US20120190780A1 - Additive compositions and thermoplastic polymer compositions comprising the same - Google Patents

Additive compositions and thermoplastic polymer compositions comprising the same Download PDF

Info

Publication number
US20120190780A1
US20120190780A1 US13/013,277 US201113013277A US2012190780A1 US 20120190780 A1 US20120190780 A1 US 20120190780A1 US 201113013277 A US201113013277 A US 201113013277A US 2012190780 A1 US2012190780 A1 US 2012190780A1
Authority
US
United States
Prior art keywords
thermoplastic polymer
polymer composition
ppm
value
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/013,277
Other languages
English (en)
Inventor
Todd D. Danielson
Jamie B. Myers
Jennifer S. Morgan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Milliken and Co
Original Assignee
Milliken and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45496291&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20120190780(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Milliken and Co filed Critical Milliken and Co
Priority to US13/013,277 priority Critical patent/US20120190780A1/en
Priority to BR112013018623A priority patent/BR112013018623A2/pt
Priority to EP11809023.2A priority patent/EP2668229B1/en
Priority to AU2011356604A priority patent/AU2011356604C1/en
Priority to CN201180068470.6A priority patent/CN103391966B/zh
Priority to KR1020207028549A priority patent/KR102330795B1/ko
Priority to KR1020187026006A priority patent/KR102165551B1/ko
Priority to KR1020157027192A priority patent/KR20150117714A/ko
Priority to SG2013051057A priority patent/SG191809A1/en
Priority to KR1020217037761A priority patent/KR102477402B1/ko
Priority to JP2013551970A priority patent/JP5897604B2/ja
Priority to PCT/US2011/065987 priority patent/WO2012102805A1/en
Priority to RU2013135666/05A priority patent/RU2553300C2/ru
Priority to KR1020137022179A priority patent/KR20130108669A/ko
Assigned to MILLIKEN & COMPANY reassignment MILLIKEN & COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DANIELSON, TODD D., MORGAN, JENNIFER S., MYERS, Jamie B.
Publication of US20120190780A1 publication Critical patent/US20120190780A1/en
Priority to JP2016001897A priority patent/JP2016166325A/ja
Priority to US15/485,916 priority patent/US10800902B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575—Six-membered rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • 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
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix

Definitions

  • thermoplastic polymers have become ubiquitous in the modern world.
  • the versatility of thermoplastic polymers and the relative ease with which they can be processed into myriad different forms have contributed to their rise to ubiquity.
  • This versatility is partly attributable to the nature of the thermoplastic polymers themselves, but at least a portion of this versatility is attributable to the development of additives that permit the modification of the physical properties of these polymers.
  • polypropylene homopolymers and polypropylene copolymers which are typically only slightly translucent, can be made more translucent or even virtually transparent using a class of additives known as clarifying agents.
  • clarifying agents a class of additives known as clarifying agents.
  • the development and use of such clarifying agents have opened up an entirely new range of applications for polypropylene polymers, a range of applications that was previously reserved for those polymers which are naturally or more readily made translucent or transparent (e.g., polystyrene).
  • clarifying agents have made it possible to use polypropylene polymers in transparent packaging and containers.
  • thermoplastic polymers While the development and use of certain additives (e.g., clarifying agents) have enabled improvements in certain physical properties of thermoplastic polymers, there remains room for improvement. In particular, Applicants believe that a need remains for combinations of additives that will further improve the aesthetic qualities of thermoplastic polymers, such as clarified polypropylene polymers. This application and the inventions described herein seek to address this need.
  • additives e.g., clarifying agents
  • the invention generally provides additive compositions suitable for addition to thermoplastic polymers, thermoplastic polymer compositions containing a clarifying agent and at least one coloring agent, and methods for making such thermoplastic polymer compositions.
  • the additive compositions comprise a clarifying agent and a relatively low level of at least one coloring agent, where the type and amount of coloring agent is selected so that a thermoplastic polymer composition containing the additive composition exhibits CIE L*, a*, and b* values falling within a specified color space.
  • thermoplastic polymer compositions of the invention contain a clarifying agent and at least one coloring agent, where the type and amount of coloring agent(s) is selected so that the thermoplastic polymer composition exhibits CIE L*, a*, and b* values falling within a specified color space.
  • this color space can be defined in terms of either the absolute L*, a*, and b* values of the thermoplastic polymer composition or the change in the a* and b* values exhibited by the thermoplastic polymer composition relative to a control thermoplastic polymer composition that does not contain the coloring agent(s).
  • the compositions of the invention are designed so that the thermoplastic polymer composition (e.g., a thermoplastic polymer composition containing the additive composition or a thermoplastic polymer composition containing the recited clarifying agent and coloring agent(s)) is not perceived to be substantially colored.
  • the compositions of the invention generally employ levels of coloring agent(s) that are substantially lower than those used in polymer compositions that are designed to be colored.
  • compositions are based upon Applicant's discovery that clarified thermoplastic polymers containing relatively small amounts of coloring agent(s) (e.g., amounts and types of coloring agent(s) which produce a polymer falling within a specified portion of the CIE L*a*b* color space) are generally perceived as more visually appealing than clarified thermoplastic polymers that do not contain the coloring agent(s).
  • these thermoplastic polymers are perceived and described as appearing more transparent (e.g., exhibiting less haze) than a clarified thermoplastic polymer that does not contain the coloring agent(s), even though there is no measurable decrease in the haze of the thermoplastic polymer.
  • the invention provides a method for producing a thermoplastic polymer composition, the method comprising the steps of:
  • thermoplastic polymer (a) providing a thermoplastic polymer
  • thermoplastic polymer composition (c) mixing the thermoplastic polymer and the additive composition to produce a thermoplastic polymer composition
  • thermoplastic polymer and the additive composition are separately provided; wherein the amount of clarifying agent in the thermoplastic polymer composition is from about 100 ppm to about 5,000 ppm based on the total weight of the thermoplastic polymer composition; wherein the amount of coloring agent present in the thermoplastic polymer composition is sufficient to produce a thermoplastic polymer composition exhibiting a ⁇ a* value and a ⁇ b* value satisfying each of the following inequalities
  • ⁇ b* is not zero; wherein the ⁇ a* value and the ⁇ b* value are calculated by measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from a control thermoplastic polymer composition, measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from the thermoplastic polymer composition, and subtracting the a* and b* values for the plaque made from the control thermoplastic polymer composition from the a* and b* values for the plaque made from the thermoplastic polymer composition; and wherein the control thermoplastic polymer composition contains the thermoplastic polymer and the clarifying agent but does not contain the coloring agent.
  • the invention provides a method for producing a thermoplastic polymer composition, the method comprising the steps of:
  • thermoplastic polymer (a) providing a thermoplastic polymer
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, alkenyl groups, aryl groups, and halogens; and wherein R 11 is a hydroxyalkyl group selected from the group consisting of —CH 2 OH and —CHOHCH 2 OH;
  • thermoplastic polymer composition (d) mixing the thermoplastic polymer, the clarifying agent, and the coloring agent to produce a thermoplastic polymer composition
  • thermoplastic polymer, the clarifying agent, and the coloring agent are each separately provided; wherein the amount of clarifying agent present in the thermoplastic polymer composition is from about 100 ppm to about 5,000 ppm based on the total weight of the thermoplastic polymer composition; wherein the amount of coloring agent in the thermoplastic polymer composition is sufficient to produce a thermoplastic polymer composition exhibiting a ⁇ a* value and a ⁇ b* value satisfying each of the following inequalities
  • ⁇ b* is not zero; wherein the ⁇ a* value and the ⁇ b* value are calculated by measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from a control thermoplastic polymer composition, measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from the thermoplastic polymer composition, and subtracting the a* and b* values for the plaque made from the control thermoplastic polymer composition from the a* and b* values for the plaque made from the thermoplastic polymer composition; and wherein the control thermoplastic polymer composition contains the thermoplastic polymer and the clarifying agent but does not contain the coloring agent.
  • the invention provides an additive composition consisting essentially of:
  • a clarifying agent selected from the group consisting of trisamides, aluminum 2,2′-methylenebis-(4,6-di-tert-butylphenyl) phosphate, lithium 2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate, monocarboxylate compounds, and acetal compounds conforming to the structure of Formula (I)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, alkenyl groups, aryl groups, and halogens; and wherein R 11 is a hydroxyalkyl group selected from the group consisting of —CH 2 OH and —CHOHCH 2 OH; and
  • coloring agent is present in the additive composition in an amount such that a thermoplastic polymer composition exhibits a ⁇ a* value and a ⁇ b* value satisfying each of the following inequalities
  • thermoplastic polymer composition comprises a thermoplastic polymer and the additive composition in an amount sufficient to provide about 100 ppm to about 5,000 ppm of the clarifying agent in the thermoplastic polymer composition, based on the total weight of the thermoplastic polymer composition; and wherein the ⁇ a* value and the ⁇ b* value are calculated by measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from a control thermoplastic polymer composition, measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from the thermoplastic polymer composition, and subtracting the a* and b* values for the plaque made from the control thermoplastic polymer composition from the a* and b* values for the plaque made from the thermoplastic polymer composition; and wherein the control thermoplastic polymer composition contains the thermoplastic polymer and the clarifying agent but does not contain the coloring agent.
  • the invention provides a method for producing a thermoplastic polymer composition, the method comprising the steps of:
  • thermoplastic polymer (a) providing a thermoplastic polymer
  • thermoplastic polymer composition (c) mixing the thermoplastic polymer and the additive composition to produce a thermoplastic polymer composition
  • thermoplastic polymer and the additive composition are separately provided; wherein the amount of clarifying agent in the thermoplastic polymer composition is from about 100 ppm to about 5,000 ppm based on the total weight of the thermoplastic polymer composition; wherein the amount of coloring agent present in the thermoplastic polymer composition is sufficient to produce a thermoplastic polymer composition exhibiting an a* value and a b* value satisfying each of the following inequalities
  • a* value and the b* value are determined by measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from the thermoplastic polymer composition.
  • the invention provides a method for producing a thermoplastic polymer composition, the method comprising the steps of:
  • thermoplastic polymer (a) providing a thermoplastic polymer
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, alkenyl groups, aryl groups, and halogens; and wherein R 11 is a hydroxyalkyl group selected from the group consisting of —CH 2 OH and —CHOHCH 2 OH;
  • thermoplastic polymer composition (d) mixing the thermoplastic polymer, the clarifying agent, and the coloring agent to produce a thermoplastic polymer composition
  • thermoplastic polymer, the clarifying agent, and the coloring agent are each separately provided; wherein the amount of clarifying agent present in the thermoplastic polymer composition is from about 100 ppm to about 5,000 ppm based on the total weight of the thermoplastic polymer composition; wherein the amount of coloring agent in the thermoplastic polymer composition is sufficient to produce a thermoplastic polymer composition exhibiting an a* value and a b* value satisfying each of the following inequalities
  • a* value and the b* value are determined by measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from the thermoplastic polymer composition.
  • the invention provides an additive composition consisting essentially of:
  • a clarifying agent selected from the group consisting of trisamides, aluminum 2,2′-methylenebis-(4,6-di-tert-butylphenyl) phosphate, lithium 2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate, monocarboxylate compounds, and acetal compounds conforming to the structure of Formula (I)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, alkenyl groups, aryl groups, and halogens; and wherein R 11 is a hydroxyalkyl group selected from the group consisting of —CH 2 OH and —CHOHCH 2 OH; and
  • coloring agent is present in the additive composition in an amount such that a thermoplastic polymer composition exhibits a a* value and a b* value satisfying each of the following inequalities
  • thermoplastic polymer composition comprises a thermoplastic polymer and the additive composition in an amount sufficient to provide about 100 ppm to about 5,000 ppm of the clarifying agent in the thermoplastic polymer composition, based on the total weight of the thermoplastic polymer composition; and wherein the a* value and the b* value are determined by measuring an a* value and a b* value exhibited by a 1.27 mm (50 mil) plaque made from the thermoplastic polymer composition.
  • FIG. 1 is a plot of the ⁇ a* and ⁇ b* values for the polymer compositions described in the Example.
  • FIG. 2 is a plot of the a* and b* values for the polymer compositions described in the Example.
  • thermoplastic polymers suitable for addition to thermoplastic polymers, thermoplastic polymer compositions containing a clarifying agent and at least one coloring agent, and methods for making such thermoplastic polymer compositions.
  • thermoplastic polymer utilized in the invention can be any suitable thermoplastic polymer.
  • thermoplastic polymer refers to a polymeric material that will melt upon exposure to sufficient heat to form a flowable liquid and will return to a solidified state upon sufficient cooling.
  • the thermoplastic polymer is a polyolefin.
  • the thermoplastic polymer can be any suitable polyolefin, such as a polypropylene, a polyethylene, a polybutylene, and a poly(4-methyl-1-pentene), and combinations or mixtures thereof.
  • the thermoplastic polymer is a polyolefin selected from the group consisting of polypropylene homopolymers (e.g., atactic polypropylene, isotactic polypropylene, and syndiotactic polypropylene), polypropylene copolymers (e.g., polypropylene random copolymers), and mixtures thereof.
  • Suitable polypropylene copolymers include, but are not limited to, random copolymers made from the polymerization of propylene in the presence of a comonomer selected from the group consisting of ethylene, but-1-ene (i.e., 1-butene), and hex-1-ene (i.e., 1-hexene).
  • the comonomer can be present in any suitable amount, but typically is present in an amount of about 10 wt. % or less (e.g., about 1 to about 7 wt. %, or about 1 to about 4.5 wt. %).
  • the clarifying agent utilized in the additive compositions and methods of the invention can be any suitable clarifying agent.
  • suitable clarifying agents include, but are not limited to, trisamides, bisphenol phosphates, monocarboxylate compounds, and acetal compounds.
  • suitable trisamide clarifying agents include, but are not limited to, amide derivatives of benzene-1,3,5-tricarboxylic acid, derivatives of N-(3,5-bis-formylamino-phenyl)-formamide (e.g., N-[3,5-bis-(2,2-dimethyl-propionylamino)-phenyl]-2,2-dimethyl-propionamide), derivatives of 2-carbamoyl-malonamide (e.g., N,N′-bis-(2-methyl-cyclohexyl)-2-(2-methyl-cyclohexylcarbamoyl)-malonamide), and combinations thereof.
  • Suitable bisphenol phosphate clarifying agents include 2,2′-methylenebis-(4,6-di-tert-butylphenyl) phosphate salts, such as aluminum 2,2′-methylenebis-(4,6-di-tert-butylphenyl) phosphate, lithium 2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate, and combinations thereof.
  • Suitable acetal clarifying agents include the acetal compounds produced by the condensation reaction of a polyhydric alcohol and an aromatic aldehyde. Polyhydric alcohols suitable for producing such acetal clarifying agents include, but are not limited to, acyclic polyols, such as xylitol and sorbitol.
  • Aromatic aldehydes suitable for producing such acetal clarifying agents include, but are not limited to, aromatic aldehydes containing a single aldehyde group with the remaining positions on the aromatic ring being either unsubstituted or substituted.
  • suitable aromatic aldehydes include benzaldehyde and substituted benzaldehydes (e.g., 3,4-dimethyl-benzaldehyde).
  • the acetal compound produced by the above-described reaction can be a mono-acetal, di-acetal, or tri-acetal compound (i.e., a compound containing one, two, or three acetal groups, respectively), with the di-acetal compounds being preferred.
  • the clarifying agent is selected from the group consisting of acetal compounds conforming to the structure of Formula (I)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, alkenyl groups, aryl groups, and halogens.
  • R 11 is a hydroxyalkyl group selected from the group consisting of —CH 2 OH and —CHOHCH 2 OH.
  • the acetal compound is a compound of Formula (I) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each hydrogen and R 11 is —CHOHCH 2 OH.
  • the acetal compound is a compound of Formula (I) in which R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 9 , and R 10 are each hydrogen, R 3 and R 8 are each a methyl group, and R 11 is —CHOHCH 2 OH.
  • the acetal compound is a compound of Formula (I) in which R 1 , R 4 , R 5 , R 6 , R 7 , and R 10 are each hydrogen, R 2 , R 3 , R 8 , and R 9 are each a methyl group, and R 11 is —CHOHCH 2 OH.
  • the compositions of the invention can contain any suitable mixture of the clarifying agents described above.
  • the composition of the invention can contain a mixture of two or more different acetal compounds conforming to the structure of Formula (I), such as a mixture of any of the specific acetal compounds described above.
  • the clarifying agent can be present in the compositions of the invention in any suitable amount.
  • the suitable amount of the clarifying agent will depend upon several factors, such as the identity of the particular clarifying agent, the particular polymer that is to be clarified using the clarifying agent, and the desired level of clarity and/or haze for the finished polymer composition.
  • the clarifying agent is present in the thermoplastic polymer composition in an amount of about 100 ppm to about 5,000 ppm based on the total weight of the thermoplastic polymer composition.
  • the clarifying agent is an acetal compound conforming to the structure of Formula (I)
  • the clarifying agent is present in the thermoplastic polymer composition in an amount of about 1,000 ppm to about 2,500 ppm based on the total weight of the thermoplastic polymer composition.
  • compositions of the invention contain at least one coloring agent.
  • Suitable coloring agents include, but are not limited to, pigments, dyes, polymeric colorants, and mixtures thereof.
  • the term “polymeric colorant” refers to a colorant comprising a chromophore and at least one oligomeric or polymer constituent bound to the chromophore.
  • Suitable polymeric colorants include, but are not limited to, the polymeric colorants sold by Milliken & Company.
  • the dye can be any suitable dye, such as an acid dye, a solvent dye, a vat dye, or mixtures thereof.
  • Suitable dyes include, but are not limited to, Acid Blue 9, Acid Blue 74, Solvent Blue 97, Vat Blue 6, and mixtures or combinations thereof.
  • the coloring agent can comprise a mixture of Vat Blue 6 and Acid Blue 74.
  • the coloring agent comprises a pigment. Suitable pigments include, but are not limited to, Pigment Blue 29, Pigment Blue 63, Pigment Violet 15, and mixtures thereof.
  • compositions of the invention contain a relatively small amount of the coloring agent.
  • the amount of coloring agent present in the thermoplastic polymer compositions of the invention is sufficiently low that most observers would describe the polymer composition or any article made therefrom as being not substantially colored.
  • the hue imparted to the polymer composition or an article made therefrom by the coloring agent may be perceptible only after the polymer composition or article is compared to a similar composition or article that does not contain the coloring agent.
  • the amount of coloring agent present in the compositions of the invention is best quantified and bound by specifying the CIE L*a*b* color space of a 1.27 mm (50 mil) thick plaque made using the composition (i.e., a plaque made from a thermoplastic polymer composition containing the additive composition of the invention or a plaque made from the thermoplastic polymer composition of the invention).
  • a composition containing an amount of the coloring agent sufficient to produce a plaque having certain L*, a*, and b* values would be perceived as visually appealing (both by itself and also as compared to a control that did not contain the coloring agent) and yet would still be perceived and described as not substantially colored.
  • articles produced from such a composition are often perceived to have lower haze or greater clarity than similar articles produced from a composition that does not contain the coloring agent, even though haze measurements of such articles reveal that the haze values are not lower.
  • the amount of coloring agent can be expressed in terms of the change in the a* and b* values relative to a control, or the amount of the coloring agent can be expressed in terms of the absolute L*, a*, and b* values exhibited by a plaque made using the thermoplastic polymer composition.
  • the ⁇ a* and ⁇ b* values are calculated by measuring the a* and b* values exhibited by a 1.27 mm (50 mil) thick plaque made from a control thermoplastic polymer composition and measuring the a* and b* values exhibited by a 1.27 mm (50 mil) thick plaque made from the thermoplastic polymer composition of the invention (i.e., the thermoplastic polymer composition made by a method of the invention or a thermoplastic polymer composition made by adding an additive composition of the invention to a thermoplastic polymer).
  • the control thermoplastic polymer composition is substantially identical to the thermoplastic polymer composition of the invention, differing only in the fact that it does not contain the coloring agent(s).
  • the a* and b* values for the plaque made from the control thermoplastic polymer composition are then respectively subtracted from the a* and b* values for the plaque made from the thermoplastic polymer composition of the invention to yield the ⁇ a* and ⁇ b* values resulting from the presence of the coloring agent in the composition of the invention.
  • Applicants have found that the compositions of the invention have ⁇ a* and ⁇ b* values satisfying each of the following inequalities
  • the ⁇ a* and ⁇ b* values satisfy each of the following inequalities
  • the ⁇ a* and ⁇ b* values satisfy each of the following inequalities
  • the amount of the coloring agent can be expressed in terms of the absolute L*, a*, and b* values exhibited by a plaque made using the thermoplastic polymer composition.
  • the L*, a*, and b* values are determined by measuring the a* and b* values exhibited by a 1.27 mm (50 mil) thick plaque made from the thermoplastic polymer composition of the invention (i.e., the thermoplastic polymer composition made by a method of the invention or a thermoplastic polymer composition made by adding an additive composition of the invention to a thermoplastic polymer).
  • the compositions of the invention have a* and b* values satisfying each of the following inequalities
  • the a* and b* values satisfy each of the following inequalities
  • the a* and b* values satisfy each of the following inequalities
  • the inequalities for both the change in a* and b* values and the absolute a* and b* values do not specify the L* values of the plaque produced using the thermoplastic polymer composition.
  • the plaques made from the compositions of the invention can exhibit any suitable L* value. In certain possibly preferred embodiments, the plaques exhibit an L* value of about 88 or greater.
  • the L*, a*, and b* values of the compositions can be measured using any suitable technique.
  • the L*, a*, and b* values typically are measured using a spectrophotometer.
  • the L*, a*, and b* values can be measured using the spectrophotometer in reflectance mode with a large area view under a cool white fluorescent light source (a UV filter is used to exclude UV light from the light source) and a 10° observer with specular reflectance included in the measurement.
  • the measurements can be taken with the spectrophotometer's white calibration tile placed behind the sample.
  • a measurement can be taken on at least five separate 50.8 mm ⁇ 76.2 mm ⁇ 1.27 mm (2.00 inch ⁇ 3.00 inch ⁇ 0.05 inch) test plaques made from the polymer composition, and the measurements can be averaged to yield a single set of L*, a*, and b* values for the polymer composition from which the plaques are made.
  • the above-described procedure was used by Applicants to determine the L*, a*, and b* values during their experiments and, therefore, the L*, a*, and b* values preferably are determined using this procedure.
  • the invention provides an additive composition consisting essentially of a clarifying agent and a coloring agent.
  • the term “consisting essentially of” is used to distinguish the additive composition from a thermoplastic polymer to which the additive composition has been added.
  • the term is used to indicate that the additive composition is formulated in such a way that it is intended to be added to a thermoplastic polymer, rather than being used by itself in the fabrication of finished articles.
  • the term “consisting essentially of” indicates that, if a thermoplastic polymer is present in the additive composition, the relative amount of thermoplastic polymer present in the additive composition is substantially less than the amount of thermoplastic polymer that is present in a “finished” polymer composition that is to be used in molding or other processes for producing an article.
  • the additive composition contains about 90 wt. % or less (e.g., about 85 wt. % or less or about 80 wt. % or less) thermoplastic polymer based on the total weight of the additive composition. In certain other embodiments, the additive composition contains about 25 wt. % or less (e.g., about 20 wt.
  • thermoplastic polymer based on the total weight of the additive composition.
  • the term “consisting essentially of” is not intended to exclude the presence of other additives that are typically used in thermoplastic polymers, such as nucleating agents, antioxidants, acid scavengers, slip agents, antistatic agents, optical brighteners, and polymer processing aids.
  • the additive composition of the invention can be a masterbatch containing the clarifying agent, the coloring agent, a carrier resin, and, optionally, other additives, or the additive composition can be a non-dusting blend (NDB) containing the clarifying agent, the coloring agent, and, optionally, other additives.
  • NDB non-dusting blend
  • the invention provides methods for producing thermoplastic polymer compositions.
  • the method comprises the steps of providing a thermoplastic polymer, providing an additive composition comprising at least one clarifying agent and a coloring agent, and mixing the thermoplastic polymer and the additive composition to produce a thermoplastic polymer composition.
  • the thermoplastic polymer, the clarifying agent, and the coloring agent can be any of those described above.
  • the thermoplastic polymer and the additive composition are separately provided. In other words, the thermoplastic polymer and the additive composition are provided in separate forms or compositions that are not mixed together until the recited mixing step.
  • thermoplastic polymer can be provided in a composition comprising other additives typically used in polymer processing, such as antioxidants, acid scavengers, slip agents, and polymer processing aids.
  • additive composition can also comprise other additives typically used in polymer processing, such as those described above.
  • the method comprises the steps of providing a thermoplastic polymer, providing a clarifying agent, providing a coloring agent, and mixing the thermoplastic polymer, the clarifying agent, and the coloring agent to produce a thermoplastic polymer composition.
  • the thermoplastic polymer, the clarifying agent, and the coloring agent can be any of those described above.
  • the thermoplastic polymer, the clarifying agent, and the coloring agent are separately provided.
  • the thermoplastic polymer, the clarifying agent, and the coloring agent are provided in separate forms or compositions that are not mixed together until the recited mixing step.
  • the thermoplastic polymer can be provided in a composition comprising other additives typically used in polymer processing.
  • the clarifying agent and the coloring agent can be contained in separate compositions comprising other additives typically used in polymer processing.
  • each of the method embodiments described above involves a mixing step.
  • the separate components can be mixed using any suitable technique or apparatus.
  • the components can be mixed in a paddle blender, ribbon blender, double cone blender, vertical screw mixer (e.g., Nauta mixer), plough mixer, or high shear mixer.
  • the mixing apparatus listed above can be operated in either a batch or continuous mode and, therefore, the mixing step can be performed in either a batchwise or continuous fashion.
  • the components can be mixed for any suitable amount of time, but generally the components are mixed until they are substantially uniformly blended.
  • thermoplastic polymer compositions according to the invention and certain properties of such polymer compositions.
  • Several different polymer compositions were prepared using an 11 MFR (Melt Flow Rate) Ziegler-Natta catalyzed polypropylene random copolymer as the thermoplastic polymer.
  • Each polymer composition labeled as “Sample” was prepared by incorporating into the thermoplastic polymer 1800 ppm of a clarifying agent (i.e., Millad® 3988i clarifying agent from Milliken & Company), a standard stabilization package (i.e., 500 ppm Irganox 1010, 1000 ppm Irgafos 168, and 800 ppm calcium stearate), and one or more coloring agents.
  • a clarifying agent i.e., Millad® 3988i clarifying agent from Milliken & Company
  • standard stabilization package i.e., 500 ppm Irganox 1010, 1000 ppm Irgafos
  • each polymer composition The particular coloring agent(s) used in each polymer composition and the amount of such coloring agent(s) are set forth in Tables 1, 2, and 3 below.
  • Control polymer compositions (labeled “Control”) were also prepared and contained the same thermoplastic polymer, the same additive package, and 1800 ppm of the clarifying agent. Thus, the only difference between the “Sample” polymer compositions and the “Control” polymer compositions is the presence of the coloring agent(s).
  • a blend of the clarifying agent and the desired coloring agent(s) was first prepared. This blend contained a higher level of the coloring agent(s) than was ultimately desired, so that it could be more easily measured and blended with the polymer.
  • the desired coloring agent(s) were added to one hundred (100.0) gram batches of the clarifying agent to yield a mixture containing approximately 5.2632 wt. % coloring agent.
  • the resulting mixture was then blended on a Cuisinart® Classic food processor (Model DFP-14BCN) for approximately 2 minutes.
  • the resulting mixture was further diluted by adding additional clarifying agent to yield a mixture containing approximately 1.3699 wt. % coloring agent and then blended on the Cuisinart® Classic food processor (Model DFP-14BCN) for approximately 2 minutes.
  • the resulting blend of clarifying agent and coloring agent(s) was then added to the polymer to produce the thermoplastic polymer composition.
  • the required amount of the clarifying agent and coloring agent(s) blend was mixed with 1000 grams of the polypropylene polymer, the standard stabilization package, and an additional amount of the clarifying agent.
  • the amount of additional clarifying agent used brought the total of amount of clarifying agent in the polymer composition up to 1800 ppm. All of the components were mixed using a KitchenAid® Artisan® 5 quart tilt-head mixer set on the lowest setting (Stir) for approximately 5 minutes.
  • the resulting mixture was then melt compounded on a Deltaplast 1 inch diameter, L/D 30:1 single screw extruder with a temperature profile ramping up to 230° C.
  • the melt-compounded polymer composition was then injection molded using a 40-ton ARBURG ALLROUNDER 221K injection molding machine to produce twenty-five 50.8 mm ⁇ 76.2 mm ⁇ 1.27 mm (2.00 inch ⁇ 3.00 inch ⁇ 0.05 inch) test plaques with a 230° C. flat profile barrel temperature and no backpressure. These plaques were then used to conduct the CIE L*a*b* measurements described below and were also used during the panel evaluations described below.
  • Coloring Agent(s) and Coloring Agent Loadings used in Control 1 and Samples 1-61 Coloring Agent Sample Coloring Agent(s) Loadings Control 1 None — 1 Pigment Blue 29/ 4.5 ppm/3 ppm Pigment Violet 15 2 Pigment Blue 29/ 4.05 ppm/2.7 ppm Pigment Violet 15 3 Pigment Blue 29/ 9 ppm/6 ppm Pigment Violet 15 4 Acid Blue 74 25 ppm 5 Acid Blue 74 100 ppm 6 Acid Blue 9 25 ppm 7 Vat Blue 6 2 ppm 8 Solvent Blue 97 2 ppm 9 Pigment Blue 63 2 ppm 10 Pigment Blue 29 2 ppm 11 Pigment Blue 29 25 ppm 12 Acid Blue 9/Food Red 7/ 0.36 ppm/0.18 ppm/ Food Yellow 5 0.45 ppm 13 Solvent Black 7 0.54 ppm 14 Solvent Black 7 2 ppm 15 Solvent Black 7 25 ppm 16 Acid Blue 74 2 ppm 17 Acid Blue 9 1.8 ppm 18 Acid Blue 9 2 — 1 Pig
  • Coloring Agent(s) and Coloring Agent Loadings used in Control 2 and Samples 62-107.
  • CIE L*a*b* color values were determined for each sample using a GretagMacBeth Color-Eye 7000A spectrophotometer. Measurements were taken in reflectance mode with a large area view using a cool white fluorescent light source and a 10° observer with specular reflectance included in the measurement. A UV filter was used to exclude UV light from the light source. The spectrophotometer's white calibration tile was placed behind the test plaques during the measurements. Measurements were taken on five separate 50.8 mm ⁇ 76.2 mm ⁇ 1.27 mm (2.00 inch ⁇ 3.00 inch ⁇ 0.05 inch) test plaques made using the polymer composition, and the five measurements were averaged to yield a single set of L*, a*, and b* values for the polymer composition.
  • the L*, a*, and b* values for each sample are reported in Table 4, 5, or 6 below.
  • the ⁇ L*, ⁇ a*, and ⁇ b* values for each sample are also reported in Table 4, 5, or 6 below.
  • the ⁇ L*, ⁇ a*, and ⁇ b* values were determined by respectively subtracting the L*, a*, and b* values for the relevant control from the L*, a*, and b* values for the sample.
  • the plaques were also presented to a panel of evaluators for qualitative comparison to the relevant control.
  • each panelist was presented with two plaques, one made using one of the above-described samples and the other made from the relevant control, laid flat against a white surface in an area lit by a cool white fluorescent light source.
  • Each panelist was then asked to determine if the plaque made from the above-described sample was, compared to the relevant control, more visually appealing, less visually appealing, no different, or substantially colored.
  • the sample plaques rated as more visually appealing by a majority of the panelists are identified in Table 4, 5, or 6 with a “yes” in the “Enhanced” column.
  • Those sample plaques that were rated as less visually appealing, no different than the control plaque, or substantially colored are identified in Table 4, 5, or 6 with a “no” in the “Enhanced” column.
  • the CIE L*a*b* measurements and the visual evaluations were used to generate plots of the ⁇ a* and ⁇ b* values and the absolute a* and b* values for each plaque.
  • the plot of the ⁇ a* and ⁇ b* values is depicted in FIG. 1 .
  • the plaques which were determined to be more visually appealing than the relevant control are represented by a dot (•) located at the coordinates of the appropriate ⁇ a* and ⁇ b* values and those plaques which were determined to be less visually appealing, no different than the control, or substantially colored are represented by a circle ( ⁇ ) located at the coordinates of the appropriate ⁇ a* and ⁇ b* values.
  • the area in which the more visually appealing plaques fall can be defined as those points in which the ⁇ a* and A/D* values satisfy each of the following inequalities:
  • This area can be defined as those points in which the ⁇ a* and A/D* values satisfy each of the following inequalities:
  • This area can be defined as those points in which the ⁇ a* and ⁇ b* values satisfy each of the following inequalities:
  • the CIE L*a*b* measurements and the visual evaluations were used to generate plots of the absolute a* and b* values for each plaque.
  • the plot of the a* and b* values is depicted in FIG. 2 .
  • the plaques which were determined to be more visually appealing than the relevant control are represented by a dot (•) located at the coordinates of the appropriate a* and b* values and those plaques which were determined to be less visually appealing, no different than the control, or substantially colored are represented by a circle ( ⁇ ) located at the coordinates of the appropriate a* and b* values.
  • ⁇ located at the coordinates of the appropriate a* and b* values.
  • those plaques which were determined to be more visually appealing than the relevant control fall within a particular area of the plot. This area is bound by the line segments L, M, N, and P, and each line segment can be defined by one of the following equations:
  • the area in which the more visually appealing plaques fall can be defined as those points in which the a* and b* values satisfy each of the following inequalities:
  • This area can be defined as those points in which the a* and b* values satisfy each of the following inequalities:
  • This area can be defined as those points in which the a* and b* values satisfy each of the following inequalities:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
US13/013,277 2011-01-25 2011-01-25 Additive compositions and thermoplastic polymer compositions comprising the same Abandoned US20120190780A1 (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
US13/013,277 US20120190780A1 (en) 2011-01-25 2011-01-25 Additive compositions and thermoplastic polymer compositions comprising the same
KR1020137022179A KR20130108669A (ko) 2011-01-25 2011-12-20 첨가제 조성물 및 이를 포함하는 열가소성 중합체 조성물
SG2013051057A SG191809A1 (en) 2011-01-25 2011-12-20 Additive compositions and thermoplastic polymer compositions comprising the same
JP2013551970A JP5897604B2 (ja) 2011-01-25 2011-12-20 添加剤組成物およびそれを含む熱可塑性ポリマー組成物
AU2011356604A AU2011356604C1 (en) 2011-01-25 2011-12-20 Additive compositions and thermoplastic polymer compositions comprising the same
CN201180068470.6A CN103391966B (zh) 2011-01-25 2011-12-20 添加剂组合物及包含其的热塑性聚合物组合物
KR1020207028549A KR102330795B1 (ko) 2011-01-25 2011-12-20 첨가제 조성물 및 이를 포함하는 열가소성 중합체 조성물
KR1020187026006A KR102165551B1 (ko) 2011-01-25 2011-12-20 첨가제 조성물 및 이를 포함하는 열가소성 중합체 조성물
KR1020157027192A KR20150117714A (ko) 2011-01-25 2011-12-20 첨가제 조성물 및 이를 포함하는 열가소성 중합체 조성물
BR112013018623A BR112013018623A2 (pt) 2011-01-25 2011-12-20 composições de aditivo e composições de polímero termoplástico compreendendo as mesmas
KR1020217037761A KR102477402B1 (ko) 2011-01-25 2011-12-20 첨가제 조성물 및 이를 포함하는 열가소성 중합체 조성물
EP11809023.2A EP2668229B1 (en) 2011-01-25 2011-12-20 Additive compositions and thermoplastic polymer compositions comprising the same
PCT/US2011/065987 WO2012102805A1 (en) 2011-01-25 2011-12-20 Additive compositions and thermoplastic polymer compositions comprising the same
RU2013135666/05A RU2553300C2 (ru) 2011-01-25 2011-12-20 Аддитивные композиции и содержащие их термопластичные полимерные композиции
JP2016001897A JP2016166325A (ja) 2011-01-25 2016-01-07 添加剤組成物およびそれを含む熱可塑性ポリマー組成物
US15/485,916 US10800902B2 (en) 2011-01-25 2017-04-12 Additive compositions and thermoplastic compositions comprising the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US13/013,277 US20120190780A1 (en) 2011-01-25 2011-01-25 Additive compositions and thermoplastic polymer compositions comprising the same

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/485,916 Continuation US10800902B2 (en) 2011-01-25 2017-04-12 Additive compositions and thermoplastic compositions comprising the same

Publications (1)

Publication Number Publication Date
US20120190780A1 true US20120190780A1 (en) 2012-07-26

Family

ID=45496291

Family Applications (2)

Application Number Title Priority Date Filing Date
US13/013,277 Abandoned US20120190780A1 (en) 2011-01-25 2011-01-25 Additive compositions and thermoplastic polymer compositions comprising the same
US15/485,916 Active US10800902B2 (en) 2011-01-25 2017-04-12 Additive compositions and thermoplastic compositions comprising the same

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15/485,916 Active US10800902B2 (en) 2011-01-25 2017-04-12 Additive compositions and thermoplastic compositions comprising the same

Country Status (10)

Country Link
US (2) US20120190780A1 (ru)
EP (1) EP2668229B1 (ru)
JP (2) JP5897604B2 (ru)
KR (5) KR102330795B1 (ru)
CN (1) CN103391966B (ru)
AU (1) AU2011356604C1 (ru)
BR (1) BR112013018623A2 (ru)
RU (1) RU2553300C2 (ru)
SG (1) SG191809A1 (ru)
WO (1) WO2012102805A1 (ru)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150096918A1 (en) * 2012-05-11 2015-04-09 Adeka Corporation Clarifying agent composition, resin composition and molded article
US20180312313A1 (en) * 2015-11-30 2018-11-01 Hitachi Chemical Company, Ltd. Food packaging film, and gift-boxed small roll of food packaging film

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10493682B2 (en) * 2015-12-31 2019-12-03 Milliken & Company Method for molding a polymer composition
US10081690B2 (en) 2016-06-23 2018-09-25 Sunko Ink Co., Ltd. Powdery diacetal clarifying agent and method of preparing the same
BR112021006938A2 (pt) 2018-12-21 2021-07-13 Milliken & Company composições de aditivo e composições de polímero termoplástico compreendendo as mesmas

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852237A (en) 1972-09-08 1974-12-03 Phillips Petroleum Co Clearer polyefins by combination of aryl carboxlic acid phthalocyanine, and quinacridone
JPS58180543A (ja) * 1982-04-19 1983-10-22 Mitsubishi Petrochem Co Ltd プロピレン重合体組成物
US4731400A (en) 1984-12-18 1988-03-15 Mitsui Petrochemical Industries, Ltd. Thermoplastic resin composition
JPS6422952A (en) 1987-07-18 1989-01-25 Mitsubishi Rayon Co Methacrylic polymer composition of outstanding color tone and tinge
US4820755A (en) 1987-08-18 1989-04-11 American Cyanamid Company Radiation sterilizable composition and articles made therefrom
US5003500A (en) 1988-09-05 1991-03-26 Ciba-Geigy Corporation Process and apparatus for the preparation of color formulations utilizing polarized light in spectrophotometry
US5262471A (en) 1988-11-21 1993-11-16 Fuji Photo Film Co., Ltd. Method of preparing packaging material for photographic photosensitive material and masterbatch therefor
JPH05339442A (ja) * 1992-06-15 1993-12-21 Tokyo Ink Kk ポリオレフイン用カラーマスターバッチ
JP2777509B2 (ja) 1992-09-30 1998-07-16 出光石油化学株式会社 色調検査方法
JPH06220270A (ja) * 1993-01-27 1994-08-09 Mitsubishi Petrochem Co Ltd 耐傷性プロピレン系樹脂組成物
JPH06286009A (ja) 1993-03-30 1994-10-11 Hannou Koki Seisakusho:Kk プラスチックレンズおよびその製造方法
JP3478604B2 (ja) * 1994-09-08 2003-12-15 新日本理化株式会社 着色ポリオレフィン系樹脂組成物
JP3743029B2 (ja) * 1994-12-29 2006-02-08 株式会社エーピーアイ コーポレーション ポリオレフイン系樹脂に対する透明化剤、その製造方法及び透明性が改良されたポリオレフイン系樹脂組成物
US5961914A (en) 1996-05-03 1999-10-05 Milliken & Company Method of thermoforming polyolefin resin
JPH1017848A (ja) 1996-07-03 1998-01-20 Ii C Kagaku Kk ポリオレフイン系樹脂に対する透明化剤、その製造方法及び透明性が改良されたポリオレフイン系樹脂組成物
US5859708A (en) 1997-09-02 1999-01-12 General Electric Company Sensing blend color homogeneity
WO1999024496A1 (fr) * 1997-11-06 1999-05-20 New Japan Chemical Co., Ltd. Procede de moulage de gel de composition de resine polyolefinique orientee et objet moule produit par ce procede
JPH11158361A (ja) 1997-12-01 1999-06-15 Teijin Ltd ポリエステル中空容器及びその製造方法
JPH11349740A (ja) 1998-06-11 1999-12-21 Asahi Denka Kogyo Kk 射出成形用着色合成樹脂組成物
JP4033563B2 (ja) 1998-10-08 2008-01-16 住化カラー株式会社 透明樹脂成形体の調色方法
JP4201431B2 (ja) 1999-04-19 2008-12-24 株式会社Ａｄｅｋａ 着色合成樹脂組成物
US6534574B1 (en) * 2001-03-24 2003-03-18 Milliken & Company Highly nucleated thermoplastic articles
CN1443801A (zh) 2002-03-12 2003-09-24 中国石化北京燕化石油化工股份有限公司树脂应用研究所 一种透明聚丙烯组合物
US6875811B2 (en) 2002-05-07 2005-04-05 Milliken & Company Single compound toners for use in polyesters
JP2004083852A (ja) 2002-06-24 2004-03-18 Asahi Denka Kogyo Kk 造核剤及び該造核剤を含有してなる結晶性高分子組成物
US7303795B2 (en) 2003-03-13 2007-12-04 Invista North America S.A. R.L. Molding of polypropylene with enhanced reheat characteristics
US20040219319A1 (en) 2003-04-30 2004-11-04 Brooks Gary T. High clarity formed articles of polypropylene
US7291669B2 (en) 2004-03-16 2007-11-06 Ciba Specialty Chemicals Corporation Stabilized polyolefin compositions
FR2869563B1 (fr) 2004-04-30 2007-09-07 Sidel Sas Preforme en polypropylene pour la fabrication de bouteilles ou analogues par soufflage ou etirage-soufflage et procede de soufflage ou d'etirage-soufflage de cette preforme
ES2328611T3 (es) 2004-12-17 2009-11-16 Exxonmobil Chemical Patents Inc. Peliculas de mezclas de polimeros.
JP2006225576A (ja) * 2005-02-21 2006-08-31 Dainichiseika Color & Chem Mfg Co Ltd 樹脂組成物
US7786203B2 (en) 2005-09-16 2010-08-31 Milliken & Company Polymer compositions comprising nucleating or clarifying agents and articles made using such compositions
EP1928938A1 (en) * 2005-09-30 2008-06-11 Ciba Holding Inc. Microporous films
JP2007161958A (ja) 2005-12-16 2007-06-28 Nippon Ester Co Ltd ポリエステル
US8232335B2 (en) * 2006-02-07 2012-07-31 Milliken & Company Compositions and methods for making clarified aesthetically enhanced articles
US8105686B2 (en) * 2006-07-17 2012-01-31 Avery Dennison Corporation Asymmetric multilayered polymeric film and label stock and label thereof
JP5388263B2 (ja) * 2007-09-04 2014-01-15 株式会社Ａｄｅｋａ ポリオレフィン樹脂用造核剤マスターバッチ
US9029446B2 (en) * 2009-12-07 2015-05-12 Basf Se Clarified polypropylene articles with improved optical properties and/or increased temperature of crystallization

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150096918A1 (en) * 2012-05-11 2015-04-09 Adeka Corporation Clarifying agent composition, resin composition and molded article
US10577483B2 (en) * 2012-05-11 2020-03-03 Adeka Corporation Clarifying agent composition, resin composition and molded article
US20180312313A1 (en) * 2015-11-30 2018-11-01 Hitachi Chemical Company, Ltd. Food packaging film, and gift-boxed small roll of food packaging film

Also Published As

Publication number Publication date
EP2668229A1 (en) 2013-12-04
RU2553300C2 (ru) 2015-06-10
AU2011356604C1 (en) 2017-08-03
KR102165551B1 (ko) 2020-10-14
AU2011356604B2 (en) 2015-03-12
RU2013135666A (ru) 2015-03-10
EP2668229B1 (en) 2017-09-06
BR112013018623A2 (pt) 2016-10-18
JP5897604B2 (ja) 2016-03-30
KR20210145308A (ko) 2021-12-01
JP2014503679A (ja) 2014-02-13
CN103391966B (zh) 2015-09-09
JP2016166325A (ja) 2016-09-15
US10800902B2 (en) 2020-10-13
CN103391966A (zh) 2013-11-13
WO2012102805A1 (en) 2012-08-02
US20170218175A1 (en) 2017-08-03
AU2011356604A1 (en) 2013-07-18
KR102330795B1 (ko) 2021-12-01
KR20180102698A (ko) 2018-09-17
KR20200119886A (ko) 2020-10-20
SG191809A1 (en) 2013-08-30
KR20150117714A (ko) 2015-10-20
KR102477402B1 (ko) 2022-12-13
KR20130108669A (ko) 2013-10-04

Similar Documents

Publication Publication Date Title
US10800902B2 (en) Additive compositions and thermoplastic compositions comprising the same
US20230416535A1 (en) Grinding aid for titanium dioxide particles
US10611895B2 (en) Additive composition, method of blending same and a low haze polyolefin material and preparation thereof
US11834558B2 (en) Additive compositions and thermoplastic polymer compositions comprising the same
RU2819363C2 (ru) Композиции добавок и содержащие их термопластичные полимерные композиции
US10844195B2 (en) Additive composition, method of blending same and a low haze polyolefin material and preparation thereof
US20140088227A1 (en) Colouring composition for thermoplastic polymers and process of preparing and using same
JPH05339442A (ja) ポリオレフイン用カラーマスターバッチ
MXPA98001267A (en) Stabilization of pigmen

Legal Events

Date Code Title Description
AS Assignment

Owner name: MILLIKEN & COMPANY, SOUTH CAROLINA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DANIELSON, TODD D.;MYERS, JAMIE B.;MORGAN, JENNIFER S.;REEL/FRAME:027549/0535

Effective date: 20120112

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION