CA1248677A - Composition and process for making an amber colored polyester - Google Patents
Composition and process for making an amber colored polyesterInfo
- Publication number
- CA1248677A CA1248677A CA000454782A CA454782A CA1248677A CA 1248677 A CA1248677 A CA 1248677A CA 000454782 A CA000454782 A CA 000454782A CA 454782 A CA454782 A CA 454782A CA 1248677 A CA1248677 A CA 1248677A
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- Prior art keywords
- polyester
- titanium
- carbon atoms
- parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
Abstract
Abstract of the Disclosure A COMPOSITION AND PROCESS
FOR MAKING AN AMBER COLORED POLYESTER
Specific color imparting compounds, including colorants and catalysts are used to produce a polyester resin having an amber color. The compounds are added during the preparation of the polymer and the resins produced can be utilized to make various containers or packages to hold liquids or solids.
FOR MAKING AN AMBER COLORED POLYESTER
Specific color imparting compounds, including colorants and catalysts are used to produce a polyester resin having an amber color. The compounds are added during the preparation of the polymer and the resins produced can be utilized to make various containers or packages to hold liquids or solids.
Description
A CO~IPOSITION AND PROCESS
FOR MAKING AN AMBRR COI.ORED POLYESTER
Technical Field The present invention rela-tes to an amber colored polyester made using specific color-imparting compounds.
Heretofore, various desired colors have been imparted to items, for example, glass, paint, paper, etc., through the use of various minerals, pigments, inks, and the like. However, to impart a color, for example, amber, to a polyester whlch can be made into a container, e.g., a bottle, for containing liquids or solids as Eor human consumption 9 requires that specific safe color-impàrting compounds be used. Furthermore, the pigments or catalysts must not adversely affect the properties of the polymer.
Disclosure of Invention There is disclosed a polyester article, the improvement which comprises a small amount of various color-imparting compounds contained in the polyester for imparting an amber color thereto, said compounds comprising a yellow colorant, a titanium catalyst, a blue pigment, and a red colorant; the proportion of `said compounds being sufficient to effect an amber color.
Also disclosed is an amber colored polyester resin comprising color-imparting compounds dispersed in the polyester resin, said compounds being a yellow colorant, a titanium catalyst, a red colorant and a blue pigment, the amount of said compounds being such so that an amber color is imparted to sald polyester resln .
~}
:~L2~ '7'7 There is also disclosed a process for making a polyester resin having an amber color comprising the steps of preparing a polyester resin; adcling a yellow colorant to said polyester resin during preparation thereof; adding a titanium catalyst to said polyester resin during preparation thereof; adding a blue pigment to said polyester resin during preparation thereof;
adding a red colorant to said polyester resin, and imparting an amber color to said resin by utilizing ln sufficient amounts of said yellow colorant, said titanium catalyst, said red colorant and said blue pigment.
Best Mode for Carrying Out the Invention According to the concepts of the present invention, an amber colored polyester resin suitable for the production of containers, packages, etc., and especially for carbonated beverages, is produced. The polyester to ~hich an amber color can be imparted are conventional or known polyesters made according to conventional or known methods, processes and the like.
Generally, such polyesters include polymers formed from dicarboxylic acids containing a total of from 2 to 16 carbon atoms reacted with polyhydric alcohols such as glycols or diols containing from 2 to 12 carbon atoms.
The alkyl dicar~oxylic acids may contain a total of from 2 to 16 carbon atoms. Preferably, the acids are aryl or an alkyl substituted aryl acid containing from 8 to 16 carbon atoms. Specific examples of linear or alkyl dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, plmelic acid~ suberic acid, azelaic acid, sebacic acid, and the like. Specific examples of an aryl acid include the various isomers of phthalic acid, such as terephthalic acid, isophthalic acid and naphthalene 6'7~
dicarboxylic acids. Specific examples of alkyl subs~ituted aryl acids include the various isomers of dimethylphthalic acid such as dimethylisophthalic acid, dimethylorthophthalic acid, dimethylterephthalic acid, the various isomers of diethylphthalic acid such as diethylisophthalic acid, diethylorthophthalic acid, diethylterephthalic acid, the various isomers of dimethylnaphthalene dicarboxylic acid such as dimethyl substituted napthalene 2,6 dicarboxylic acid and dimethyl substituted naph-thalene 2,7 dicarboxylic acid, and the various isomers of diethyl substituted naphthalene dicarboxylic acids. Generally, terephthalic acid is highly preferred.
It is well known to those skilled in the art, in lieu of the various dicarboxylic acids, the various diesters thereof may be utilized. Thus, alkyl diesters containing a total of from 2 to about 20 carbon atoms as well as alkyl substituted aryl diesters containing from about 10 to about 20 carbon atoms may be utilized.
Examples of diesters include the diesters of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, or sebacic acid, and the like. Specific examples of various alkyl substituted aryl diesters include the various isomers of dimethylphthalate such as dimethylterephthalate, a preferred compound, the various isomers of diethylphthalate, the various isomers of dimethylnaphthalate, and the various isomers of diethylnaphthalate.
The diols or glycols may be straight chain or branched. Specific examples include ethylene glycol, propylene glycol, trimethylene glycol, 112-butane diol, 1,3-butane diol, 1,4-butane diol, 2,3-butane diol, neopentyl glycol, and the like. Of the various glycols, those having from 2 to 8 carbon atoms are '77 preferred with ethylene glycol and l,/-~-butane diol being highly pre~erred. In lieu of the various glycols, another class of polyhydric alcohols, s~lch as the glycol ethers containing from ~ to 12 carbon atoms, can be utilized as for example diethylene glycol and 1,4-dihydroxyethoxy benzene.
The polyesters can be made according to melt polymerization, or melt and solid state poly~erization.
As known to those skilled in the art, polyesters are generally made in two stages. In the first stage or esterification stage, the diacid is reacted with the diol at elevated temperatures and pressures with water being produced. In the second stage or the polycondensation stage, a vacuum is gradually applied, generally catalyst are utilized, and water and a diol are withdrawn as a condensation product. Various polyesters can be made by such a polymerizatlon including polyethyleneterephthalate, a preferred polyester resin. Moreover, the process may be modi~ied slightly by reacting the dicarboxylic acid with the diol in a solvent which is a low molecular weight linear polyester in a manner as set forth in U.~.
Patent No. ~,020,0~9 to ~inehart. Another well known variation utilizes dimethylterephthalate which is reacted with ethylene glycol in the presence of a catalyst with a transesterification reaction yielding a bishydroxy- ethylterephthalate compound. A stabilizer may then be added as well as a catalyst and a polycondensation reaction is carried out to yield a polyester. Regardless of the exact process, such reactions can be carried out in situ. When prepared by a melt polymerization process, the resin is thermally .0~ . ) r crystallize(~ to prevent sticking during drying prior to subsequent melt conversion into an article.
Solid state polymerization can also be utilized.
In this process, the polycondensation reaction is c~rried out until generally the intrinsic viscosity of the polymer melt reaches about 0.20 or higher, for example, up to about 0.80. At this point, the solution melt is cooled to produce a solid which is then pelletized, chopped, etc. The pellets are then subjected to a solid state polymerization wherein the vacuum is applied or a stream of inert gas passed at a temperature below the melting point of the partially formed polymer. Thus, the polymer is actually polymerized in a solid state, with the polycondensation reaction being continued in such a state. Generally, the solid state polymeriz.ation is continued until the intrinsic viscosity reaches any desirable level, such as from about 0.60 to about 1.0, or even higher.
Desirably, the intrinsic viscosity ranges from about 0.70 to about 0.85 and preferably from about 0.70 to about 0.30. By intrinsic viscosity it is meant that the value obtained when n specific/C or LOG _ rel./C is extrapolated to zero concentration; where the relative viscosity is defined as the quotient of the solution viscosi-ty, n soln and the viscosity of the solvent n solv , i.e. ? n rel n soln.
n solv.
The specific viscosity _ sp. - rel.
are deciliters/gram using a 60/l~0 phenol/tetrachlorothane at 25C. The symbol _ is for the Greek letter eta.
IJhen the polyester resin is intended for use in contact with food, only those polyesters which are regulated by the Federal Food and Drug Administration ~ 77 should be utilized, such as set forth in Title 21, ~177.1630, for example, the polyethylenephthalate polymers, and s-lch polyesters are preferred in -the present in~ention.
r) An amber colored polyester resin is produced by utilizing specific color-imparting compounds to produce the amber color. Specifically, a yellow colored compound is utilized wit~ a blue colored compound, and a red colored compound to yield an intermediate amber color. The resin color is measured by a Gardner Colormeter, or a ~unter Lab instrument is utilized for beverage bottle measurements. The Gardner meter utilizes re~lectance (Rd) values as a measure of brightness, whereas the Hunter instrument utilizes luminance (L) as a measure of the brightness. The color hue is defined in either case by (a~ or Ib) values. Positive (a) coordinates (that is, an X axis) measures rednes$ whereas Negative (a) values indicate greeness. Positive (b) (that is, positive Y
coordinates) define yellowness whereas negative (b) values indicate blueness. The brightness (reflec-tance or luminance) of the sample is required as a point from 0 (black) to 100 (white) using both instruments. These measurements enable an approximation of the visual color used in the instrument coordinates. The measured (a) and (b) values therefore place a resin or a bottle made from the resin in one of the colored quadrants formed by their axes. In an anti-clockwise direction, star-ting at the three o'clock position, the first quadrant is red/yellow, the second quadrant is yellow/green, the third quadrant is green/blue, and the fourth quadrant is blue/red. The color amber of the resin of the present invention is in the first quadrant, that is basically a reddish-brown compound with a yellow tinge thereto.
7 ~
Regardless of the type (that is, chemical formulatlon) of polyester or the process utilized, an amber color is imparted to the polyester by utilizing specific color imparting compounds. The compounds which are utilized include yellow colorant 7 red colorant, titanium catalysts, and a blue pigment.
Additionally, the polyester can contain conventional additives such as stabili7ers, antioxidants, and the like.
The titanium catalysts can be alkyl esters having from 3 to 10 carbon atoms, or titanium chelates having from 4 to 50 carbon atoms with from 6 to 32 carbon atoms being preferred. The titanium catalysts act as a polycondensation catalyst as well as influence the shade of the polyester. Of the numerous titanates which may be utilized, the following are desirable, titanium triethanolamine, titanium acetyl acetonate, tetrabutyl titanate, tetraisopropyl titanate, and titanium glycolate. Examples of suitable titanium chelates include titanium acetyl acetonate, triethanolamine titanium chelate, lactic acid titanium chelate, tetraoctylene glycol chelate, and the li~e.
The first two chelates are often referred to as titanium alkyl esters and thus have also been previously listed as such. A specific source of chelates are the DuPont Co. under the name "TYZOR"TM.
Of the various titanium compounds, titanium triethanolamine chelate is preferred with tetrabutyl titanate being highly preferred. The amount of the titanium catalysts as titanium (Ti), based upon one million parts by weight of the final amount of polyester resin produced generally ranges from about 2 parts to about 150 parts, with from about 40 to about 70 parts being desirable and approximately 50 parts by wei~ht being preferred. The titanium catalysts can be ., ~
dded clurillg the esterification or polycondensation S tage .
A blue pigment is utilized so that in combination with the yellow and red colorant and the titanium catalysts, an amber color is produced. That is, the amber colorecl resin of the present invention resides within t~le first above-noted color quadrant. Based upon the (a) and (b) coordinates, the color utilizing a one-eighth inch thermally crystallized resin cube having a density of approximately 1.37 grams per cc is as follows: Gardner values of from about 0 to about +10 and preferably from about +2 to about +6 on the (a) scale, and from about 0 to about 12 and preferably from about 3 to about 9 on the (b) scale or coordinate. The Hun~er value ranges ~rom about -2 to about +6 and preferably from about 0 to about +3 on the (a) coordinate and from about -1 to about +9 and preferably from about -~1 to about +5 on the (b) coordinate. When a bottle, a 2 liter beverage bottle, is produced, the Hunter values generally, depending on the bottle design, range from about -~2 to about -~16 and preferably from about +8 to about +14 on the (a~ coordinate and frorn about -~1~ to about ~36 and pre~erably from about +23 to about ~-32 on the ~b) coordinate. Thus, essentially a amber color is produced or more exactly, a reddish-brown color having a yellow tlnge thereto.
The blue pigment which is utilized can be any blue pigment which produces, in combination with the other pigments and catalysts, the desired amber color.
Desirably, a pigment blue number 15 is desired, that is C.I. (color index number) of 74160. A specific example of the blue pigment which is preferably added during the esterification stage, but it can also be added during the polycondensation stage, is phthalocyanine blue Phthalocyanine blue is commercially available ~ 7~
from many suppllers such as Pa]iofastT~ ~lue manufactured by BASF, or as Monas~ralTM Blue, manufactured by DuPon-t. The amount of phthalocyanine blue utilized per million parts of the final polyester resin produced ranges from about 20 to ahout 100 parts by weight, ~ith a preferred range being from about 30 to about 50 parts by weight.
The yellow colorant which is utilized can be any pigment which produces, in combination with the other pigment and titanium catalyst, the desired amber color.
Preferably the yellow colorant is SolvapermTM Yellow G
(CAS No. 10319-14-9) which is commercially available from American Hoechst Corporation. The yellow colorant is preferably added during the esterification stage, but it can also be added during the polycondensation stage. The amount of SolvapermT~ Yellow G utilized per million parts of the final polyester resin produced ranges from about 100 to about 800 parts by weight with a preferred range being from about 250 to 600 by weight.
The red colorant which is utilized can be any pigment which produces, in combination with the other pigment and titanium catalyst, the desired amber color.
The red pigment is preferably added during the esterification stage, but it can also be added durlng the polycondensation stage. A speci-fic example of the red pigment is SolvapermT~ Red G also designated as Solvent Red 135 and is commercially available from American Hoechst Corporation. The amount of Solvaperm Red G utilized per million parts of final resin produced ranges from about 100 to 800 parts by weight with a preferred range being from 250 to 600 by weight.
The polyester resins of the present invention can be utilîzed in various conventional process apparatus such as calendars, injection molding machines, blow molding machines, extruslon machines, and the like, to , .:
~2~
produce anY desired article which has a amber color thereto. A particular area of use is a container area, such as bottles, and more particularly beverage bottles, for example liquor bottles.
The invention will be better understood by reference to the following examples.
Amber PET resins have been prepared according to the invention via batch processes (although continuous processes can also be utilized). In the following examples, titanium catalyst level used are indicated by parts per million of Ti by weight of PET. The phthalocyanine blue pigment, the red pigment and yellow pigment amount used is also in parts per million by weight of PET.
The appropriate amount of phthalocyanine blue pigment, red pigment and yellow pigment is slurried in ethylene glycol and added to a low molecular weight oligomeric mixture of PET at 270-290C in a manner as set forth in United States Patent No. ~l,020,049 to Rinehart. A portion of this esterification product mixture is transformed to another vessel where separately prepared solutions and TyzorTn TBT
~tetrabutyl titanate) in ethylene glycol are added.
The pressure of the vessel is gradually reduced to less than 1 millimeter of mercury to polycondense the mixture ~o an amber PET with the desired molecular weight (I.V.). A thermal crystallization is then carried out to yield a resin which doesn't stick together during drying prior to conversion to carbonated beverage bottles. The amounts of the various compounds as well as the color is set forth in Table I.
TABLE I
Composi~ion COLOR
GARDNER HUNTER LAB
_ a b L a b_ _ _ _ RESIN
Amorphous 2.1 1.5 -0.6 Crystalized 5.8 4.1 6.7 22.3 1.9 3.9 PREFORM (2 liter) 4.6 1.1 0.7 BOTTLE ~2 liter) 45.1 12.4 27.9 TBT = TyzorTM TBT (tetrabutyl titanate) SY = SolvapermTM Yellow G
SR ~ SolvapermT~ Red &
PB = Phthalocyanine Blue Pigment 15 Color Index No. 74160 ~ s app~rent from the above table, the bottle tencls to have a slightly different color than the crystallized resln. This is due to the fact that the bottle thickness is generally thinner than the resin S and thus imparts a different color. In any event, a suitable end color can be readily achieved.
While having described the best mode as well as the preferred embodiments of the present invention, in accordance with the patent statutes, it is noted that the invention is not limited thereto, the scope of the invention being measured by the attached claims.
FOR MAKING AN AMBRR COI.ORED POLYESTER
Technical Field The present invention rela-tes to an amber colored polyester made using specific color-imparting compounds.
Heretofore, various desired colors have been imparted to items, for example, glass, paint, paper, etc., through the use of various minerals, pigments, inks, and the like. However, to impart a color, for example, amber, to a polyester whlch can be made into a container, e.g., a bottle, for containing liquids or solids as Eor human consumption 9 requires that specific safe color-impàrting compounds be used. Furthermore, the pigments or catalysts must not adversely affect the properties of the polymer.
Disclosure of Invention There is disclosed a polyester article, the improvement which comprises a small amount of various color-imparting compounds contained in the polyester for imparting an amber color thereto, said compounds comprising a yellow colorant, a titanium catalyst, a blue pigment, and a red colorant; the proportion of `said compounds being sufficient to effect an amber color.
Also disclosed is an amber colored polyester resin comprising color-imparting compounds dispersed in the polyester resin, said compounds being a yellow colorant, a titanium catalyst, a red colorant and a blue pigment, the amount of said compounds being such so that an amber color is imparted to sald polyester resln .
~}
:~L2~ '7'7 There is also disclosed a process for making a polyester resin having an amber color comprising the steps of preparing a polyester resin; adcling a yellow colorant to said polyester resin during preparation thereof; adding a titanium catalyst to said polyester resin during preparation thereof; adding a blue pigment to said polyester resin during preparation thereof;
adding a red colorant to said polyester resin, and imparting an amber color to said resin by utilizing ln sufficient amounts of said yellow colorant, said titanium catalyst, said red colorant and said blue pigment.
Best Mode for Carrying Out the Invention According to the concepts of the present invention, an amber colored polyester resin suitable for the production of containers, packages, etc., and especially for carbonated beverages, is produced. The polyester to ~hich an amber color can be imparted are conventional or known polyesters made according to conventional or known methods, processes and the like.
Generally, such polyesters include polymers formed from dicarboxylic acids containing a total of from 2 to 16 carbon atoms reacted with polyhydric alcohols such as glycols or diols containing from 2 to 12 carbon atoms.
The alkyl dicar~oxylic acids may contain a total of from 2 to 16 carbon atoms. Preferably, the acids are aryl or an alkyl substituted aryl acid containing from 8 to 16 carbon atoms. Specific examples of linear or alkyl dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, plmelic acid~ suberic acid, azelaic acid, sebacic acid, and the like. Specific examples of an aryl acid include the various isomers of phthalic acid, such as terephthalic acid, isophthalic acid and naphthalene 6'7~
dicarboxylic acids. Specific examples of alkyl subs~ituted aryl acids include the various isomers of dimethylphthalic acid such as dimethylisophthalic acid, dimethylorthophthalic acid, dimethylterephthalic acid, the various isomers of diethylphthalic acid such as diethylisophthalic acid, diethylorthophthalic acid, diethylterephthalic acid, the various isomers of dimethylnaphthalene dicarboxylic acid such as dimethyl substituted napthalene 2,6 dicarboxylic acid and dimethyl substituted naph-thalene 2,7 dicarboxylic acid, and the various isomers of diethyl substituted naphthalene dicarboxylic acids. Generally, terephthalic acid is highly preferred.
It is well known to those skilled in the art, in lieu of the various dicarboxylic acids, the various diesters thereof may be utilized. Thus, alkyl diesters containing a total of from 2 to about 20 carbon atoms as well as alkyl substituted aryl diesters containing from about 10 to about 20 carbon atoms may be utilized.
Examples of diesters include the diesters of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, or sebacic acid, and the like. Specific examples of various alkyl substituted aryl diesters include the various isomers of dimethylphthalate such as dimethylterephthalate, a preferred compound, the various isomers of diethylphthalate, the various isomers of dimethylnaphthalate, and the various isomers of diethylnaphthalate.
The diols or glycols may be straight chain or branched. Specific examples include ethylene glycol, propylene glycol, trimethylene glycol, 112-butane diol, 1,3-butane diol, 1,4-butane diol, 2,3-butane diol, neopentyl glycol, and the like. Of the various glycols, those having from 2 to 8 carbon atoms are '77 preferred with ethylene glycol and l,/-~-butane diol being highly pre~erred. In lieu of the various glycols, another class of polyhydric alcohols, s~lch as the glycol ethers containing from ~ to 12 carbon atoms, can be utilized as for example diethylene glycol and 1,4-dihydroxyethoxy benzene.
The polyesters can be made according to melt polymerization, or melt and solid state poly~erization.
As known to those skilled in the art, polyesters are generally made in two stages. In the first stage or esterification stage, the diacid is reacted with the diol at elevated temperatures and pressures with water being produced. In the second stage or the polycondensation stage, a vacuum is gradually applied, generally catalyst are utilized, and water and a diol are withdrawn as a condensation product. Various polyesters can be made by such a polymerizatlon including polyethyleneterephthalate, a preferred polyester resin. Moreover, the process may be modi~ied slightly by reacting the dicarboxylic acid with the diol in a solvent which is a low molecular weight linear polyester in a manner as set forth in U.~.
Patent No. ~,020,0~9 to ~inehart. Another well known variation utilizes dimethylterephthalate which is reacted with ethylene glycol in the presence of a catalyst with a transesterification reaction yielding a bishydroxy- ethylterephthalate compound. A stabilizer may then be added as well as a catalyst and a polycondensation reaction is carried out to yield a polyester. Regardless of the exact process, such reactions can be carried out in situ. When prepared by a melt polymerization process, the resin is thermally .0~ . ) r crystallize(~ to prevent sticking during drying prior to subsequent melt conversion into an article.
Solid state polymerization can also be utilized.
In this process, the polycondensation reaction is c~rried out until generally the intrinsic viscosity of the polymer melt reaches about 0.20 or higher, for example, up to about 0.80. At this point, the solution melt is cooled to produce a solid which is then pelletized, chopped, etc. The pellets are then subjected to a solid state polymerization wherein the vacuum is applied or a stream of inert gas passed at a temperature below the melting point of the partially formed polymer. Thus, the polymer is actually polymerized in a solid state, with the polycondensation reaction being continued in such a state. Generally, the solid state polymeriz.ation is continued until the intrinsic viscosity reaches any desirable level, such as from about 0.60 to about 1.0, or even higher.
Desirably, the intrinsic viscosity ranges from about 0.70 to about 0.85 and preferably from about 0.70 to about 0.30. By intrinsic viscosity it is meant that the value obtained when n specific/C or LOG _ rel./C is extrapolated to zero concentration; where the relative viscosity is defined as the quotient of the solution viscosi-ty, n soln and the viscosity of the solvent n solv , i.e. ? n rel n soln.
n solv.
The specific viscosity _ sp. - rel.
are deciliters/gram using a 60/l~0 phenol/tetrachlorothane at 25C. The symbol _ is for the Greek letter eta.
IJhen the polyester resin is intended for use in contact with food, only those polyesters which are regulated by the Federal Food and Drug Administration ~ 77 should be utilized, such as set forth in Title 21, ~177.1630, for example, the polyethylenephthalate polymers, and s-lch polyesters are preferred in -the present in~ention.
r) An amber colored polyester resin is produced by utilizing specific color-imparting compounds to produce the amber color. Specifically, a yellow colored compound is utilized wit~ a blue colored compound, and a red colored compound to yield an intermediate amber color. The resin color is measured by a Gardner Colormeter, or a ~unter Lab instrument is utilized for beverage bottle measurements. The Gardner meter utilizes re~lectance (Rd) values as a measure of brightness, whereas the Hunter instrument utilizes luminance (L) as a measure of the brightness. The color hue is defined in either case by (a~ or Ib) values. Positive (a) coordinates (that is, an X axis) measures rednes$ whereas Negative (a) values indicate greeness. Positive (b) (that is, positive Y
coordinates) define yellowness whereas negative (b) values indicate blueness. The brightness (reflec-tance or luminance) of the sample is required as a point from 0 (black) to 100 (white) using both instruments. These measurements enable an approximation of the visual color used in the instrument coordinates. The measured (a) and (b) values therefore place a resin or a bottle made from the resin in one of the colored quadrants formed by their axes. In an anti-clockwise direction, star-ting at the three o'clock position, the first quadrant is red/yellow, the second quadrant is yellow/green, the third quadrant is green/blue, and the fourth quadrant is blue/red. The color amber of the resin of the present invention is in the first quadrant, that is basically a reddish-brown compound with a yellow tinge thereto.
7 ~
Regardless of the type (that is, chemical formulatlon) of polyester or the process utilized, an amber color is imparted to the polyester by utilizing specific color imparting compounds. The compounds which are utilized include yellow colorant 7 red colorant, titanium catalysts, and a blue pigment.
Additionally, the polyester can contain conventional additives such as stabili7ers, antioxidants, and the like.
The titanium catalysts can be alkyl esters having from 3 to 10 carbon atoms, or titanium chelates having from 4 to 50 carbon atoms with from 6 to 32 carbon atoms being preferred. The titanium catalysts act as a polycondensation catalyst as well as influence the shade of the polyester. Of the numerous titanates which may be utilized, the following are desirable, titanium triethanolamine, titanium acetyl acetonate, tetrabutyl titanate, tetraisopropyl titanate, and titanium glycolate. Examples of suitable titanium chelates include titanium acetyl acetonate, triethanolamine titanium chelate, lactic acid titanium chelate, tetraoctylene glycol chelate, and the li~e.
The first two chelates are often referred to as titanium alkyl esters and thus have also been previously listed as such. A specific source of chelates are the DuPont Co. under the name "TYZOR"TM.
Of the various titanium compounds, titanium triethanolamine chelate is preferred with tetrabutyl titanate being highly preferred. The amount of the titanium catalysts as titanium (Ti), based upon one million parts by weight of the final amount of polyester resin produced generally ranges from about 2 parts to about 150 parts, with from about 40 to about 70 parts being desirable and approximately 50 parts by wei~ht being preferred. The titanium catalysts can be ., ~
dded clurillg the esterification or polycondensation S tage .
A blue pigment is utilized so that in combination with the yellow and red colorant and the titanium catalysts, an amber color is produced. That is, the amber colorecl resin of the present invention resides within t~le first above-noted color quadrant. Based upon the (a) and (b) coordinates, the color utilizing a one-eighth inch thermally crystallized resin cube having a density of approximately 1.37 grams per cc is as follows: Gardner values of from about 0 to about +10 and preferably from about +2 to about +6 on the (a) scale, and from about 0 to about 12 and preferably from about 3 to about 9 on the (b) scale or coordinate. The Hun~er value ranges ~rom about -2 to about +6 and preferably from about 0 to about +3 on the (a) coordinate and from about -1 to about +9 and preferably from about -~1 to about +5 on the (b) coordinate. When a bottle, a 2 liter beverage bottle, is produced, the Hunter values generally, depending on the bottle design, range from about -~2 to about -~16 and preferably from about +8 to about +14 on the (a~ coordinate and frorn about -~1~ to about ~36 and pre~erably from about +23 to about ~-32 on the ~b) coordinate. Thus, essentially a amber color is produced or more exactly, a reddish-brown color having a yellow tlnge thereto.
The blue pigment which is utilized can be any blue pigment which produces, in combination with the other pigments and catalysts, the desired amber color.
Desirably, a pigment blue number 15 is desired, that is C.I. (color index number) of 74160. A specific example of the blue pigment which is preferably added during the esterification stage, but it can also be added during the polycondensation stage, is phthalocyanine blue Phthalocyanine blue is commercially available ~ 7~
from many suppllers such as Pa]iofastT~ ~lue manufactured by BASF, or as Monas~ralTM Blue, manufactured by DuPon-t. The amount of phthalocyanine blue utilized per million parts of the final polyester resin produced ranges from about 20 to ahout 100 parts by weight, ~ith a preferred range being from about 30 to about 50 parts by weight.
The yellow colorant which is utilized can be any pigment which produces, in combination with the other pigment and titanium catalyst, the desired amber color.
Preferably the yellow colorant is SolvapermTM Yellow G
(CAS No. 10319-14-9) which is commercially available from American Hoechst Corporation. The yellow colorant is preferably added during the esterification stage, but it can also be added during the polycondensation stage. The amount of SolvapermT~ Yellow G utilized per million parts of the final polyester resin produced ranges from about 100 to about 800 parts by weight with a preferred range being from about 250 to 600 by weight.
The red colorant which is utilized can be any pigment which produces, in combination with the other pigment and titanium catalyst, the desired amber color.
The red pigment is preferably added during the esterification stage, but it can also be added durlng the polycondensation stage. A speci-fic example of the red pigment is SolvapermT~ Red G also designated as Solvent Red 135 and is commercially available from American Hoechst Corporation. The amount of Solvaperm Red G utilized per million parts of final resin produced ranges from about 100 to 800 parts by weight with a preferred range being from 250 to 600 by weight.
The polyester resins of the present invention can be utilîzed in various conventional process apparatus such as calendars, injection molding machines, blow molding machines, extruslon machines, and the like, to , .:
~2~
produce anY desired article which has a amber color thereto. A particular area of use is a container area, such as bottles, and more particularly beverage bottles, for example liquor bottles.
The invention will be better understood by reference to the following examples.
Amber PET resins have been prepared according to the invention via batch processes (although continuous processes can also be utilized). In the following examples, titanium catalyst level used are indicated by parts per million of Ti by weight of PET. The phthalocyanine blue pigment, the red pigment and yellow pigment amount used is also in parts per million by weight of PET.
The appropriate amount of phthalocyanine blue pigment, red pigment and yellow pigment is slurried in ethylene glycol and added to a low molecular weight oligomeric mixture of PET at 270-290C in a manner as set forth in United States Patent No. ~l,020,049 to Rinehart. A portion of this esterification product mixture is transformed to another vessel where separately prepared solutions and TyzorTn TBT
~tetrabutyl titanate) in ethylene glycol are added.
The pressure of the vessel is gradually reduced to less than 1 millimeter of mercury to polycondense the mixture ~o an amber PET with the desired molecular weight (I.V.). A thermal crystallization is then carried out to yield a resin which doesn't stick together during drying prior to conversion to carbonated beverage bottles. The amounts of the various compounds as well as the color is set forth in Table I.
TABLE I
Composi~ion COLOR
GARDNER HUNTER LAB
_ a b L a b_ _ _ _ RESIN
Amorphous 2.1 1.5 -0.6 Crystalized 5.8 4.1 6.7 22.3 1.9 3.9 PREFORM (2 liter) 4.6 1.1 0.7 BOTTLE ~2 liter) 45.1 12.4 27.9 TBT = TyzorTM TBT (tetrabutyl titanate) SY = SolvapermTM Yellow G
SR ~ SolvapermT~ Red &
PB = Phthalocyanine Blue Pigment 15 Color Index No. 74160 ~ s app~rent from the above table, the bottle tencls to have a slightly different color than the crystallized resln. This is due to the fact that the bottle thickness is generally thinner than the resin S and thus imparts a different color. In any event, a suitable end color can be readily achieved.
While having described the best mode as well as the preferred embodiments of the present invention, in accordance with the patent statutes, it is noted that the invention is not limited thereto, the scope of the invention being measured by the attached claims.
Claims (25)
- The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
l. In a polyester article the improvement comprising a small amount of various color-imparting compounds contained in the polyester for imparting an amber color thereto, said compounds comprising a titanium catalyst, a blue pigment, a yellow colorant and a red colorant, the proportion of said compounds being sufficient to effect an amber color. - 2. A polyester article according to claim 1, wherein said blue pigment is phthalocyanine blue and wherein said titanium catalyst is a titanium chelate or a titanium ester.
- 3. A polyester article having an amber color according to claim 2, wherein the amount of titanium catalyst utilized is such that amount of titanium ranges from 2 to 150 parts by weight based upon one million parts of said polyester, wherein the amount of yellow colorant ranges from 100 to 800 parts by weight based upon one million parts of said polyester, wherein the amount of phthalocyanine blue ranges from 20 to 100 parts by weight based upon one million parts of said polyester and wherein said red colorant ranges from 100 to 800 parts by weight based upon one million parts of said polyester.
- 4. A polyester article according to claim 3 wherein said titanium catalysts is selected from the group consisting of titanium triethanolamine, titanium acetyl acetonate, tetrabutyl titanate, tetraisopropyl titanate, titanium glycolate, lactic acid titanium chelate, tetraoctylene glycol titanium chelate, and combinations thereof.
- 5. A polyester article according to claim 2 wherein said article is in the form of a bottle and wherein said bottle has a Hunter (a) coordinate value of from +2 to +16 and a (b) coordinate value of from +18 to +36.
- 6. A polyester article according to claim 2 wherein said article is in the form of a preform.
- 7. A polyester article according to claim 6 wherein said polyester is made from the reaction of dicarboxylic acid and diesters with a polyhydric alcohol, said dicarboxylic acid selected from the group consisting of alkyl dicarboxylic acids having a total of from 2 to 16 carbon atoms, aryl or alkyl substituted aryl dicarboxylic acids containing a total of from 8 to about 16 carbon atoms, and combinations thereof, said diester selected from the group consisting of an alkyl diester having from 4 to 20 carbon atoms, an alkyl substituted aryl ester having from 10 to 20 carbon atoms, and combinations thereof, and wherein said polyhydric alcohol is selected from the group consisting of glycols having from 2 to 12 carbon atoms, from glycol ethers containing from 4 to 12 carbon atoms, and combinations thereof.
- 8. A polyester article according to claim 7 wherein said polyester is polyethylene terephthalate.
- 9. An amber colored polyester resin comprising color imparting compounds dispersed in the polyester resin, said compounds comprising a titanium catalyst, a blue pigment, a yellow colorant and a red colorant, the proportion of said compounds being sufficient to effect an amber color.
- 10. A polyester resin according to claim 9, wherein said blue pigment is phthalocyanine blue, wherein said titanium catalyst is a titanium chelate or a titanium ester.
- 11. A polyester resin according to claim 10, wherein the amount of titanium catalyst utilized is such that amount of titanium ranges from 2 to 150 parts by weight based upon one million parts of said polyester, wherein the amount of yellow colorant ranges from 100 to 800 parts by weight based upon one million parts of said polyester, wherein the amount of phthalocyanine blue ranges from 20 to 100 parts by weight based upon one million parts of said polyester and wherein said red colorant ranges from 100 to 800 parts by weight based upon one million parts of said polyester.
- 12. A polyester resin according to claim 11 wherein said titanium catalyst is selected from the group consisting of titanium triethanolamine, titanium acetyl acetonate, tetrabutyl titanate, tetraisopropyl titanate, titanium glycolate, lactic acid titanium chelate, tetraoctylene glycol titanium chelate, and combinations thereof.
- 13. A polyester resin according to claim 12 wherein the intrinsic viscosity of said resin ranges from 0.60 to about 1Ø
- 14. A polyester resin according to claim 13 wherein said polyester is made from the reaction of dicarboxylic acid and diesters, with polyhydric alcohol, said dicarboxylic acid selected from the group consisting of alkyl dicarboxylic acids having a total of from 2 to 16 carbon atoms, aryl or alkyl substituted aryl dicarboxylic acids containing a total of 8 to 16 carbon atoms, and combinations thereof, said diester selected from the group consisting of an alkyl diester having from 4 to 20 carbon atoms, an alkyl substituted aryl ester having from 10 to 20 carbon atoms, and combinations thereof, and wherein said polyhydric alcohol is selected from the group consisting of glycols having from 2 to 12 carbon atoms, from glycol ethers containing from 4 to 12 carbon atoms, and combinations thereof.
- 15. A polyester resin according to claim 14, wherein said polyester resin is polyethylenetere-phthalate.
- 16. A polyester resin according to claim 15, wherein said resin has a Gardner (a) coordinate of from about 0 to about +10 and a (b) coordinate of from 0 to 12.
- 17. A process for making a polyester resin having an amber color comprising the steps of preparing a polyester resin, adding a titanium catalyst to said polyester resin during the preparation thereof, adding a blue pigment to said polyester resin during the preparation thereof, adding a yellow colorant to said polyester resin during the preparation thereof, adding a red colorant to said polyester resin during the preparation thereof and imparting an amber color to said resin by utilizing sufficient amounts of said titanium catalyst, said blue pigment, said yellow colorant and said red colorant.
- 18. A process according to claim 17, wherein said blue pigment is phthalocyanine blue and wherein said titanium catalyst is a titanium chelate or a titanium ester.
- 19. A process according to claim 18, wherein the amount of titanium catalyst utilized is such that amount of titanium ranges from 2 to 150 parts by weight based upon one million parts of said polyester, wherein the amount of yellow colorant ranges from 100 to 800 parts by weight based upon one million parts of said polyester, wherein the amount of phthalocyanine blue ranges from 20 to 100 parts by weight based upon one million parts of said polyester and wherein said red colorant ranges from 100 to 800 parts by weight based upon one million parts of said polyester.
- 20. A process according to claim 19, wherein said titanium catalysts is selected from the group consisting of titanium triethanolamine, titanium acetyl acetonate, tetrabutyl titanate, tetraisopropyl titanate, titanium glycolate, lactic acid titanium chelate, tetraoctylene glycol titanium chelate, and combinations thereof.
- 21. A process according to claim 20, including polymerizing said polyester resin during preparation thereof so that the intrinsic viscosity ranges from about 0.60 to about 1Ø
- 22. A process according to claim 21, wherein said titanium catalyst is tetrabutyl titanate and wherein said intrinsic viscosity of said resin ranges from 0.70 to 0.85.
- 23. A process according to claim 22, wherein said polyester is polyethylene terephthalate.
- 24. A process according to claim 22, wherein said polyester is made from the reaction of dicarboxylic acid and diesters with a polyhydric alcohol, said dicarboxylic acid selected from the group consisting of alkyl dicarboxylic acids having a total of from 2 to 16 carbon atoms, aryl or alkyl substituted aryl dicarboxylic acids containing a total of from 8 to about 16 carbon atoms, and combinations thereof, said diester selected from the group consisting of an alkyl diester having from 4 to 20 carbon atoms, an alkyl substituted aryl ester having from 10 to 20 carbon atoms, and combinations thereof, and wherein said polyhydric alcohol is selected from the group consisting of glycols having from 2 to 12 carbon atoms, from glycol ethers containing from 4 to 12 carbon atoms, and combinations thereof.
- 25. A process according to claim 24, including adding said yellow colorant, said phthalocyanine blue and red colorant during the esterification stage of preparation and including adding said titanium catalysts during the polycondensation stage of preparation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/500,499 US4654399A (en) | 1983-06-02 | 1983-06-02 | Composition and process for making an amber colored polyester |
| US500,499 | 1983-06-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1248677A true CA1248677A (en) | 1989-01-10 |
Family
ID=23989683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000454782A Expired CA1248677A (en) | 1983-06-02 | 1984-05-22 | Composition and process for making an amber colored polyester |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4654399A (en) |
| EP (1) | EP0128109B1 (en) |
| JP (1) | JPH0651828B2 (en) |
| BR (1) | BR8402406A (en) |
| CA (1) | CA1248677A (en) |
| DE (1) | DE3478115D1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100465481B1 (en) * | 2000-09-15 | 2005-01-13 | 이동권 | A Buddhist image composition For Use Amber And Process For Preparing Thereof |
| US6599596B2 (en) * | 2000-12-15 | 2003-07-29 | Wellman, Inc. | Methods of post-polymerization injection in continuous polyethylene terephthalate production |
| JP2004515621A (en) | 2000-12-15 | 2004-05-27 | ウェルマン・インコーポレーテッド | Post-polymerization injection method in the production of condensation polymers |
| US6500890B2 (en) * | 2000-12-15 | 2002-12-31 | Wellman, Inc. | Polyester bottle resins having reduced frictional properties and methods for making the same |
| US7759449B2 (en) * | 2000-12-15 | 2010-07-20 | Wellman, Inc. | Methods for introducing additives into polyethylene terephthalate |
| US6569991B2 (en) | 2000-12-15 | 2003-05-27 | Wellman, Inc. | Methods of post-polymerization extruder injection in polyethylene terephthalate production |
| US6590069B2 (en) | 2000-12-15 | 2003-07-08 | Wellman, Inc. | Methods of post-polymerization extruder injection in condensation polymer production |
| US20030039783A1 (en) | 2001-03-30 | 2003-02-27 | Stafford Steven Lee | Polyesters and polyester containers having a reduced coefficient of friction and improved clarity |
| US6787589B2 (en) * | 2002-10-31 | 2004-09-07 | Eastman Chemical Company | Amber polyester compositions and container articles produced therefrom |
| CN100378149C (en) | 2003-01-31 | 2008-04-02 | M&G聚合物意大利有限公司 | Article comprising light absorbent composition to mask visual haze and related methods |
| AU2004254229B2 (en) * | 2003-07-07 | 2009-12-17 | Teijin Frontier Co., Ltd. | Orthochromatic polyester resin composition and molding product thereof |
| US7368523B2 (en) * | 2004-11-12 | 2008-05-06 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing titanium nitride particles |
| US20060051542A1 (en) * | 2004-09-03 | 2006-03-09 | Zhiyong Xia | Polyester polymer and copolymer compositions containing metallic molybdenum particles |
| US7662880B2 (en) * | 2004-09-03 | 2010-02-16 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing metallic nickel particles |
| US20060105129A1 (en) * | 2004-11-12 | 2006-05-18 | Zhiyong Xia | Polyester polymer and copolymer compositions containing titanium carbide particles |
| US7300967B2 (en) * | 2004-11-12 | 2007-11-27 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing metallic titanium particles |
| US7262476B2 (en) * | 2004-11-30 | 2007-08-28 | Agere Systems Inc. | Semiconductor device having improved power density |
| US20060122300A1 (en) * | 2004-12-07 | 2006-06-08 | Zhiyong Xia | Polyester polymer and copolymer compositions containing steel particles |
| JP2006176627A (en) * | 2004-12-22 | 2006-07-06 | Teijin Fibers Ltd | Catalyst for polyester polymerization, polyester obtained using the same and its manufacturing method |
| US20060177614A1 (en) * | 2005-02-09 | 2006-08-10 | Zhiyong Xia | Polyester polymer and copolymer compositions containing metallic tantalum particles |
| US20060222795A1 (en) * | 2005-03-31 | 2006-10-05 | Howell Earl E Jr | Polyester polymer and copolymer compositions containing particles of one or more transition metal compounds |
| US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
| US7776942B2 (en) | 2005-09-16 | 2010-08-17 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron |
| US7745512B2 (en) | 2005-09-16 | 2010-06-29 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing carbon-coated iron particles |
| US7655746B2 (en) * | 2005-09-16 | 2010-02-02 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
| US20070260002A1 (en) * | 2006-05-04 | 2007-11-08 | Zhiyong Xia | Titanium nitride particles, methods of making them, and their use in polyester compositions |
| US20080058495A1 (en) * | 2006-09-05 | 2008-03-06 | Donna Rice Quillen | Polyester polymer and copolymer compositions containing titanium and yellow colorants |
| US9725602B2 (en) * | 2006-12-19 | 2017-08-08 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for preparing an organic film at the surface of a solid support under non-electrochemical conditions, solid support thus obtained and preparation kit |
| DE102007028348A1 (en) * | 2007-06-20 | 2008-12-24 | Mitsubishi Polyester Film Gmbh | Amber-colored polyester film with particular suitability for metallization and steel lamination |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3056818A (en) * | 1955-10-13 | 1962-10-02 | Goodrich Co B F | Titanium and zirconium esterification catalysts |
| US3406153A (en) * | 1962-05-16 | 1968-10-15 | Du Pont | Process of producing polyethylene terephthalate |
| FR1386181A (en) * | 1964-03-26 | 1965-01-15 | Zimmer Verfahrenstechnik | Process for preparing polyesters with high thermal stability |
| AT261220B (en) * | 1965-05-19 | 1968-04-10 | Alpine Chemische Ag | Process for the production of new copolyesters |
| US3441540A (en) * | 1965-06-28 | 1969-04-29 | Engels Chemiefaserwerk Veb | Method for the production of highmolecular polyesters or co-polyesters |
| DE1953706C3 (en) * | 1968-10-25 | 1978-10-26 | Kanebo, Ltd., Tokio | Process for the production of polyesters |
| US3644291A (en) * | 1968-11-20 | 1972-02-22 | Fmc Corp | Titanium compounds as polycondensation catalysts in preparation of linear polyesters |
| US3644270A (en) * | 1969-04-21 | 1972-02-22 | Du Pont | Process for coloring polyesters with rhodamine xanthene or benzophenyl safranine dyes |
| GB1326941A (en) * | 1970-07-10 | 1973-08-15 | Ici Ltd | Coloured filaments |
| US3870688A (en) * | 1971-05-12 | 1975-03-11 | Toyo Boseki | Titanium tartrate catalyzed polyesterification |
| US4260735A (en) * | 1980-02-12 | 1981-04-07 | Allied Chemical Corporation | Catalytic process for preparation of polyesters |
| US4374949A (en) * | 1980-10-27 | 1983-02-22 | The Goodyear Tire & Rubber Company | Composition and process for making a green colored polyester |
| US4365031A (en) * | 1980-10-27 | 1982-12-21 | The Goodyear Tire & Rubber Company | Composition and process for making a green colored polyester |
| JPS5853943A (en) * | 1981-09-25 | 1983-03-30 | Sanyo Kako Kk | Coloring of polyethylene terephthalate |
| JPS58125743A (en) * | 1982-01-20 | 1983-07-26 | Teijin Ltd | Polyester molded article colored in green color, and its preparation |
| JPS58180552A (en) * | 1982-04-19 | 1983-10-22 | Dainichi Seika Kogyo Kk | Colored polyethylene terephthalate resin composition |
-
1983
- 1983-06-02 US US06/500,499 patent/US4654399A/en not_active Expired - Lifetime
-
1984
- 1984-05-18 BR BR8402406A patent/BR8402406A/en not_active IP Right Cessation
- 1984-05-22 CA CA000454782A patent/CA1248677A/en not_active Expired
- 1984-05-30 JP JP59110655A patent/JPH0651828B2/en not_active Expired - Lifetime
- 1984-06-01 EP EP84630084A patent/EP0128109B1/en not_active Expired
- 1984-06-01 DE DE8484630084T patent/DE3478115D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3478115D1 (en) | 1989-06-15 |
| EP0128109A3 (en) | 1986-05-28 |
| BR8402406A (en) | 1985-04-02 |
| EP0128109B1 (en) | 1989-05-10 |
| JPH0651828B2 (en) | 1994-07-06 |
| US4654399A (en) | 1987-03-31 |
| JPS604549A (en) | 1985-01-11 |
| EP0128109A2 (en) | 1984-12-12 |
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