• 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:
    A) rigid or semi-rigid PVC having a plasticizer content of 20% or less, and B) at least one compound of the formula (1) It is to be noted that the perchlorate compound, the glycidyl compound, the beta-diketone, the beta-ketoester, the dihydropyridine, the polydihydropyridine, the polyol, the disaccharide alcohol, the sterically hindered amine (tetraalkylpiperidine compound) (Zeolite), hydrotalcite, alkali alumocarbonate (doosonite) are not present: Wherein X is O or S and R is H or phenyl.
    公开号:KR19980024864A
    申请号:KR1019970048183
    申请日:1997-09-23
    公开日:1998-07-06
    发明作者:울프강 베너；한스-헬무트 프리드리히；롤프 드레베스；말자츄어
    申请人:한스-피터 위트린；시바 스페셜티 케미칼스 홀딩 인코포레이티드；
    IPC主号:
    专利说明:

    Stable PVC stabilized with N, N-dimethyl-6-aminouracil
    The present invention relates to stabilizing hard or semi-rigid PVC with heavy metals by using certain N, N-dimethyl-6-aminouracils defined by the formula (1) below.
    DE 1 694 873 describes the use of certain uracil compounds to stabilize PVC from heat and oxidative stresses. However, this document describes only a soft PVC composition comprising aminourasil. Other aminoauracyl and aminothiouracil compounds are also described as PVC stabilizers. (EP 0 065 934, EP 0 354 179, EP 0 041 479). It is currently known that these aminouracil and aminothiouracil compounds have a limited fitness for soft PVC since they cause contamination or decolorization in systems where their presence is stabilized. Surprisingly, however, PVC containing less than 20% plasticizer, so-called hard, semi-rigid PVC, can be highly stabilized using the compound of formula (1) described below. Pollution is no longer a problem.
    It is an object of the present invention to stabilize a hard or semi-rigid PVC by using a specific N, N-dimethyl-6-aminouracil.
    Therefore,
    A) rigid or semi-rigid PVC with up to 20% plasticizer, and
    B) at least one compound of the formula (1)
    It is to be noted that the perchlorate compound, the glycidyl compound, the beta-diketone, the beta-ketoester, the dihydropyridine, the polydihydropyridine, the polyol, the disaccharide alcohol, the sterically hindered amine (tetraalkylpiperidine compound) (Zeolite), hydrotalcite, alkali alumocarbonate (doosonite) are not present in the composition:
    Wherein X is O or S, and R is H or a phenyl group.
    B) is a compound of formula (1) wherein X is O, in particular B)
    Is preferred.
    The present invention relates to the use of a compound of formula (1) for stabilizing hard or semi-rigid PVC under the above-mentioned cues.
    The compound of formula (1) is advantageously incorporated into hard or semi-rigid PVC to be stabilized in an amount advantageously from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, in particular from 0.1 to 3% by weight, based on the total composition .
    The compositions of the present invention may also contain other additives such as stabilizers, adjuvants and processing aids, typical alkali metal compounds, alkaline earth metal compounds, lubricants, plasticizers, pigments, fillers, phosphates, thiophosphates, thiophosphates, mercaptocarboxylates, , Antioxidants, UV absorbers, light stabilizers, fluorescent brighteners, impact modifiers, gelling agents, antistatic agents, biological poisons, metal deactivators, flame retardants, foaming agents as well as defoamers. John Wiley Sons New York 1993). A detailed example of such an additive is as follows:
    I. Fillers: fillers (HANDBOOK OF PVC FORMULATING EJ Wickson John Wiley Sons, Inc., 1993 pp. 393-449) and reinforcing agents (TASCHENBUCH der KA , e R. Gachter H. Muller, Carl Hanser, 1990, pp. ), Typically calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicate, talc, talc, glass fiber, glass beads, wood flour, mica, metal oxides, metal hydroxides, carabons black, graphite, mineral powders, , Kaolin and chalk. Chalk is preferred. The filler is preferably used in an amount of 1 part by weight or more, typically 5 to 200 parts by weight, advantageously 10 to 150 parts by weight, and particularly preferably 15 to 100 parts by weight, based on 100 parts by weight of PVC.
    II. Metal soap: The metal soap is mainly a metal carboxylate of long chain carboxylic acid. The basic examples are stearates, laurates, oleates and salts of short-chain alkylcarboxylic acids. Metal soaps are also understood to mean alkylbenzoic acids. Synergistic mixtures such as so-called barium / zinc, magnesium / zinc, calcium / zinc or calcium / magnesium / zinc stabilizers are also frequently used. Metal soap can be used alone or as a mixture. A record of commonly used metal soaps is found in Ullmanns Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A16 (1985) p.361 and later. Aliphatic saturated C 2 -C 22 carboxylates, aliphatic unsaturated C 3 -C 22 carboxylates, aliphatic C 2 -C 22 carboxylates substituted with one or more OH groups, cyclic or bicyclic carboxylates including 5-22 carbons, ring or substituted with one or more OH groups or C 1 -C 16 alkyl phenyl carboxylate, unsubstituted or at least one OH group or a C 1 -C 16 alkyl group substituted with a naphthyl carboxylate, phenyl -C 1 -C 16 alkyl It is advantageous to use organometallic soaps of the phenate, tallate, or renate system substituted with carboxylate, naphthyl-C 1 -C 16 alkylcarboxylate or unsubstituted or C 1 -C 12 alkyl.
    Typical examples mentioned are monocarboxylic acids (such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, P-tert-butylbenzoic acid, N, N, -dimethylhydroxybenzoic acid, 3, 5-dihydroxystearic acid, Zinc, calcium, and magnesium of 5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, Or barium salts; Dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1,7-dicarboxylic acid, octane-1,6-dicarboxylic acid, Calcium, magnesium and zinc salts of monoesters of 1,8-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; And di- or triesters of 3,4-dicarboxylic acids (typically hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid).
    Magnesium carboxyrate, zinc carboxylate (metal soap of more stringent meaning), typically benzoates or alkanoates, preferably stearates, oleates, laurates, carboxymethylcellulose, Palmitate, behenate, hydroxystearate, dihydroxystearate or 2-ethylhexanoate is preferably used. Overbased carboxylates such as overbased zinc octanoate are also preferred.
    Mixtures of carboxylates of different structures may also be used if desired.
    A preferred composition is a composition comprising an organozinc compound and / or a calcium compound as described above.
    In addition to the cited compounds, organoaluminum compounds, preferably those similar to those described above, are also suitable. Details of suitable, more suitable aluminum compounds are given in US 4 060 512 and US 3 234 394. In addition to the compounds described so far, organic rare earth compounds, particularly those similar to those described above, are also suitable. The term rare earth compound refers to a compound of cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, tulium, ytterbium, lutetium, lanthanum and yttrium elements and particularly preferably a mixture with cerium. Other preferred rare earth compounds are described in EP-A-0 108 023.
    Mixtures of zinc, alkaline earth metals, aluminum, lanthanum or lanthanoid compounds of different structures can also be used if desired. Organozinc, aluminum, lanthanum or lanthanoid compounds may also be coated on the anilato salt compound. See DE-A-4 031 818.
    The metal soap or mixture thereof is typically used in an amount of typically 0.001 to 10 parts by weight, advantageously 0.01 to 8 parts by weight, and particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight of PVC. The same applies to other metal stabilizers.
    III. Other metal stabilizers: Organotin stabilizers are particularly worthy of mention here. These are preferably carboxylates, mercaptides and sulfides. Suitable examples are described in US 4 743 640.
    IV. Alkali metal compounds and alkaline earth metal compounds: These are understood in particular as the carboxylates of the acids mentioned, the corresponding oxides or hydroxides or carbonates. Mixtures of these and organic acids are also suitable. Typical examples are NaOH, KOH, CaO, Ca (OH) 2 , MgO, Mg (OH) 2 , CaCO 3 and MgCO 3 as well as fatty acid sodium salts and fatty acid potassium salts. In the case of alkaline earth metal carboxylate and zinc carboxylate, an adduct of MO or M (OH) 2 (M = Ca, Mg, Sr or Zn) called so-called overbased compound can be used. It is preferred to use alkali metal carboxylates, alkaline earth metal carboxylates and aluminum carboxylates in addition to the new stabilizer combination.
    V. Lubricants: Suitable lubricants are Montan waxes, fatty acid esters, PE waxes, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps. Mainly used lubricants are Kunststoffadditive, R. Gachter / H. Muller, Carl Hanser Verlag, 3rd Ed., 1989, pages 478-488. (Described in DE 4 204 887) and silicone based lubricants (as described in EP 225 261), or combinations thereof, as described in EP 259 783.
    VI. Plasticizers: Suitable organic plasticizers are:
    A) Phthalates: Typical examples of these plasticizers are dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, di- Dicyclohexyl phthalate, di-methyl cyclohexyl phthalate, dimethyl glycol phthalate, dibutyl glycol phthalate, benzyl butyl phthalate and diphenyl phthalate, as well as nonyl phthalate, di-iso-decyl phthalate, Such as C 7 -C 9 and C 9 -C 11 alkyl phthalates of linear alcohols, C 6 -C 10 -n-alkyl phthalates, C 8 -C 10 -n-alkyl phthalates. Of these, dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-iso-octyl phthalate, di- Tridecyl phthalate and benzyl butyl phthalate as well as mixtures of the alkyl phthalates cited are preferred. Particular preference is given to using di-2-ethylhexyl phthalate, di-iso-nonyl phthalate and di-iso-decyl phthalate, which are commonly known by the generic name DOP (dioctyl phthalate, di-2-ethylhexyl phthalate) DINP (diisononyl phthalate), DIDP (diisodecyl phthalate).
    B) Esters of aliphatic dicarboxylic acids, mainly adipic acid, azelaic acid, sebacic acid: Typical examples of such plasticizers are di-2-ethylhexyl adipate, diisooctyl adipate (mixture), diisononyl adipate (Mixture), diisodecyl adipate (mixture), benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl sebacate . Di-2-ethylhexyl adipate and diisooctyl adipate are preferred.
    C) trimellitate, typically tri-2-ethylhexyl trimellitate, tri isodecyl trimellitate (mixture), tri isotridecyl trimellitate, teuriyi sook butyl trimellitate (mixture), tri -C 6 -C 8 alkyl, tri -C 6 -C 10 alkyl trimellitate, tri -C 7 -C 9 alkyl trimellitate and tri -C 9 -C 11 alkyl trimellitate. The latter trimellitate can be obtained by esterifying the trimellitate and the corresponding alkanol mixture. A preferred trimellitate is trimellitate of a mixture of tri-2-ethylhexyl trimellitate and the alkanol mentioned. Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimellitate), and TITDTM (triisotridecyl trimellitate).
    D) Epoxidized plasticizer: Most of these are epoxidized unsaturated fatty acids such as epoxidized soybean oil.
    E) Polymeric plasticizers: Definitions and examples of such plasticizers are given in Kunststoffadditive, R. Gachter / H. Muller, Carl Hanser Verlag, 3rd Ed., 1989, pages 412-415 and PVC Technology, W. V. Titow, 4th Ed Elsevier Pulb., 1984, pages 165-170. Most starting materials for the preparation of polyester plasticizers are dicarboxylic acids, typically adipic acid, phthalic acid, azelaic acid, sebacic acid; 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol.
    F) Phosphoric esters: The definition of these esters is given in Taschenbuch der Kunststoffadditive, cited above, 5.9.5, p. 408-412. Specific examples of the phosphate include tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphopet, trichloroethyl phosphate, 2-ethylhexyl-di-phenyl phosphate, cresyldiphenyl phosphate, triphenyl phosphate , Tricresyl phosphate, trixylenyl phosphate, tri-2-ethylhexyl phosphate, Reofos 50 and 95 (Ciba-Geigy) are preferred.
    G) Chlorinated hydrocarbons (paraffin)
    H) Hydrocarbon
    I) monoesters, typically butyl oleate, phenoxy ethyl oleate, tetrahydryl furfuryl oleate, alkyl sulphonates.
    J) glycol esters such as diglycol benzoate.
    Examples and definitions of plasticizers in groups G) to J) are described in the following brochure.
    Kunststoffadditive, R. Gachter / H. Muller, Carl Hanser Verlag, 3rd Ed., 1989, chapter 5.9.14.2, p 422-425 (group G), and chapter 5.9.14.1 p 422 (group H).
    (Group G), Section 6.10.5, page 174 (Group H), Group 6.10.3, page 173 (Group I), " PVC Technology, WVTitow, 4th Ed Elsevier Published, 1984, 6.10.2, pages 171-173 , 6.10.4, pages 173-174 (J group).
    It is also possible to use mixtures of different plasticizers.
    The plasticizer may be used in an amount of typically from 5 to 20 parts by weight, advantageously from 10 to 20 parts by weight, based on 100 parts by weight of PVC. Rigid or semi-rigid PVC preferably contains no more than 10%, particularly preferably no more than 5% of a plasticizer.
    VII. Pigments: Suitable materials are known to those skilled in the art. Typical examples of the inorganic pigments are TiO 2 , BaSO 4 , Carbone black, Fe 2 O 3 , Sb 2 O 3 , (Ti, Ba, Sb) O 2 , Cr 2 O 3 , spinel (for example, cobalt blue and cobalt green) Cd (S, Se) and ultramarine blue. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments. The form of superfine pulverized TiO 2 is also preferred. Definitions and detailed techniques are described in Handbook of PVC Formulating, EJ Wickson, John Wiley Sons, New York 1993.
    VIII. Phosphites: Typical examples are triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bisisodecyloxyl pentaerythritol diphosphite, bis (2,4-di- tert -butyl-6-methylphenyl) pentaerythritol diphosphite, bis Bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4,6-tri-tert- butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, Di-tert-butyl-6-methylphenyl) ethyl phosphite. Trioctyl phosphite, tridecyl phosphite, tridecyl phosphite, tridecyl phosphite, tridecyl phosphite, tridecyl phosphite, tridecyl phosphite, tridecyl phosphite, Phenylphosphite and tricyclohexylphosphite are particularly suitable, and aryldialkyl phosphites and alkyldiaryl phosphites (for example, phenyldodecylphosphite, (2,4-di-tert-butylphenyl) decyl phosphite, (2,6-di-tert-butylphenyl) - di-dodecyl phosphite and dialkyl-and diaryl pentaerythritol diphosphite, distearyl penta diphosphite eriseuroyi tolyl and example composition (H 19 C 9 C 9 H 4 O) 1.5 P (OC 12 , 13 H 25 , 27 ) 1.5 ) is particularly preferred. Preferred organic phosphites are distearyl pentaerythritol diphosphite, trisnonyl phenyl phosphite, and phenyldodecyl phosphite. The organic phosphite may be used in an amount of typically 0.01 to 10 parts by weight, advantageously 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of PVC.
    IX. Thiophosphites and thiophosphates: Thiophosphites and thiophosphates have the general type (RS) 3 P, (RS) 3 P = O as described in patent publications DE 28 09 492, EP 090. 770 and EP 573. 394 Or (RS) 3 P = S. Typical examples of such compounds include, but are not limited to, trithiohexyl phosphite, trithiooctyl phosphite, trithioauryl phosphite, trithiobenzyl phosphite, methyl tris (carbo-i-octyloxy) trithiophosphite, methyl tris S-tris (carbo-i-octyloxy) trithiophosphate, methyl-S, S, S-tris (carbo-2-carboxy- -Ethylhexyloxy) trithiophosphate, ethyl-S, S, S-tris-1- (carbohexyloxy) trithiophosphate, ethyl-S, S, S- Ethylhexyloxy) trithiophosphate, ethyl-S, S, S-tris-2- (carbo-2-ethylhexyloxy) trithiophosphate.
    X. Mercaptocarboxylates: Typical examples of such compounds are thioglycolic acid, thiomalic acid, mercaptopropionic acid, as described in patent FR 2 459 816, EP 90,748, FR 2 552 440, EP 365. 483 , Esters of mercaptobenzoic acid or thiouric acid. The mercaptocarboxylate also includes polyol esters or partial esters thereof.
    XI. Epoxidized fatty acid esters: The combination of the novel stabilizers may additionally contain one or more epoxidized fatty acid esters. Suitable esters are especially fatty acid esters of fatty acids (fatty acid glycerides), such as soybean oil and rapeseed oil. However, synthetic products such as epoxidized butyl oleate may also be used.
    XII. Antioxidants: Suitable antioxidants are:
    1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6- Butyl-4-iso-butylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6- ( -methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6- 4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- Mixtures thereof.
    2. Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl- Phenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
    3. Alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di- tert -butylhydroquinone, 2,5-di- tert-amylhydroquinone, Di-tert-butyl-4-hydroxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di- 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
    4. Hydroxyated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol) Thiobis- (6-tert-butyl-3-methylphenol), 4,4'-thiobis- (6-tert- - secondary-amylphenol), 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.
    5. Alkydene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis Methylene-bis (4-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'- Methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6- (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) Methylenebis [2,6-di-tert-butylphenol], 4,4'-methylenebis [6- (alpha, alpha -dimethylbenzyl) (Tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6- Butylphenyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy- Hydroxy-2-methyl-phenyl) -3-n-dodecyl (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentane Dienes such as bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6- tert- Bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2- Methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
    6. Benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercapto Acetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di- tert -butyl-4-hydroxybenzyl) amine, bis Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di- tertiary -Butyl-4-hydroxybenzyl mercaptoacetate.
    7. Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl 2- Butyl-4-hydroxybenzyl) malonate, di-dodecyl mercaptoethyl-2,2-bis- (3,5-di- tert- Bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
    8. An aromatic hydroxybenzyl compound such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis , 3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris Benzyl) phenol.
    9. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5- Bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis , 3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris ) -1,2,3-triazine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (Tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3, 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
    10. Phosphonates and phosphonites such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di- tert -butyl-4-hydroxybenzyl Butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl- Di-tert-butyl-4-hydroxybenzylphosphonic acid, tetrakis (2,4-di-tert-butylphenyl) -4,4 , -biphenylene diphosphonite , 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro- 8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine.
    11. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
    12. A process according to any one of the preceding claims, wherein the mono- or polyhydric alcohol such as methanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, Triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and - (3,5- - < / RTI > hydroxyphenyl) propionic acid.
    13. Use of mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene (Diethyleneglycol), triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecane Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and - (5-tert-butyl- 3-methylphenyl) propionic acid .
    14. A process for the production of a mono- or polyhydric alcohol such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene (Diethyleneglycol), triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecane Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and - (3,5-dicyclohexyl- - < / RTI > hydroxyphenyl) propionic acid .
    15. The process according to claim 1, wherein the mono- or polyhydric alcohol is selected from the group consisting of methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, (Diethyleneglycol), triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecane Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and 3,5-di- Esters of hydroxyphenylacetic acid .
    16. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as N, N'-bis (3,5-di- tert -butyl-4-hydroxyphenylpropionyl N, N'-bis (3,5-di-tert-butyl) methylene diamine, N, -4-hydroxyphenylpropionyl) hydrazide.
    17. Vitamin D (tocopherol) and its derivatives
    Preferred antioxidants are antioxidants of the groups 1-5, 10 and 12, in particular 2,2-bis (4-hydroxyphenyl) -propane, 3,5-di- tert -butyl-4-hydroxyphenylpropionic acid and octadecane Or an ester of pentaerythritol or tris- (2,4-di-tert-butylphenyl) -phosphite.
    If desired, antioxidant mixtures of different structures may be used.
    The antioxidant may be used in an amount of typically 0.01 to 10 parts by weight, advantageously 0.1 to 10 parts by weight, and especially 0.1 to 5 parts by weight, based on 100 parts by weight of PVC.
    XIII. UV absorbers and light stabilizers: Detailed examples are as follows.
    1. 2- (2'-hydroxyphenyl) benzotriazole such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'- 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'- , 3'-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'- 3'-tert-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole Benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (2'- (3 ', 5'-bis- ( , - dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) -carbonylethyl] -phenyl) -5-chloro-benzotriazole 2'-hydroxyphenyl) -5-cl Benzotriazole, 2- (3 ' -tert-butyl-2 ' -hydroxy-5 '-( 2-methoxycarbonylethyl) (3'-tert-butyl-2'-hydroxy-5'- (2-methoxy-carbonylethyl) phenyl) benzotriazole, (3-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzoate Triazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'- Bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazole-2-ylphenol]; 2- Transesterification reaction product of [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; -Butyl-4'-hydroxy-5'-2H-benzotriazol- 2 -ylphenyl [R-CH 2 CH 2 -COO (CH 2 ) 3 ] -.
    2. 2-Hydroxybenzophenones , such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, Trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivative.
    3. Esters of unsubstituted or substituted benzoic acids such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl- Benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid ester, 3,5-di- tert -butyl-4-hydroxybenzoic acid Di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl- Butyl phenyl ester.
    4. Acrylates such as alpha -cyano-beta, beta -diphenylacrylic acid ethyl ester or isooctyl ester, alpha -methoxycarbonylninic acid methyl ester, alpha -cyano- beta -methyl- Cinnamic acid methyl ester or butyl ester, -Methoxycarbonyl-p-methoxycinnamic acid methyl ester and N- ( -Methoxycarbonyl - - cyanovinyl) -2-methylindoline.
    5. Nickel compounds , such as 2,2'-thio-bis [4- (1,1,3,3-tetramethylpiperidin-4-yl) Tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl ester Such as the nickel salt of a methyl ester or ethyl ester, a nickel complex of a ketoxime such as 2-hydroxy-4-methylphenyl undecylketoxime, if appropriate 1-phenyl-4-lauroyl- Nickel complexes of Roxy pyrazoles.
    6. Oxamides such as 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy Di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy- 5-tert-butyl-2'-ethyloxanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, o- and p- - and o- and p-ethoxy-disubstituted oxanilides.
    2,2- (2-hydroxyphenyl) -1,3,5-triazine such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2 (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) - (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- ) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis 4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy- (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy- - octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
    XIV. Blowing agent: The blowing agent is, for example, sodium azide and hydrogen carbonate as well as organic azo and hydrazo compounds, tetrazole, oxazine, isotactic anhydride. Azodicarbonamide, sodium hydrogen carbonate and mixtures thereof are preferred.
    Definitions and examples of impact modifiers, processing aids, gelling agents, antistatic agents, biological poisons, metal deactivators, fluorescent brighteners, flame retardants, defoamers are given in Kunststoffadditive, R. Gachter / H. Muller, Carl Hanser Verlag, 3rd Ed., 1989 and Handbook of Polyvinyl Chloride Formulating E. J. Wickson, John Wiley Sons, New York 1993. Impact modifiers are also described in Impact Modifiers for PVC, JT Lutz / D.L. Dunkelberger, John Wiley Sons, 1992. Typical examples of rigid PVC materials to be stabilized include vinyl chloride polymers, vinyl resins containing vinyl chloride in the structure (e.g., copolymers of vinyl chloride and aliphatic acid vinyl esters, especially vinyl acetate, vinyl chloride and acrylic acid, and methacrylic acid Copolymers of vinyl chloride and diene compounds and unsaturated dicarboxylic acids or their anhydrides, copolymers of vinyl chloride and diethyl maleate, diethyl fumarate or maleic anhydride Copolymers of postchlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and other such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether; Polymers of vinylidene chloride and copolymers thereof with vinyl chloride and other polymerizable compounds , Polymers of vinyl chloroacetate and dichlorodevinyl ether, polymers of vinyl acetate and chlorine and polymers of acrylic acid, chlorinated polymeric esters of alpha-substituted acrylic acid, polymers of chlorinated styrene, for example dichlorostyrene, chlorinated rubber, chlorinated polymers of ethylene, Butadiene polymers and post-chlorinated polymers and copolymers thereof with vinyl chloride, rubber hydrochlorides and chlorinated rubber hydro- chlorides, as well as mixtures with one or more other polymeric compounds with the polymers mentioned.
    These materials also include graft polymers of EVA, ABS, MBS and PVC. Preferred materials are the above homopolymers or copolymers, preferably mixtures of vinyl chloride homopolymers and thermoplastic or elastomeric polymers, in particular ABS, MBS, NBR, SAN, EVA, MBAS, PMA, PMMA, EPDA and poly It is a blend of lactones.
    Specific examples of such component A include (i) 20 to 80 parts by weight of a vinyl chloride homopolymer (PVC) and (ii) one or more of styrene and acrylonitrile, preferably ABS, NBR, NAR, SAN and EVA And 80 to 20 parts by weight of the above thermoplastic copolymer. The abbreviations used in the copolymer are familiar to those skilled in the art and have the following meanings. ABS: acrylonitrile / butadiene / styrene; SAN: styrene / acrylonitrile; NBR: acrylonitrile / butadiene; NAR: acrylonitrile / acrylate; EVA: Ethylene / vinyl acetate. Acrylate based styrene / acrylonitrile copolymers (ASA) are particularly suitable. Component A in this context is a polymer composition comprising as components (i) and (ii) a mixture of 75 to 25 wt.% PVC weight and 25 to 75 wt. Typical examples of such compositions are 25-50 wt% PVC and 75-50 wt% copolymer or 40-75 wt% PVC and 60-25 wt% copolymer. The preferred copolymers are also particularly suitable for ABS, SAN and modified EVA, preferably ABS, NBR, NAR, EVA. One or several of the mentioned copolymers may be present in the novel composition. Particularly important component A comprises (i) 100 parts by weight of PVC and (ii) 0 to 300 parts by weight of ABS and / or SAN, modified ABS and 0 to 80 parts by weight of copolymer NBR, NAR and / or EVA, preferably EVA ≪ / RTI >
    Other suitable compounds that can be used for stabilization within the scope of the present invention are recycled materials of the chlorine-containing polymers which are detailed above and which can be damaged during processing, use or storage. PVC regenerating materials are particularly preferred. The recycling material may contain small amounts of impurities such as paper, pigments and adhesives that are difficult to remove. Such foreign materials can be caused by adhering to various materials such as fuel residues, paint ingredients, metal trace amounts and initiator residues during use or processing:
    The new stabilizers are particularly useful in the case of PVC compounds commonly used in pipes. Stabilization can be used without any heavy metals (Sn, Pb, Zn stabilizers). This property is useful in some areas because heavy metals (except possibly zinc) are often undesirable in the production and use of certain PVCs as environmental factors.
    The present invention relates to a hard, semi-rigid PVC which comprises perchlorate compounds, glycidyl compounds, -Diketones, -Keto-esters, dihydropyridines, polydihydropyridines, polyols, disaccharide alcohols, (1) in the absence of a compound selected from the group consisting of an alkaline earth metal compound, an alkaline earth metal compound, an alkaline earth metal compound, an alkaline earth metal compound, an alkaline earth metal compound, To a method of stabilizing rigid or semi-rigid PVC.
    The incorporation of stabilizers can usually be carried out by the following method.
    As an emulsion or dispersant (a possible form is a paste mixture. In this type of case, an advantage of the novel composition is that the paste is stable).
    As a dry mixture in admixture of an additional component or of a polymer mixture
    By direct application to processing equipment (eg, calenders, mixers, kneaders, extruders, etc.), or
    As a solution or melt
    PVC stabilized by the present invention for the purpose of the present invention can be prepared by known methods of blending a novel stabilizer combination and optional additives with PVC as a known apparatus such as the above-described processing apparatus. The stabilizers may be added alone or in a mixture in masterbatch form.
    The stabilized PVC according to the invention can be made into a desired shape by known methods. Such methods include, for example, grinding, calendaring, extrusion, injection molding or spinning and extrusion blow molding. Stabilized PVC can be processed into foam.
    The rigid PVC stabilized by the present invention is particularly suitable for use in hollow articles (bundles), packaging films (thermoform films), foam films, conduits, foams, thick profiles (window frames), light wall profiles, building profiles, Film and household products (computer, home appliance).
    PVC rigid foaming products and PVC pipes are suitable for water and wastewater, pressure pipes, gas conduits, cable channel tubes and cable sheathed tubes, industrial systems conduits, drain conduits, earth conduits, drain conduits and sewage conduits. Further details are given in Kunststoffhandbuch PVC, Vol.2 / 2, W. Becker / H. Braun, 2nd Ed., 1985, Carl Hanser Verlag, pages 1236-1277.
    The compounds of formula (1) are prepared by known methods as described in more detail in the following examples. Parts and percentages are by weight unless otherwise indicated.
    Example 1: Preparation of 6-amino- 1, 3-dimethyluracil.
    224.8 g of N, N , -dimethylurea, 238.7 g of cyanoacetic acid and 310.9 g of acetic anhydride were heated to 80 DEG C with stirring under nitrogen. The mixture was stirred at 80 DEG C for 2 hours and evacuated to 50 mbar to distill off the acetic acid. After cooling, 35 g of cooling water of 250 g was added to this mixture. The mixture was stirred for 10 minutes and then 567 g of 15% sodium hydroxide solution was added dropwise while cooling with ice. The pH does not rise above 7 to 475 ml. When the pH exceeds 7, the precipitation changes, and when the mixture is heated from 23 ° C to about 50 ° C, the pH is 10.2. After 200 g of water was added, the mixture was stirred for 10 minutes and heated under reflux. After refluxing for 1 hour, the mixture was cooled to 20 < 0 > C and suction filtered. The filtered cake was washed with 2 x 100 g of cooling water and then dried in a vacuum dryer at 90 < 0 > C.
    Yield: 334 g (86.1% of theory), m.p .: 282 캜.
    Example 2: Preparation of 6-phenylamino-1,3-dimethyluracil.
    A mixture of 39.1 g of aniline and 24.5 g of 1,3-dimethylbarbituric chloride was placed in a 100 ml three-necked flask and refluxed with stirring at 190 DEG C for 15 minutes. The mixture was cooled to room temperature and then 300 ml of water was added. Upon stirring, a pale blue precipitate forms, which is collected by suction, washed with ether and dried to constant weight.
    Recrystallization from methylene chloride / activated carbon gave the product as a colorless product which was dried.
    Yield: 22.5 g (69.5% of theory), m.p. 190 ° C.
    Example 3: Electrostatic test.
    The dry mixture consisting of the components recited in the following production variables was rolled for 5 minutes at 180 DEG C on a mixer roller. A 0.3 mm test piece was taken from the rolled sheet thus obtained. The film samples were subjected to a thermal stress test in an oven at 180 ° C. Yellowness Index (YI) was measured at 5 to 10 minute intervals according to ASTM D-1925-70. The results are shown in the following table. A low yellowness index value means good stability.
    Mixture I Mixture II
    S-PVC (K value 64) 100 100
    Epoxidized soybean oil 2 2
    Example 1 Compound - 0.4
    Stress duration (minutes) 0 10 20 30 40 50 60 YI (mixture 1) 24.9 86.9 100 YI (mixture 2) 3.1 9.4 18.0 27.4 44.0 73.5 100
    Mixture III
    S-PVC (K value 64) 100
    Calcium stearate 0.35
    Zinc stearate 0.15
    Epoxidized Soybean Oil 4
    Wax 368 (ester wax) 0.6
    Partially oxidized polyethylene wax 0.1
    Acrylate-based processing aid 0.5
    Impact modifier 8
    Example 1 Compound 0.6
    Stress duration (minutes) 0 10 20 30 40 50 YI (mixture III) 9.3 11.0 17.9 26.0 37.1 59.8
    Mixture IV Mixture V
    S-PVC (K value 64) 100 100
    Epoxidized soybean oil 2 2
    Example 2 Compound-0.6
    Stress duration (minutes) 0 10 20 YI (mixture IV) 13.2 73.6 100 YI (mixture V) 4.2 18.9 53.7
    Mixture VI
    S-PVC (K value 64) 100
    Calcium stearate 0.35
    Zinc stearate 0.15
    Epoxidized Soybean Oil 4
    Wax 368 (ester wax) 0.6
    Partially oxidized polyethylene wax 0.1
    Acrylate-based processing aid 0.5
    Impact modifier 8
    Example 2 Compound 0.6
    Stress duration (minutes) 0 10 20 30 40 50 YI (mixture VI) 7.3 11.9 22.1 62.4 87.0 100
    Mixture VII
    S-PVC (K value 64) 100
    Epoxidized soybean oil 0.15
    Calcium stearate 3
    Zinc stearate 0.35
    Example 1 Compound 0.3
    Stress duration (minutes) 0 10 20 30 40 50 YI (mixture VII) 5.2 7.1 8.4 15.8 34.5 60.4
    Mixture VIII Mixture IX
    S-PVC (K value 64) 100 100
    Epoxidized soybean oil 2 2
    Example 1 Compound-0.4
    Stress duration (minutes) 0 10 20 30 40 50 60 YI (mixture VIII) 48.6 115 173.9 YI (mixture XI) 7.0 13.4 24.1 32.3 52.5 79.4 100
    By using certain compounds according to the present invention, hard or semi-rigid PVC can be stabilized without problems of discoloration or contamination.
    权利要求:
    Claims (11)
    [1" claim-type="Currently amended] A) a hard or semi-rigid PVC comprising up to 20% of a plasticizer, and
    B) one or more compounds of the formula (1)
    It is to be noted that the perchlorate compound, the glycidyl compound, the beta-diketone, the beta-ketoester, the dihydropyridine, the polydihydropyridine, the polyol, the disaccharide alcohol, the sterically hindered amine (tetraalkylpiperidine compound) (Zeolite), hydrotalcite, alkali alumocarbonate (doosonite) are not present:

    Wherein X is O or S and R is H or phenyl.
    [2" claim-type="Currently amended] The composition of claim 1, wherein A) is a hard PVC comprising up to 10% plasticizer.
    [3" claim-type="Currently amended] The composition of claim 1, wherein A) is a hard PVC comprising up to 5% plasticizer.
    [4" claim-type="Currently amended] The composition of claim 1 wherein A) is a rigid PVC without any plasticizer.
    [5" claim-type="Currently amended] The composition of claim 1, wherein B) is a compound of formula (1) wherein X is O.
    [6" claim-type="Currently amended] 6. The method according to claim 5, wherein B)
    / RTI >
    [7" claim-type="Currently amended] The composition of claim 1, wherein the heavy metal is substantially absent.
    [8" claim-type="Currently amended] The composition of claim 1, further comprising a phosphite.
    [9" claim-type="Currently amended] Perchlorate compounds, glycidyl compounds, beta-diketones, beta-keto esters, dihydropyridines, polydihydropyridines, polyols, disaccharide alcohols, sterically hindered amines (tetraalkylpiperidine compounds), alkali alumosilicates (1) for stabilizing a hard or semi-rigid PVC having a plasticizer content of 20% or less in the absence of a compound selected from the group consisting of hydrotalcite, alkali alumocarbonate (doosonite) .
    [10" claim-type="Currently amended] Use of a composition according to claim 1 for producing a pipe.
    [11" claim-type="Currently amended] Perchlorate compounds, glycidyl compounds, beta-diketones, beta-keto esters, dihydropyridines, polydihydropyridines, polyols, disaccharide alcohols, sterically hindered amines (tetraalkylpiperidine compounds), alkali alumosilicates ) Containing at least one compound of formula (1) as defined in claim 1, in the absence of a compound selected from the group consisting of hydrotalcite, alkali alumocarbonate (doosonite) Lt; RTI ID = 0.0 >% < / RTI > of plasticizer.
    类似技术:
    公开号 | 公开日 | 专利标题
    KR100286116B1|2001-04-16|3-|benzofuran-2-one stabilizer
    DE10309385B4|2007-01-18|Flame retardant stabilizer combination for thermoplastic polymers and their use as well as flameproof plastic molding compounds
    US5216052A|1993-06-01|Bisbenzofuran-2-ones
    KR100228412B1|1999-11-01|Stabilised polymers containing heteroatoms in the main chain
    AU767538B2|2003-11-13|Synthetic polymers comprising additive blends with enhanced effect
    EP0119160B1|1986-11-05|N-substituted 4-hydroxyphenylthiomethyl amines or urides
    EP0570337B1|1998-03-18|Stabilised chlorine-containing polymer compositions
    CA2526879C|2009-12-15|Stabiliser combinations for chlorine-containing polymers
    US7077981B2|2006-07-18|Chlorate-containing stabilizer system with nitrogen-containing synergists for stabilizing halogen-containing polymers
    CN102099364B|2015-05-13|High purity monoalkyltin compounds and uses thereof
    KR101039285B1|2011-06-07|Stabilizer System For Stabilizing PVC
    SU713536A3|1980-01-30|Polyvinil chloride based composition
    EP0433230B1|1997-05-14|Beta-ketoesters as stabilizers for chlorine containing polymerisates
    EP2083044A1|2009-07-29|Composition for stabilizing halogen-containing polymers
    ES2265603T3|2007-02-16|antistatic composition.
    EP0052579B1|1984-11-14|Stabilisers against photo degradation
    EP2315805B1|2015-05-27|Filled poly vinyl chloride composition
    CZ20031643A3|2003-09-17|Stabilizer system for stabilization of halogen-containing polymers
    US20040138354A1|2004-07-15|Stabiliser combination for halogen-containing polymers and the use thereof
    CA1154898A|1983-10-04|Chlorinated thermoplastics stabilised withaminothiouracils
    ES2136823T5|2004-03-16|Poly | stabilized.
    US7282527B2|2007-10-16|Stabilization system for halogen-containing polymers
    US20090306257A1|2009-12-10|Stabilizer System for Halogenated Polymers
    EP0625546B1|1998-05-13|Stabilized polyvinyl chloride
    EP0716123B1|1999-04-07|Stabilized polyvinyl chloride
    同族专利:
    公开号 | 公开日
    DE19741778A1|1998-03-26|
    CA2216141A1|1998-03-25|
    IT1295058B1|1999-04-27|
    NL1007121C2|1998-05-18|
    NO315165B1|2003-07-21|
    NO974416D0|1997-09-24|
    TW404964B|2000-09-11|
    US5859100A|1999-01-12|
    GB9720124D0|1997-11-19|
    FR2753709A1|1998-03-27|
    FI973734A|1998-03-26|
    FI973734A0|1997-09-19|
    ZA9708531B|1998-03-25|
    DK106297A|1998-03-26|
    ITMI972161A1|1999-03-24|
    ATA162497A|2000-07-15|
    ES2131017A1|1999-07-01|
    NO974416L|1998-03-26|
    GB2318118B|2000-12-27|
    FR2753709B1|1998-11-27|
    MX9707314A|1998-08-30|
    AU3834597A|1998-04-02|
    ES2131017B1|2000-03-01|
    SE9703423D0|1997-09-23|
    BR9704856A|1998-12-29|
    AU715135B2|2000-01-20|
    SE9703423L|1998-03-26|
    NL1007121A1|1998-03-31|
    GB2318118A|1998-04-15|
    AT407395B|2001-02-26|
    BE1011371A3|1999-08-03|
    FI973734D0|
    JPH10158454A|1998-06-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-09-25|Priority to CH234496
    1996-09-25|Priority to CH2344/96
    1997-09-23|Application filed by 한스-피터 위트린, 시바 스페셜티 케미칼스 홀딩 인코포레이티드
    1998-07-06|Publication of KR19980024864A
    优先权:
    申请号 | 申请日 | 专利标题
    CH234496|1996-09-25|
    CH2344/96|1996-09-25|
    [返回顶部]