, Pest Control Pony Gear (be warned on this equipment, it is somewhat inconsistent shot to shot, and uses a LOT of colors. We will likely try to cut down the color set purposely or simplify the colors). A note that the Twittermites have no clear shot to get good colors off of, so they are not presently included. (much thanks to Pirill-Poveniy on color picking here, and dasprid for use of his vector of the twittermite bug catcher for reference)
E05: The four pegasi involved in the "Who's On First" gag - Open Skies, Clear Skies, Sunshowers, and Fluffy Clouds, and the winter gear that the mane 6 have at the end of the episode. Also includes RD + Tank's robes/slippers (from near the end) , and RD's beach outfit (during the song).
E06: Troubleshoes Clyde, including his clown outfit, and Sheriff Silverstar's two deputies; also adds in the catcus hat Scootaloo wore and the rodeo banner headband that Apple Bloom wore.
E07: Tree Hugger, the Smooze, and Gala dresses for : Mane 6, CMC, Celestia, Maud Pie, Tree Hugger, and Discord. Please note that with the dresses 1) I am going off my limited knowledge of fashion based on being a closet Project Runway fan, so any suggestions in naming improvements will help and 2) I have marked where they have used duplicate colors for these dresses , so while some may see to have large color keys (RARITY) they actually are a limited number of colors. Added in this are some small pics of Rarity's gems to help with ID'ing color, and small reorg.
E08: Greta and "Gimme Moore" (the shopkeeper griffon), and Grandpa Gruff. (Please note, if you used this guide prior to June 2, 2015, the previous colors were found to be off due to iTunes and have now been fixed)
E09: Steven Magnet (first daytime shots of him); Derpy Hooves to include her eye highlights, Button Mash, Dance Fever, and Hugh Jelly, Cranky and Matilda's outfits, Doctor Whooves' bowtie and scarf, the bugbear, and the three Big Lebowski ponies.
E10: Delegate ponies (~13 of them) and the two repair/maintenance ponies.

Please note if there is a character or element you want color keyed that we could add. Keep in mind, we need to have the character in a clear closeup shot as to sample the colors cleanly, with no lighting or other filter effects. (For example, prior to "Daring Don't" it was difficult to get accurate colors for Daring Do and Ahuiztol due to the blur filter they used). If we can't get a clear shot we will probably not color key it.

Description
As to try to keep up to date on character colors, we as the MLP-VectorClub are trying to keep a better handle on the colors of new or recurring characters as they come up. As such, this is a preliminary color guide to all characters we've determined important to pick from. We will probably recheck some of these when we append to our more common guide (here i4.minus.com/iurGZ8Q9WHQVp.png ) but these should be good to use for now for your vectors. I will keep this deviation up to date as reasonably soon after a new episode comes out and iTunes uploads the HD version, with obvious things that need color keys.

Important Note: Prior to adding in the S5E10 "Princess Spike" colors, we've discovered that the way I have been taking screenshots through VLC to get the color keys produces colors in some ranges that are are a notch desaturated (between 3-6 RGB values lower on each channel) than what other methods that, we come to determine, are more direct sampling approaches. The difference is visually difficult to catch unless you overlap sections, but for exactness I'll need to go back through sections to get them up to spec. I will try to note when those have been changed on the sheet. In terms of submitting vectors, as long as it uses or other sets of colors (to avoid the normal saturation/desaturation that other video sources have), we'll be fine.

Note that all colors are sampled off the US iTunes release (our default "proper" color set).

The full color guide in PNG form can be found here:

Link to current AI CS6 file:
AI No Preview

Current version: Through E04, includes:
E01/E02 - Starlight Glimmer, Double Diamond, Party Favor, Sugar Belle, and Night Glider (equalized and normal), and the equalized Mane 6
E03 - Davenport (first best chance to color key)
E04 - Babs Seed's (apparent) cutie mark, Apple Bloom's 3 False Cutie Marks, Pest Control Pony, Pest Control Pony Gear (be warned on this equipment, it is somewhat inconsistent shot to shot, and uses a LOT of colors. We will likely try to cut down the color set purposely or simplify the colors). A note that the Twittermites have no clear shot to get good colors off of, so they are not presently included. (much thanks to Pirill-Poveniy on color picking here, and dasprid for use of his vector of the twittermite bug catcher for reference)
E05: The four pegasi involved in the "Who's On First" gag - Open Skies, Clear Skies, Sunshowers, and Fluffy Clouds, and the winter gear that the mane 6 have at the end of the episode. Also includes RD + Tank's robes/slippers (from near the end) , and RD's beach outfit (during the song).
E06: Troubleshoes Clyde, including his clown outfit, and Sheriff Silverstar's two deputies; also adds in the catcus hat Scootaloo wore and the rodeo banner headband that Apple Bloom wore.
E07: Tree Hugger, the Smooze, and Gala dresses for : Mane 6, CMC, Celestia, Maud Pie, Tree Hugger, and Discord. Please note that with the dresses 1) I am going off my limited knowledge of fashion based on being a closet Project Runway fan, so any suggestions in naming improvements will help and 2) I have marked where they have used duplicate colors for these dresses , so while some may see to have large color keys (RARITY) they actually are a limited number of colors. Added in this are some small pics of Rarity's gems to help with ID'ing color, and small reorg.
E08: Greta and "Gimme Moore" (the shopkeeper griffon), and Grandpa Gruff. (Please note, if you used this guide prior to June 2, 2015, the previous colors were found to be off due to iTunes and have now been fixed)
E09: Steven Magnet (first daytime shots of him); Derpy Hooves to include her eye highlights, Button Mash, Dance Fever, and Hugh Jelly, Cranky and Matilda's outfits, Doctor Whooves' bowtie and scarf, the bugbear, and the three Big Lebowski ponies.
E10: Delegate ponies (~13 of them) and the two repair/maintenance ponies.

Please note if there is a character or element you want color keyed that we could add. Keep in mind, we need to have the character in a clear closeup shot as to sample the colors cleanly, with no lighting or other filter effects. (For example, prior to "Daring Don't" it was difficult to get accurate colors for Daring Do and Ahuiztol due to the blur filter they used). If we can't get a clear shot we will probably not color key it.