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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
  • C08K5/3435—Piperidines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D211/40—Oxygen atoms
  • C07D211/44—Oxygen atoms attached in position 4
• • 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

Definitions

• the invention relates to the use of certain piperidine compounds of the formula I below for the stabilization of natural or synthetic, organic or inorganic pigments or pigment mixtures in natural or synthetic, polymeric or prepolymeric substrates against the negative effects of heat and / or light on the lightfastness or Color stability, especially against color shifts or light-induced fading.
• the invention also relates to a masterbatch composition comprising at least one piperidine compound according to formula I below, at least one inorganic or organic pigment and a natural or synthetic material which is identical or compatible with the natural or synthetic, polymeric or prepolymeric substrate to be pigmented.
• the invention also relates to a process for stabilizing organic or inorganic pigments or pigment mixtures in natural or synthetic, polymeric or prepolymeric substrates against the negative effects of heat and / or light on light fastness or color stability, in particular against color shifts or light-induced fading by addition an amount sufficient to stabilize at least one piperidine compound according to formula I below as such or in the form of a masterbatch composition to the pigment or pigment mixture to be stabilized or to the natural or synthetic, polymeric or prepolymeric substrate containing the pigment or pigment mixture.
• Pigments are insoluble or extremely poorly soluble dyes.
• Dyes generally contain atomic groups, called chromophoric groups, which produce the color in molecules and auxochromic groups, which themselves do not produce color, but which intensify the color intensity and depth. These aforementioned groups of atoms can be damaged by energy supplied in the form of heat or light.
• chromophoric groups which produce the color in molecules
• auxochromic groups which themselves do not produce color, but which intensify the color intensity and depth.
• These aforementioned groups of atoms can be damaged by energy supplied in the form of heat or light.
• the invention is therefore based on the object of improving the light fastness and color intensity of pigments and the period of use of the pigmented end articles.
• HALS hindered amine light stabilizer
• the invention thus relates to the use of piperidine compounds of the formula I.
• R hydrogen, hydroxyl, low molecular weight alkyl, low molecular weight alkoxy or acyl
• R 3 is oxygen, -NH- or -N (C M -alkyl) - and
• R 8 are independently hydrogen or methyl
• Low molecular weight alkyl is preferably to be understood as meaning residues with 1 to 8, in particular 1 or 2, carbon atoms; as “acyl” are preferably the residues of formic, acetic or propionic acid.
• All R are preferably hydrogen, hydroxyl, methyl, or C ,. 8 alkoxy, especially methyl.
• R 2 of aromatic character there are, for example, five- or six-membered rings containing benzene, naphthalene and nitrogen and / or sulfur, which are optionally fused to a benzene ring and which, for example, carry sterically hindered hydroxyl as substituents (3, 5-di-tert-butyl-4-hydroxyphenyl), or a thienyl radical.
• Aromatic six-membered rings are preferred.
• substituents on these rings for example hydroxyl, low molecular weight alkyl or alkoxy, preferably methyl, tert. -Butyl, methoxy, ethoxy, hydroxyl and one or two groups of the formula
• All R 8 are preferably hydrogen.
• R ' H, CH 3 , OC g H, 7 (n), C (O) CH 3
• R 4 H, OCH 3 ,
• the substrate is particularly selected from the group comprising plastics, paints and coatings.
• piperidine compounds of the formula I in addition to piperidine compounds of the formula I, other commercially available additives, such as e.g. phenolic antioxidants, secondary aromatic amines, thioethers, phosphorus compounds, bioeides, metal deactivators, further HALS compounds, UV absorbers, antistatic agents and the like as well as various paint auxiliaries or inert fillers, e.g. Talc, chalk, glass, barite, etc. can also be used.
• additives such as e.g. phenolic antioxidants, secondary aromatic amines, thioethers, phosphorus compounds, bioeides, metal deactivators, further HALS compounds, UV absorbers, antistatic agents and the like as well as various paint auxiliaries or inert fillers, e.g. Talc, chalk, glass, barite, etc. can also be used.
• End articles the pigmentation of which are stabilized according to the invention, are distinguished from articles according to the prior art by a considerably longer service life.
• the invention also relates to a masterbatch composition which comprises at least one piperidine compound of the formula I, optionally also at least one inorganic or organic pigment and a natural or synthetic carrier material which is identical or compatible with the natural or synthetic, polymeric or prepolymeric substrate to be pigmented is included.
• Piperidine compounds of the formula I or a masterbatch composition containing the piperidine compound can be added to the substrate to be pigmented before, during or after the addition of a pigment or pigment mixture.
• the concentration of the piperidine compounds of the formula I is at least 0.01%, preferably 0.05 to 3.0% by weight, particularly preferably 0.1 to 1.7% by weight, of the weight of the total mixture processing the end product, which is the polymeric or includes prepolymeric substrate, and the weight ratio to the total pigmentation is at least 1: 100 to 100: 1, preferably 1: 50 to 50: 1, particularly preferably 1:20 to 20: 1.
• the pigmentation can be added by the generally customary methods in pure form as so-called full pigments, in predispersed form as concentrates, masterbatches and the like. Like. Or in combination with other additives to the plastics, paints or coatings.
• Another object of the invention is a method for stabilizing organic or inorganic pigments or pigment mixtures in natural or synthetic, polymeric or prepolymeric substrates against the negative effects of heat and / or light on light fastness or color stability, in particular against color shifts or light-induced fading Adding an amount sufficient for stabilization of at least one piperidine compound of the formula I as such or in the form of a masterbatch composition to the pigment or pigment mixture to be stabilized or to the natural or synthetic, polymeric or prepolymeric substrate containing the pigment or pigment mixture.
• the parts mean parts by weight, the percentages by weight and the degrees Celsius degrees.
• Pigmentation 1.2 This color setting is a masterbatch (MB) from Clariant under the name Sanylen Blau 39-93 [CI. Pigment Blue 29J available. This is a polysulfide containing sodium aluminum silicate.
• Pigmentation 1.3 This color setting is available as a master batch (MB) from Clariant under the name Sanylen Gray AU 604 / S5, and consists of:
• Polymer 2.1 polypropylene homopolymer
• Polymer 2.2 polyethylene homopolymer (HDPE, Ziegler type)
• Sandostab ® P-EPQ is a processing stabilizer from Clariant based on a sterically hindered phosphonite
• Irganox ® 1010 is an antioxidant from Ciba-Geigy based on a sterically hindered phenol.
• Irganox ® B-225 is an antioxidant from Ciba-Geigy based on Irganox ® 1010 and Irgafos ® 1 68, a phosphite processing stabilizer .
• HALS-1 Chimassorb ® 944 FL, an oligomeric HALS compound from Ciba-Geigy
• HALS-2 Sanduvor ® 3944, an oligomeric, high molecular HALS type from Clariant
• HALS-3 Tinuvin ® 770, a low-molecular HALS compound from Ciba-Geigy
• HALS-4 Uvasorb ® HA-88, an oligomeric, high molecular HALS compound from 3V France SA
• the processing is carried out by intensive mixing of powdered polymer with the likewise powdered full pigment or, if the pigments are used in masterbatch form, by mixing polymer and masterbatch granulate and subsequent homogenization in the melt by extrusion under the usual conditions for processing the respective Polymers.
• the piperidine compounds according to the invention or the HALS compounds used in comparative experiments are also incorporated by adding them to the exclusively powdery constituents or, if masterbatches are used, by adding them in granulated form as MB-20, ie as masterbatch containing 20% of the piperidine or HALS connection in the same Carrier polymer as in the end use.
• the pigmented starting material obtained in this way after cooling and strand granulation is then processed by conventional injection molding to form the actual test plates with a thickness of 1-3 mm, which are then used to measure the lightfastness of the pigmentation.
• the exposure or accelerated weathering of the pigmented test panels is carried out by exposure under the following conditions:
• condition 3.1 represents a widespread, universal laboratory method for accelerated exposure
• conditions 3.2 and 3.3 in particular condition 3.2, are used by numerous automobile manufacturers or their suppliers in order to carry out appropriate tests, in particular of pigmented substrates.
• Comparative measurements of the color fastness of the different samples are carried out after the exposure times mentioned in each case by the test plates by determining the so-called delta E or delta C values, which - put simply - the deviation of the overall color impression (nuance, intensity) or the color saturation express with respect to the unexposed comparative samples, be measured colorimetrically. Good color fastness is achieved if both delta-E and delta-C are close to zero after exposure. The more the test result differs from zero, the more clearly the eye can perceive the color deviations.
• the above-mentioned parameters are part of the so-called "CIELAB systems" (see JSDC, September 1976, p. 337-338); Further details on colorimetry are described in the standards ISO 7724/3 and DIN 6174.
• 1.5 mm injection-molded plates are produced and immediately colorimetrically characterized.
• the delta-C and delta-E values measured compared to the control sample (without HALS compound) show that even after incorporation of the stabilizer 1 according to the invention, there are significantly smaller deviations in the desired color shades than in the comparative example when using HALS-1 .
• Injection-molded plates produced according to Example 1 are exposed under exposure conditions 3.1 for 600 hours and then characterized colorimetrically.
• Injection-molded plates produced according to Example 1 are exposed to an intensive UV exposure for a period of 636 hours (time of actual exposure) under exposure conditions 3.2 and then measured colorimetrically.
• the delta-E values given in the table, measured in relation to the unexposed respective reference samples, are obtained after 9000 hours of weathering.
• the stabilizing effect of the stabilizer 1 according to the invention is clearly recognizable.
• the measured color deviation of the pigmentation is only about half that of the samples conventionally stabilized with HALS-2 or HALS-4; ie the presence of the stabilizer 1 can significantly reduce the "fading" of the coloring, which is also clearly expressed in the case of a visual inspection.
• Example 5
• the low molecular weight compound HALS-3 or its combination with the oligomeric, higher molecular weight HALS-2 is used very frequently in the present polymer 2.3 and is to be regarded as the prior art.
• the use of stabilizer 1 according to the invention in the same concentration also achieves a significant increase in the color stability of the pigmentation used and thus improves the performance properties of corresponding, colored products or maintains their original coloring over a longer period of use.

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• 1996
  • 1996-03-29 JP JP8076771A patent/JPH0952975A/ja active Pending
  • 1996-08-16 CZ CZ98465A patent/CZ46598A3/cs unknown
  • 1996-08-16 KR KR1019980701123A patent/KR19990037646A/ko not_active Application Discontinuation
  • 1996-08-16 BR BR9609927A patent/BR9609927A/pt not_active Application Discontinuation
  • 1996-08-16 SK SK205-98A patent/SK20598A3/sk unknown
  • 1996-08-16 HU HU9802451A patent/HU219759B/hu not_active IP Right Cessation
  • 1996-08-16 WO PCT/EP1996/003623 patent/WO1997007160A1/de not_active Application Discontinuation
  • 1996-08-16 US US09/011,867 patent/US6126736A/en not_active Expired - Fee Related
  • 1996-08-16 AU AU68223/96A patent/AU722470B2/en not_active Ceased
  • 1996-08-16 EP EP96928473A patent/EP0851892A1/de not_active Withdrawn

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