• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Malonates of the formula I <IMAGE> (I) in which R1 is hydrogen or C1-C4-alkyl, R2 is C1-C12-alkyl, C3-C4-alkenyl, benzyl or phenyl which is optionally substituted by C1-C8-alkyl or C1-C8-alkoxy, or is cyano, R3 is C1-C12-alkyl, C3-C4-alkenyl or benzyl and X denotes hydrogen, oxyl, C1-C12-alkyl, C3-C6-alkenyl, C3-C4-alkinyl, C2-C21-alkoxyalkyl, C7-C8-aralkyl, 2,3-epoxypropyl, an aliphatic acyl group with 1-4 C atoms or one of the groups -CH2COOR4, -CH2-CH(R5)-OR6, -COOR7 or -CONHR7, in which R4 is C1-C8-alkyl, C3-C6-alkenyl, phenyl, C7-C8-aralkyl or cyclohexyl and R5 is hydrogen, methyl or phenyl and R6 denotes hydrogen or an aliphatic or aromatic, araliphatic or alicyclic acyl group with 1-18 C atoms, in which the aromatic part can optionally be substituted by chlorine, C1-C4-alkyl or C1-C8-alkoxy and/or by hydroxyl, and R7 is C1-C12-alkyl, cyclohexyl, phenyl or benzyl as stabilizer for organic polymers.
    公开号:SU797589A3
    申请号:SU772480486
    申请日:1977-05-04
    公开日:1981-01-15
    发明作者:Роди Жан
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    (54) POLYMER COMPOSITION
    The invention relates to polymeric compositions stabilized by destruction under the action of light. Polymer compositions used in industry are known to include 2- (2-hydroxy-3, 5-ditertbutylphenyl) -5-chlorobenzotriazole Yu as a light stabilizer. However, the composition has low resistance to light aging. Most closely related to the present invention is a polymer composition comprising a synthetic polymer and hydroxybenzylmalonates of spatial hindered 4-hydroxypiperidines p. However, although it has a greater light fastness than the above, but its resistance to light aging 2Q in some cases is still insufficient. The purpose of the invention is to increase the resistance to light aging. This goal is achieved by the fact that 25 a polymer composition comprising a polymer selected from a group containing a polyolefin, polystyrene and polyester based polyester, and a derivative of malonic acid, is preferably in the form of of the latter, the formulas flj .H, R. / - d - (- CO-0 / V) i tg are not enough (bp-1 ts I R-CHj H, methyl, R Rn benzyl, alkyd C, -C, alkenyl benzyl, alkyl C-C, alkenyl Cz-Cd; H, alkyl Cj-Cg, acetyl, acryloyl, alkenyl C -) - C (,, aralkyl C-y-C, the following ratio of components, wt.%: polymer 99,5- 99.99 Malonat 0.01-0.5 By learning the compounds of forms ly (I) but different sposoi carried out, which consist of several stages in different Yelnia podovatelnosti. Separate the step m of the reactions known from the chemistry of derivatives of malonic acid.
    Synthesis can be initiated by the fact that the lower alkyl ether of mathematical acid, such as diethyl malonate, is transesterified with 4-piperidinol of the formula. (II) into the corresponding bis-piperidimyl-malonate of the formula (111)
    She CHa-ii,
    CHj (SOOC 2H5), j - «- 2X-N V OH
    ITT.
    CH
    CHj-Ri
    on oj3
     four
    (
    x-1 yr-yo dHo
     . / 2
    sns cng- (w).
    In doing so, X can represent. is already a substituent desirable in the compound of formula (I), or tetramethylpiperidol (P, XH) unsubstituted on the nitrogen atom is used and the substituent X is introduced after re-extraction or at a later stage of the synthesis.
    The introduction of K can be carried out by conventional methods of M-alkylation or N-acylation, in particular by reaction with alkyl halides, alkenyl halides, propargyl chloride, benzyl chloride or carboxylic acid chlorides, preferably in the presence of molar amounts.
    N-acylation can also be carried out using carboxylic anhydrides, in particular acetic anhydride. Oxyalkyl radicals are introduced by reacting with epoxides, in particular ethylene oxide or propylene oxide, and can be converted by reaction with anhydrides or acid chlorides Carboxylic acids to the corresponding N-acyloxyalkyl groups. N-OK forces (XO) can be obtained by oxidation with peracids or hydrogen peroxide.
    As a further step, it can be made by introducing into the compounds of formula (III) either first the substituent Rj and thereafter either introducing the substituent R and then Rj. .
    The radical Ri2 can be introduced according to the type of synthesis of malonic ester by means of the fact that the ester of formula (III) is firstly reacted with an equivalent amount of alkali metal, alkali metal alcohol, alkali metal amide,
    an alkali metal hydride or similar basic alkali compound is converted into an alkali metal compound of formula (III) and then is reacted in the usual way with 1 mole of Rr-halide.
    After that, in the specified Rrj-malonic ester, you must enter the substituent Rj. If, of course, Rr has the same meaning as R. The introduction of both radicals can be carried out simultaneously.
    The introduction of the substituent R can be carried out according to the classical C-alkylation method of malonic esters, wherein the R-malonic ester is first converted into its alkaline compound and then reacted with a halogen-containing compound of the formula Rj-Gal. This gal is a chlorine, bromine or iodine atom. Approximately one mole of the monohalogenide f (), - ran is used per mole of alkaline compound. Examples of these monohalides are alkyl, alkenyl, or benzyl halides.
    Finally, it is also possible to introduce X together with the introduction of R if X and T, are the same, for example if they mean alkyl, alkenyl or benzyl.
    Based on these various possibilities of performing the individual reaction steps: introducing the piperidinyl radical, introducing the group R, introducing the group R, and, if necessary, introducing X, the sequence of the individual stages will be chosen in the way that seems most appropriate in each case. .
    Examples of stabilized polymers are high or low density polyolefins, polypropylene, ethylene-propylene copolymers, polystyrene, mixtures of polyolefins, polyurethane-based polyesters in the form of varnishes, elastomers or foams.
    Stabilizers are added to the plastics in a concentration of from 0.01 to 0.5 wt.%. Preferably, from 0.03 to 1.5, particularly preferably from 0.2 to 0.6% by weight of the compounds are calculated, based on the material to be stabilized.
    - The introduction can be carried out after polymerization, before or during the molding, or also by applying the dissolved or dispersed compounds to the polymer, if necessary, followed by evaporation of the solvent.
    The new compounds can be added to the plastics to be stabilized, also in the form of a masterbatch, which contains these compounds, in particular, in a concentration of from 2.5 to 25% by weight.
    In the case of crosslinked polyethylene, the compounds are introduced before crosslinking.
    In addition to these malonates, other known stabilizers can also be added to the plastics. These can be, for example, antioxidants, light stabilizers, or metal deactivators, or also stabilizers, for example, of the type of phosphoric acid esters. In addition, other plastics that are common in plastics technology, such as, for example, flame retardants, antistatic agents, plasticizers, lubricants, blowing agents, pigments, reinforcing materials or fillers, can be added. The stabilized plastics may be applied in a wide variety of forms, for example, in the form of films, fibers, tapes, profiles, or in the form of binders for varnishes, adhesives or putties.
    Example 1. 188.2 g of diethylmalonic acid dimethyl ester and 320 g of 2,2,6,6-tetramethyl-4-oxypiperidine are heated in 200 ml of ligroin after adding 1 g of lithium amide in a weak stream of nitrogen to about 120 ° C. At the same time continuously
    the methanol formed during the transesterification is distilled off. After about 6 hours, the reaction is almost complete. The reaction mixture is diluted with 100 ml of ligroin and extracted three times with hot water using 100 ml of hot water each time. Upon cooling of the ligroin solution, the bis- (2,2,6., B-tetramethyl-4-piperidinyl) -loury diethylmalonic acid ester (compound 1) crystallizes with a melting point.
    Examples 2-6. If instead of diethylmalonic acid dimethyl ester according to Example 1, an equivalent amount of diethyl ether of di-n-butylmalonic acid or dimethyl acid is used. di-isobutyl malonic acid ester, or di-isobutylmalonic acid dimethyl ester, or diallyl malonic acid diethyl ester, or dibenzylmalonic acid dimethyl ester, or n-butylbenzylmalonic acid dimethyl ester, or received as described in the example This is obtained after appropriate separation of the reaction mixture: the bis- (2,2,6,6-tetramethyl-4-piperidinyl) ester di-ngbu.tylmalonic acid (compound 2) in the form of a practically colorless oil (molecular distillation at ature 120 ° C; 0.005 mm Hg), or bis (2,2,6,6-tetramethyl-4-piperidinyl) ester of diisobutylmalonic acid (compound 3) with a melting point of 81-83 ° C, or the same bis- (2,2,6,6-tetramethyl-4-piperidinyl) ester of diallyl malonic acid (compound 4) with a melting point of 84-87 s, or bis (2,2,6,6-tetramethyl) 4-piperidinyl) ester of dibenzylmalonic acid (compound 5) with a melting point of 12 V-130 ° C, or bis (2,2,6,6-tetramethyl-4-piperi dinol) ester of n-butylbeneylmalonic acids (compound b) with temperatures Melting minutes 8788 ° C.
    Example 7. 205 g of bis- (1,2, 2,6-pentamethyl-4-piperidinyl) -wow
    5 malonic acid ester, prepared according to known methods, is heated with 12 g of sodium hydride in 500 ml of absolute toluene for 6 hours under reflux. After this time, the evolution of hydrogen ceased and the reaction mixture could not be ob-. expose virtually no sodium hydride particles. Cool to 50s,
    5 g of 63 g of benzyl chloride are added dropwise within about 30 minutes and then stirred under reflux for 1 hour. After that, again cooled to a temperature of about 50 ° C,
    0 again, add 12 g of sodium hydride and heat under reflux until the complete elimination of hydrogen is stopped (about 6 h. It is cooled again until it is added dropwise
    5 for about 30 minutes, 63 g of benzyl chloride and then stirred for 3 hours. reflux condenser. The reaction solution is washed three times with 200 ml of water, dried over sodium sulfate and evaporated. By crystallizing the residue from hexane, bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) dibenzylmalonic acid ester (compound 7) with a melting point of 121-122 ° C is obtained.
    Examples are ZgE. If an equivalent amount is used instead of benzyl chloride according to example 7, ethyl iodide, or allyl chloride and
    0 do otherwise as described in Example 7, then bis (1,2,2, 6,6-pentamethyl) -4-piperidinyl} ester of diethylmalonic acid (compound 8) with melting point is obtained, or same bis-G1,2,2,
    5 6,6-pentamethyl-4-piperidinyl-ester of diallylmalonic acid (compound 9) with a melting point of 100-101 C.
    Example 10. 115.9 g of bis0 - (1-allyl-2.2, .6,6-tetramethyl-4-piperidinyl) malonic acid ester, prepared according to known methods, are heated with 6 g of yatry hydride in 300 ml
    S
    absolute toluene for b h under reflux. 31.5 g of benzidchloride are then added dropwise over about 20 min. And then stirred for one hour under reflux. After that, it is cooled again to about 500 ° C, 6 g of sodium hydride are added again and heated to reflux until complete termination of hydrogen (for about 6 hours). Cool again until 31.5 g of benzyl chloride are added dropwise in approximately 20 minutes and then stirred in a solution for 2 hours under reflux. The reaction solution is washed three times with 150 ml of water, dried over sodium sulfate and evaporated, and the crystallization of the residue from hexane gives bis ( 1-allyl-2,2,6, b-tetramethyl-4-piperidinyl) dibenzylmalonic acid ester (compound 10) with a melting point of 120-121 ° C.
    Examples 11-17. If instead of bis- (1-allyl-2,2,6, b-tetramethyl-4-piperidinyl) -oh of malonic acid ester, an equivalent amount of bis-fl-benzyl-2, 2,6 is used, b-tetramethyl -4-piperidivyl malonic acid ester, or bis (1gpropyl-2, 2, b, b-tetramethyl-47-piperidinyl) malonic acid ester, or bis (-. 1-butyl-2, 2, b, b-tetramethyl-4-piperidinyl) ester of malonic acid, or the bis- (1-hexyl-2, 2,6, b-tetramethyl-4-piperidinyl ester of malic acid, or bis- (1- (butenyl-2 -2, 2/6, b-tetramethyl-4-piperidinyl) s malonic acid ester, or bis (1- (3-methyl-butenyl-2) -2,2, b, b-tetramethyl-4-piperidinyl) ester of malonic acid, or bis (1 - (4-tert-butyl, -benzyl) -2,2,6, b-tetramethyl-4-piperidivyl) new ester of malonic acid and do the rest, as described in example 10 -, then get bis- ( 1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl) dibenzylmalonic acid ester (compound 11 with a melting point of 149-150 ° C, or
    the same bis- {1-propyl-2, 2, 6,6-tetramethyl-4-piperidinyl) dibenzylmalonic acid ester (compound 12) with a melting point of 115-11b C, or bis- (1 -butyl-2,2, b, 6-tetramethyl-4-piperidinyl) dibenzylmalonic acid ester (compound-13) with a melting point of 124-125 0, or bis- (1-hexyl-2, 2 , 6, b-tetramethyl-4-piperidinyl) ester of dibenzylmalonic acid (compound 14) with a melting point of 94-95 ° C, or bis (1- (butenyl-2) -2,2,6,6- tetramethyl-4-piperidinyl) dibenzylmalonic acid ester (compound 15) with a temp Melting point 104-10500, or bis (1- (3-methyl-butenyl-2) -2,2,6, b-tetramethyl-4-piperidinyl) dibenzylmalonic acid ester (compound- 16) with a temperature of melting 112-113 ° C, or bis (1- (4-tert-butyl-benzyl) -2,2,6, b-tetramethyl-4-piperidinyl) ester of dibenzylmalonic acid (compound 17) with melting point 151-152 0.
    Example 18: 47 g of diethyl.almonium KIS-LOTE dimethyl ether and 98.6 g of 1-allyl-2,2,6,6-tetramethyl-4-hydroxypiperidine are heated in 100 ml of xylene after adding 1 g of tetrabutyl orthotitanate in a weak stream of nitrogen. to about 140 ° C. The methanol produced by the reaction is continuously distilled off. After approximately 6 hours, the reaction is almost complete. The reaction mixture is diluted with 200 ml of toluene, extracted three times with water, using 100 ml of water each time, dried over sodium sulfate and evaporated. As a result of crystallization of the residue from hexane, bis- (1-allyl-. -2,2,6,6-tetramethyl-4-piperidinyl diethylmalonic acid ester (compound is) is obtained with a melting point of 135-136 ° C.
    PRI-m e s 19-26. If equivalent amounts of the corresponding dialkylated methyls or diethyl esters of malonic acid and alkyl 4-hydroxypiperidines are used as starting products and do otherwise as described in Example 18, bis- (1-benzyl-2,2, 6,6-tetramethyl-4-piperidinyl) ester of diethylmalonic acid (compound 19 with melting point 158-159 C, or bis (1-butyl-2,2, b, b-tetramethyl-4-piperidinyl) GENERAL ester of diethylmalonic acid (compound 20) with a melting point of 8-5-86 0, or bis (1-ben yl-2, 2, b., 6-tetramethyl-4-piperidinyl j-ov dimethylmalonic acid ester (compound 21) with a melting point of 144-145 ° C, or bis (1-allyl-2.2.6, b-tetramethyl-4-piperidinyl) dibutylmalonic acid ester (compound 22) with a melting point of 68-69 s, or bis (1-benzyl-2, 2, 6,6-tetramethyl-4-piperidinyl) dibutylmalonic acid ester (compound 23 with a melting point of 110-112 ° C, or else bis- (1., 2,2,6, 6-pentamethyl-4-piperidinyl) -acetylbenzylmalonic acid ester (compound 24 with a melting point 92 -93 0 ,, or the bis (1,2, 2, b, 6-pentamethyl-4-piperidinyl) ester of n-butyl-benzylmalonic acid (compound 25) with a melting point of 78-790 s, or .bis- (2,3, b-trimethyl-2, b-diethyl-4-piperidinyl) -diethylmalonic acid ester (compound 26) with a boiling point (0.005 mm Hg), or even a bis ( 1-octyl-2,2,6,6-tetramethyl-4-piperidinyl ester of dibenzylmalonic acid (compound 27) with a melting point of 80-81 s, or bis (1- (2-benzyloxy ethyl) -2, 2,6,6-tetramethyl-4-piperi-, dinyl) n-butyl benzylmalonic acid ester (with Compound 28) in the form of highly viscous non-distilled oil. Example 29. 131.6 g of bis- (2,2,6,6-tetramethyl-4-piperidinyl)} diethylmalonic acid ester (compound 1) are mixed with 250 ml of anhydride-acetic acid for 48 hours at a temperature of 80-85 s After that, the excess amount of anhydride and the acetic acid formed is distilled off as completely as possible under vacuum. The brownish oil is dissolved in 300 ml of toluene and the toluene solution is extracted three times with 100 ml of water. The toluene solution is dried over sodium sulfate and after this is completely evaporated). The crystalline residue is recrystallized from hexane. Bis- (1-acetyl-2,2, 6,6-tetramethyl-4-piperidinyl} ester of diethylmalonic acid (compound 29) is obtained with a melting point of 112-113 0. Examples 30-31. If according to Example 27 an appropriate amount of bis (2,2,6,6-tetramethyl-4-piperidinyl ester) is used in place of the bis (2,2, b, 6-tetra:; ethyl, 4-piperidinyl) ester of diethylmalonic acid di-n-butylmalonic .acids, or bis- (2,2,6,6-tetramethyl-4-piperid-ynyl) -o.vogo dibenzylmalonic acid ester and do the rest, as described in Example 27 ,. then get b is- (1-acetyl-2, 2,6,6-tetramethyl-4-piperidini-JV, a new ester of di-n-butylmalonic acid (compound 30) in the form of a flowing yellowish oil (molecular distillation at 135 s; 0.005 mm Hg), or bis (1-acetyl-2,2, 6,6-tetramethyl-4-piperidine) sibir dibenzylmalonic acid (compound 31) with a melting point of 132-133 ° C. Example 32. 4, 9 g of bis- (2,2, 6,6-tetramethyl-4-piperidinyl) -a-I diethylmalonic acid ester (compound 1) is dissolved in 300 ml of toluene. To this solution, a solution of 18 g of acrylic acid chloride in 50 ml of toluene is added dropwise in 45 minutes at room temperature and then stirred for 3 hours at. Then, 22.3 g of triethylamine was added dropwise to the reaction mixture for about 30 minutes and then stirred for approximately 10 hours at. After cooling to room temperature, triethylamine hydrochloride is sucked off on a suction filter and the toluene solution is completely evaporated. As a result of the crystallization of the residue from ligroin, bis is obtained. - {1-acryloyl-2, 2,6,6-tetramethyl-4-piperidinyl) - oh diethylmalonic acid complex (compound 32) with a melting point of 110 ° C. Example 33. 100 parts of powdered polypropylene (Moplen, fiber grade, firms Montadison) are homogenized with 0.2 parts of octadecyl ester p) - (3, 5-di-tert.-butyl 4-hydroxyphenyl) -propionic acid and 0.25 parts of stabilizer according to the table below in the Brabender plastograph at 200 ° C for 10 min. The mass obtained in this way is removed as quickly as possible from the mixer and pressed on a elbow press into plates with a thickness of 2-3 mm. A part of the obtained blanks is cut and pressed between two rigid aluminum sheets having a mirror gloss using a manual hydraulic laboratory press for 6 minutes at a pressure of 12 tons in a film with a thickness of 0.5 mm, which is immediately subjected to stretching in cold water. Of this film with a thickness of 0, 5 mm, a film for testing with a thickness of 0.1 mm is manufactured under exactly the same conditions. Samples of 60 x 44 mm are cut out with scissors and irradiated with xenohext 150 or xenotest 1200. At set intervals, these samples are removed for testing from a fedometer and tested for carbonyl content in an IR spectrophotometer. The increase in carbonyl extinction when irradiated with light is a measure of the photo-oxidative degradation of the polymer and is associated with a decrease in the mechanical properties of the polymer. The measure of the protective effect is the time until the extinction of the carbonyl is about 0.3, at which time the film is brittle. The protective effect of stabilizers according to the proposed polymer composition can be seen from the table. 1 (exposure to xenotest 150) and 2 (exposure to xenotest 1200). -.
    权利要求:
    Claims (1)
    [1]
    Claim
    A polymer composition comprising a polymer selected from the group consisting of polyolefin, polystyrene and polyester based on polyester and a malonic acid derivative, characterized in that, in order to increase light aging resistance, it contains total malonate as a malonic acid derivative formulas ^ c-c-co-o where
    R
    R 2
    H, methyl;
    benzyl, C 1 -C ^ alkyl, alkenyl C g -Cd;
    benzyl, alkyl C 1 nyl C 3 -C ^;
    H, alkyl C ^ -Cg, riloyl, alkenyl alkyl C 7 -C (<
    -C ^, alkaacetyl, acC 3 -C 6 , in the following ratio of component weight. %:
    with comrade
    Polymer 99.5-99.99
    Malonate 0.01-0.5.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU797589A3|1981-01-15|Polymeric composition
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    SU708995A3|1980-01-05|Polymeric composition
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    US4238613A|1980-12-09|Polyalkylpiperidine derivatives
    US5457204A|1995-10-10|Tetraalkyl-4-| piperidine compounds as stabilizers
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    US5541274A|1996-07-30|Polymeric adducts of hindered amine-epoxides as stabilizers
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    US4499273A|1985-02-12|Salts of aminic organic peroxides
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    CA1093556A|1981-01-13|Cyanuric acid derivatives
    US4569997A|1986-02-11|Polyalkylpiperidine compounds
    EP0119961B1|1988-01-20|Oligo esters containing polyalkyl piperidine groups
    US3970636A|1976-07-20|Tetramethylpiperidinylphosphine oxides as light stabilizers for polymers
    RU2081115C1|1997-06-10|Dihydropyridine derivatives and stabilized polymeric composition
    US4154722A|1979-05-15|Polyalkylpiperidinyl esters of diazocarboxylic acid and their use for stabilizing polymers
    EP0410970A1|1991-02-06|Reactive hindered amine light stabilizers.
    US5534618A|1996-07-09|Polyethers containing hindered amines which can be cleaved off as stabilizers
    KR810001105B1|1981-09-18|Process for preparing malonates
    EP0516192A2|1992-12-02|Reactive hindered amine light stabilizers
    GB2134112A|1984-08-08|Polyalkylpiperidine esters of aliphatic tetracarboxylic acids
    同族专利:
    公开号 | 公开日
    BE854197A|1977-11-03|
    AU2482777A|1978-11-09|
    GB1573770A|1980-08-28|
    DE2718458C2|1989-09-14|
    JPH0232298B2|1990-07-19|
    US4293468A|1981-10-06|
    FR2350342A1|1977-12-02|
    US4369275A|1983-01-18|
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    JPS52133990A|1977-11-09|
    CA1091235A|1980-12-09|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3640928A|1968-06-12|1972-02-08|Sankyo Co|Stabilization of synthetic polymers|
    BE792043A|1971-11-30|1973-05-29|Ciba Geigy|PIPERIDINE DERIVATIVES USED TO STABILIZE ORGANIC MATERIALS|
    US4021432A|1971-11-30|1977-05-03|Ciba-Geigy Corporation|Piperidine derivatives|
    CH589056A5|1973-12-10|1977-06-30|Ciba Geigy Ag|
    US4056507A|1973-12-28|1977-11-01|Ciba-Geigy Corporation|Hindered piperidine carboxylic acids, metal salts thereof and stabilized compositions|
    JP4643302B2|2005-02-23|2011-03-02|株式会社東芝|Mask pattern creation method, layout creation method, photomask manufacturing method, photomask, and semiconductor device manufacturing method|DE2755340A1|1976-12-23|1978-06-29|Ciba Geigy Ag|NEW POLYALKYLPIPERIDE DERIVATIVES|
    EP0002260B1|1977-12-02|1982-07-14|Ciba-Geigy Ag|Malonic acid derivatives of sterically hindered piperidines, process for their preparation and stabilised organic matter|
    IT1110826B|1979-02-01|1986-01-06|Montedison Spa|N-ALCHIL-PIPERIDIN DERIVATIVES OF HYDROXY-BENZYL MALONIC ACID AND THEIR USE AS POLYMER STABILIZERS|
    US4444928A|1981-08-14|1984-04-24|Ciba-Geigy Corporation|Polymeric malonic acid derivatives|
    US4526972A|1984-06-27|1985-07-02|Texaco Inc.|Ultraviolet light stabilizing sterically hindered polyoxyalkylene amines|
    US4965301A|1984-12-03|1990-10-23|Phillips Petroleum Company|Stabilization of polyolefins|
    US4701485A|1985-10-11|1987-10-20|Ici Americas Inc.|Malonate-based light stabilizers for plastics|
    US4762872A|1985-11-01|1988-08-09|The B. F. Goodrich Company|Oligomeric light stabilizers with substituted piperidine ends|
    DE3724223A1|1987-07-22|1989-02-02|Huels Chemische Werke Ag|STABILIZER SYSTEM|
    JPH03115496U|1990-03-12|1991-11-28|
    KR920002533A|1990-07-19|1992-02-28|베르너 발데크|Antioxidation Method of Petrochemical Extraction Solvent|
    EP0518197B1|1991-06-03|1994-12-21|Mitsubishi Chemical Corporation|Piperidine derivatives|
    KR100550224B1|1998-12-14|2006-02-08|시바 스폐셜티 케미칼스 홀딩 인코포레이티드|Sterically hindered amine compounds|
    US7081213B2|2002-05-14|2006-07-25|Clariant FinanceLimited|Stabilizer mixtures for the protection of polymer substrates|
    WO2006022405A1|2004-08-24|2006-03-02|Fujifilm Corporation|Silver halide color photographic photosensitive material and method of image forming|
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    JP5244437B2|2008-03-31|2013-07-24|富士フイルム株式会社|UV absorber composition|
    JP2010059235A|2008-09-01|2010-03-18|Fujifilm Corp|Ultraviolet absorbent composition|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH555876|1976-05-04|
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