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EP0841187A1 - Compositions polymères à mouler, marquable au laser - Google Patents

Compositions polymères à mouler, marquable au laser Download PDF

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Publication number
EP0841187A1
EP0841187A1 EP97118623A EP97118623A EP0841187A1 EP 0841187 A1 EP0841187 A1 EP 0841187A1 EP 97118623 A EP97118623 A EP 97118623A EP 97118623 A EP97118623 A EP 97118623A EP 0841187 A1 EP0841187 A1 EP 0841187A1
Authority
EP
European Patent Office
Prior art keywords
weight
parts
bis
molding compositions
hydroxyphenyl
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.)
Withdrawn
Application number
EP97118623A
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German (de)
English (en)
Inventor
Detlev Dr. Joachimi
Herbert Magerstedt
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.)
Bayer AG
Original Assignee
Bayer AG
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
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0841187A1 publication Critical patent/EP0841187A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser

Definitions

  • the invention relates to thermoplastic polymer molding compositions which are of the type be pigmented that ideally the pigments corresponding to the spectral colors optionally used with carbon black and this in the production of Shaped bodies a single color, possibly a dark to black Cause surface, so that this molded body after laser inscription on the marked areas an excellent light to white, possibly bright colored Font with very good contrast.
  • thermoplastic polymer molding compositions which are of the type be pigmented that ideally the pigments corresponding to the spectral colors optionally used with carbon black and this in the production of Shaped bodies have a single-colored, possibly a dark to black surface cause so that these moldings after laser marking on the marked Make an excellent light to white, possibly bright colored font have very good contrast.
  • the invention further relates to the use of the above thermoplastic molding compositions for the production of moldings or molded parts, which are labeled with laser energy and the ones made from them Molded body.
  • the invention further relates to a method for labeling Shaped bodies using laser energy.
  • the energy source can be used.
  • the wavelength can be between 193 and 10 600 nm, preferably 532 and 1 064 nm.
  • the molding compositions used according to the invention can be used to apply optical information in the form of patterns, graphics, numbers, letters, Characters, pictures (e.g. passport photos, portraits, photos) etc. by means of Laser energy, e.g. B. be used by laser beam recorder.
  • Laser energy e.g. B. be used by laser beam recorder.
  • Molding compounds are transferred.
  • Polymers or copolymers e.g. B. based on Polyalkylene terephthalates, aromatic polyesters, polyamide, polycarbonate, Polyacrylate, polymethacrylate, ABS graft polymers, polyolefins such as polyethylene or polypropylene, polystyrene, polyvinyl chloride, polyoxymethylene, polyimide, Polyethers and polyether ketones, individually or as a blend of different Polymers can be used.
  • Polyalkylene terephthalates in the sense of the invention are reaction products from aromatic dicarboxylic acid or its reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic Diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates can be derived from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 produce up to 10 carbon atoms using known methods (plastic manual, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Kunststoff 1973).
  • Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, Ethylene glycol and / or 1,4-butanediol residues.
  • the preferred polyalkylene terephthalates can, in addition to terephthalic acid residues 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or contain aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Succinic, adipic, sebacic, azelaic, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates can, in addition to ethylene or 1,4-butanediol glycol residues up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols containing 6 to 21 carbon atoms, e.g.
  • the polyalkylene terephthalates can be 3- or 4-valent alcohols or 3- or 4-basic carboxylic acid, such as those e.g. in the DE-OS 19 00 270 and U.S. Patent 3,692,744 are described.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol.
  • Polyalkylene terephthalates which consist solely of terephthalic acid are particularly preferred and their reactive derivatives (e.g. their dialkyl esters) and ethylene glycol and / or 1,4-butanediol have been produced (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters which consist of at least two of the above acid components and / or from at least two of the above alcohol components are produced, particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.
  • the polyalkylene terephthalates preferably used as component A have generally an intrisic viscosity of about 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
  • the diphenols can be used both individually and in a mixture.
  • Particularly preferred aromatic polycarbonates are based on polycarbonates of 2,2-bis (4-hydroxyphenyl) propane or one of the others as preferred called diphenols.
  • 2,2-bis (4-hydroxyphenyl) propane are very particularly preferred, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane or mixtures of 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • the aromatic polycarbonates can be produced by known processes e.g. by melt transesterification with a corresponding bisphenol Diphenyl carbonate and in solution from bisphenols and phosgene.
  • the solution can be homogeneous (pyridine process) or heterogeneous (two-phase interface process) (see H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, S 33ff, Intersciencs Publ. 1964).
  • the aromatic polycarbonates generally have average molecular weights M w from approx. 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration).
  • Copolycarbonates in the sense of the invention are in particular polydiorganosiloxane-polycarbonate block copolymers with medium molecular weight M w from approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration) and with a content of aromatic carbonate structural units of about 75 to 97.5% by weight, preferably 85 to 97% by weight and a content on polydiorganosiloxane structural units from about 25 to 2.5% by weight, preferably 15 to 3% by weight, the block copolymers starting from polydiorganosiloxanes containing ⁇ , ⁇ -bishydroxyaryloxy end groups and having a degree of polymerization P n of 5 to 100, preferably 20 to 80 , getting produced.
  • M w medium molecular weight
  • M w medium molecular weight
  • 20,000 to 80,000 determined by gel chromatography after prior calibration
  • a content of aromatic carbonate structural units of about 75 to 97.5% by weight, preferably 85
  • the polydiorganosiloxane-polycarbonate block polymers can also be a Mixture of polydiorganosiloxane-polycarbonate block copolymers with conventional ones be polysiloxane-free, thermoplastic polycarbonates, the total content about 2.5 to 25% by weight of polydiorganosiloxane structural units in this mixture is.
  • Alkyl in the above formula (2) is, for example, C 1 -C 20 -alkyl
  • alkenyl in the above formula (2) is, for example, C 2 -C 6 -alkenyl
  • Aryl in the above formula (2) is C 6 -C 14 aryl.
  • Halogenated in the above formula means partially or completely chlorinated, brominated or fluorinated.
  • alkyls, alkenyls, aryls, halogenated alkyls and halogenated aryls are methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, Chloromethyl, perfluorobutyl, perfluorooctyl and chlorophenyl.
  • Such polydiorganosiloxane-polycarbonate block copolymers are e.g. from US PS 3,189,662, U.S. Patent 3,821,325 and U.S. Patent 3,832,419.
  • Preferred polydiorganosiloxane-polycarbonate block copolymers are produced by using polydiorganosiloxanes containing ⁇ , ⁇ -bishydroxyaryloxy end groups together with other diphenols, optionally with the use of Branching in the usual amounts, e.g. according to the two-phase interface method (see also H. Schnell, Chemistry and Physics of Polycarbonates Polymer Rev. Vol. IX, page 27 ff, Interscience Publishers New York 1964) each selected the ratio of the bifunctional phenolic reactants is that the content of aromatic carbonate structural units according to the invention and diorganosiloxy units results.
  • Such ⁇ , ⁇ -bishydroxyaryloxy end group-containing polydiorganosiloxanes are e.g. known from US 3,419,634.
  • ABS graft polymers in the sense of the invention are graft polymers from
  • the graft monomers in the grafting reaction are not necessarily complete grafted onto the graft base arise from the graft monomers Copolymers.
  • the term ABS graft polymers are also to understand those products which, due to polymerization, are precisely these copolymers contain.
  • the average particle diameter d 50 of the ABS graft polymer is generally 0.5 to 5 nm, preferably 0.1 to 2 nm.
  • the average particle diameter d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid, Z. Polymer 250 (1972), 782-796).
  • Polyolefins are polyethylene, polypropylene, poly-1-butene and polymethylpentene, which still contain small amounts of non-conjugated dienes in copolymerized form can. These polymers are known and are in Roempp's chemistry dictionary, 8th edition 1987, vol. 5, page 3307 and in the literature cited therein. Prefers is polypropylene.
  • polyamides or polyamides with a predominantly aliphatic content are used as polyamides in the thermoplastic polyamide molding compositions.
  • diamines preferably C 4 -C 16 -, in particular C 4 -C 8 -alkylenediamines
  • dicarboxylic acids preferably C 4 -C 12 -, in particular C 4 -C 8 - are preferred Alkylenedicarboxylic acids
  • the Pigments / dyes and / or carbon blacks can optionally also be used as a batch be used.
  • the pigment mixture should be chosen so that ideally all Spectral colors are used, possibly in combination with soot.
  • inorganic pigments used as additives for discoloration used are antimony trioxide, antimony pentoxide, basic lead carbonate, basic lead sulfate or lead silicate, lithopone, titanium dioxide (anatase, rutile), Zinc oxide, zinc sulfide, metal oxides such as Berlin blue, lead chromate, lead sulfochromates, Chromium-antimony-titanate, chromium oxides, iron oxides, cobalt blue, cobalt chrome blue, Cobalt nickel gray, manganese blue, manganese violet, molybdenum orange, Molybdate red, nickel antimony titanate, ultramarine blue, and metal sulfides such as Arsenic disulfide, antimony trisulfide, cadmium sulfide, cadmium sulfoselenide, zirconium silicates such as zirconium vanadium blue, zirconium presode yellow.
  • organic pigments used as additives for discoloration are used are antrachinone, azo, azomethine, benzanthrone, Quinacridone, quinophthalone, dioxazine, flavanthrone, indanthrone, isoindo-lin, Isoindolinone, methine, perinone, perylene, phthalocyanine, pyranthrone, Pyrrolopyrrole, thioindigo pigments and metal complexes of e.g. B. azo, Azomethine, methine dyes or metal salts of azo compounds.
  • Dispersion dyes are suitable as polymer-soluble dyes, such as those of the anthraquinone series, for example alkylamino, amino, arylamino, Cyclohexylamino, hydroxy, hydroxyamino or phenylmercaptoanthraquinones, as well as metal complexes of azo dyes, in particular 1: 2 chromium or cobalt complexes of monoazo dyes, and fluorescent dyes, for example those from the benzothiazole, coumarin, oxarin, or Thiazine series.
  • polymer-soluble dyes such as those of the anthraquinone series, for example alkylamino, amino, arylamino, Cyclohexylamino, hydroxy, hydroxyamino or phenylmercaptoanthraquinones, as well as metal complexes of azo dyes, in particular 1: 2 chromium or cobalt complexes of monoazo dyes, and fluorescent dyes
  • the polymer-soluble dyes are preferred in combinations with fillers and / or pigments, in particular with inorganic pigments such as titanium dioxide used.
  • pigments or polymer-soluble dyes with or without Pigment additives are used.
  • thermoplastic used according to the invention Polymers are compatible and their mechanical or other properties do not interfere.
  • Suitable pigment additives are, for example, fatty acids with at least 12 carbon atoms, such as behenic acid or stearic acid, their amides, salts or esters, such as aluminum stearate, magnesium stearate, zinc stearate, or magnesium behenate, and quaternary ammonium compounds, such as tri (C 1 -C 4 ) alkylbenzylammonium salts Waxes, such as polyethylene wax, resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin, C 12 -C 18 paraffin disulfonic acids or alkylphenols.
  • fatty acids with at least 12 carbon atoms such as behenic acid or stearic acid, their amides, salts or esters, such as aluminum stearate, magnesium stearate, zinc stearate, or magnesium behenate
  • quaternary ammonium compounds such as tri (C 1 -C 4 ) alkylbenzylammonium salt
  • the metal-containing pigments such as the inorganic pigments
  • Pigments and the metal complexes of azo, azomethine or methine dyes are preferred Pigments and the metal complexes of azo, azomethine or methine dyes.
  • Preferred inorganic and / or organic pigments are those which Correspond colors of the spectral range.
  • the pigments are preferred which by definition are the saturated colors located on or near the curve of the CIE standard color chart correspond.
  • the inorganic metal-containing pigments phthalocyanine metal complex, Copper phthalocyanine, monoazo 1: 2 chromium complexes, azo metal complex and bismuth vanadate are particularly preferred.
  • fillers and reinforcing materials glass fibers, glass balls, mica, Silicates, quartz, talc, titanium dioxide, wollastonite, etc. used that too can be surface treated.
  • Preferred reinforcing materials are commercially available Fiberglass.
  • the glass fibers, which generally have a fiber diameter have between 8 and 14 microns, as continuous fibers or as cut or ground glass fibers are used, the fibers with a suitable Sizing system and an adhesion promoter or adhesion promoter system based on silane can be equipped.
  • the mixture is preferably 8 to 45, in particular 10 to 40 parts by weight of fillers and reinforcing materials are added.
  • organic compounds or Halogen compounds with synergists or commercially available organic nitrogen compounds or organic / inorganic phosphorus compounds are commercially available.
  • mineral flame retardants such as Mg hydroxide or Ca-Mg carbonate hydrate can be used.
  • the molding compositions according to the invention can contain up to 20, preferably 3 to 18, in particular 6 to 15 parts by weight of halogenated compounds and up to 8, preferably 2 to 6 parts by weight of antimony compounds, especially antimony trioxide or contain antimony pentoxide.
  • Pentabrom polyacrylate generally has average molecular weights M w (weight average) from 10,000 to 200,000, brominated polystyrene generally from 10,000 to 500,000.
  • Epoxidized tetrabromobisphenol-A and tetrabromobisphenol-A oligocarbonate are preferred used.
  • Expoxidized tetrabromobisphenol-A is a known diepoxide resin with a molecular weight of about 350 to about 2,100, preferably 360 to 1,000, particularly preferably 370 to 400, and consists essentially of at least one condensation product of bisphenol A and epihalohydrin and is described by the formula (I ) wherein X represents hydrogen or bromine and n is an average number between zero and less than 2.3 (see, for example, EP-A 180 471).
  • Tetrabromobisphenol A oligocarbonate or tetrachlorobisphenol A oligocarbonate is described by formula (II), the oligomers being terminated either with phenol or with tribromophenol or trichlorophenol: where X represents hydrogen, bromine or chlorine, n is an average number between 4 and 7.
  • Tetrabromo (chloro) bisphenol A oligocarbonate is known and according to known methods producible.
  • the phosphorus compounds are in accordance with EP-A 345 522 (US-PS 061.745) or DE-OS 43 28 656.9 in those described there Suitable amounts, e.g. Triphenyl phosphate, oligomeric phosphates, resorcinol diphosphate or a mixture of them.
  • EP (D) M rubbers graft rubbers come as elastomer modifiers based on butadiene, styrene, acrylonitrile (see e.g. those described above ABS graft polymers), acrylate rubbers, thermoplastic polyurethanes or EVA copolymers with or without functional coupling groups questionable. Up to 30 parts by weight of component E are preferably added.
  • Antimony trioxide is well known and can e.g. B. from Campine be acquired.
  • the molding compositions according to the invention can contain conventional additives such as lubricants and Mold release agents, Contain nucleating agents, antistatic agents, stabilizers.
  • the molding compositions according to the invention from the respective components and optionally other known additives such as stabilizers, dyes, pigments, Lubricants and mold release agents, reinforcing materials, nucleating agents and Antistatic agents can be made by adding the respective ingredients in known manner mixed and at temperatures of 180 ° C to 330 ° C in the usual Units such as internal kneaders, extruders, twin-screw extruders melt-compounded or melt extruded.
  • Nd YAG laser device from Rofin Sinar, Designation RSM Base Line 60, at a wavelength of 1,064 nm, one Character spacing of 0.2 mm and a power of 60W.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP97118623A 1996-11-07 1997-10-27 Compositions polymères à mouler, marquable au laser Withdrawn EP0841187A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19645940 1996-11-07
DE1996145940 DE19645940A1 (de) 1996-11-07 1996-11-07 Laserbeschriftbare Polymerformmassen

Publications (1)

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EP0841187A1 true EP0841187A1 (fr) 1998-05-13

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000043213A1 (fr) * 1999-01-20 2000-07-27 Societe De Technologie Michelin Procede de marquage et article susceptible d'etre marque avec un laser
US6383721B1 (en) * 1998-11-17 2002-05-07 Matsushita Electric Industrial Co., Ltd. Marking method and marked resin molded piece
WO2002068205A1 (fr) * 2001-02-28 2002-09-06 Sherwood Technology Ltd. Codage laser
WO2005102724A1 (fr) * 2004-03-23 2005-11-03 3M Innovative Properties Company Manchon marqueur retractable a froid
WO2021250053A1 (fr) * 2020-06-10 2021-12-16 Röhm Gmbh Composition de moulage thermoplastique présentant une résistance aux intempéries améliorée
CN116178881A (zh) * 2023-03-31 2023-05-30 金发科技股份有限公司 一种高耐候黄底黑字激光打标abs复合材料及其制备方法和应用
CN117425703A (zh) * 2021-03-26 2024-01-19 三菱化学株式会社 树脂组合物、成型品及其应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10053639B4 (de) * 2000-10-28 2007-04-12 Chemische Fabrik Budenheim Kg Verwendung von Eisen-, Cobalt-, Nickel- oder Molybdänsalzen
JP2006241254A (ja) * 2005-03-01 2006-09-14 Daicel Polymer Ltd レーザーマーキング可能な熱可塑性樹脂組成物
JP5677926B2 (ja) * 2011-11-14 2015-02-25 三菱エンジニアリングプラスチックス株式会社 レ−ザ−マ−キング用ポリエステル樹脂組成物及び成形体

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0190997A2 (fr) * 1985-02-05 1986-08-13 Ciba-Geigy Ag Ecriture par laser sur systèmes pigmentés
EP0327508A2 (fr) * 1988-02-03 1989-08-09 Ciba-Geigy Ag Procédé pour marquage par laser de systèmes pigmentés
WO1994012352A1 (fr) * 1992-12-02 1994-06-09 Dsm N.V. Composition polymere contenant un polymere et au moins une substance sensible aux radiations
EP0675168A1 (fr) * 1994-03-30 1995-10-04 Bayer Ag Mélange à mouler polymère pour changement partielle de couleurs par l'activité du laser, notamment pour la formation des signes en couleurs
EP0700796A1 (fr) * 1994-09-12 1996-03-13 Basf Aktiengesellschaft Procédé de préparation de corps céramiques formés multicolores
JPH0971726A (ja) * 1995-09-05 1997-03-18 Teijin Ltd レーザマーキング性を有する樹脂組成物
EP0808866A2 (fr) * 1996-05-24 1997-11-26 Bayer Ag Compositions polymères à mouler, marquable au laser

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0190997A2 (fr) * 1985-02-05 1986-08-13 Ciba-Geigy Ag Ecriture par laser sur systèmes pigmentés
EP0327508A2 (fr) * 1988-02-03 1989-08-09 Ciba-Geigy Ag Procédé pour marquage par laser de systèmes pigmentés
WO1994012352A1 (fr) * 1992-12-02 1994-06-09 Dsm N.V. Composition polymere contenant un polymere et au moins une substance sensible aux radiations
EP0675168A1 (fr) * 1994-03-30 1995-10-04 Bayer Ag Mélange à mouler polymère pour changement partielle de couleurs par l'activité du laser, notamment pour la formation des signes en couleurs
EP0700796A1 (fr) * 1994-09-12 1996-03-13 Basf Aktiengesellschaft Procédé de préparation de corps céramiques formés multicolores
JPH0971726A (ja) * 1995-09-05 1997-03-18 Teijin Ltd レーザマーキング性を有する樹脂組成物
EP0808866A2 (fr) * 1996-05-24 1997-11-26 Bayer Ag Compositions polymères à mouler, marquable au laser

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9721, Derwent World Patents Index; Class A13, AN 97-231285, XP002047073 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6383721B1 (en) * 1998-11-17 2002-05-07 Matsushita Electric Industrial Co., Ltd. Marking method and marked resin molded piece
WO2000043213A1 (fr) * 1999-01-20 2000-07-27 Societe De Technologie Michelin Procede de marquage et article susceptible d'etre marque avec un laser
US6689542B2 (en) 1999-01-20 2004-02-10 Michelin Recherche Et Technique S.A. Process for making and an article marked using a laser
WO2002068205A1 (fr) * 2001-02-28 2002-09-06 Sherwood Technology Ltd. Codage laser
US6888095B2 (en) 2001-02-28 2005-05-03 Sherwood Technology, Inc. Laser coding
WO2005102724A1 (fr) * 2004-03-23 2005-11-03 3M Innovative Properties Company Manchon marqueur retractable a froid
WO2021250053A1 (fr) * 2020-06-10 2021-12-16 Röhm Gmbh Composition de moulage thermoplastique présentant une résistance aux intempéries améliorée
CN115715307A (zh) * 2020-06-10 2023-02-24 罗姆化学有限责任公司 具有改进耐候性的热塑性模塑组合物
CN115715307B (zh) * 2020-06-10 2025-09-30 罗姆化学有限责任公司 具有改进耐候性的热塑性模塑组合物
CN117425703A (zh) * 2021-03-26 2024-01-19 三菱化学株式会社 树脂组合物、成型品及其应用
CN117425704A (zh) * 2021-03-26 2024-01-19 三菱化学株式会社 树脂组合物、成型品及其应用
EP4317314A4 (fr) * 2021-03-26 2024-08-14 Mitsubishi Chemical Corporation Composition de résine, article moulé et son utilisation
CN116178881A (zh) * 2023-03-31 2023-05-30 金发科技股份有限公司 一种高耐候黄底黑字激光打标abs复合材料及其制备方法和应用

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Publication number Publication date
DE19645940A1 (de) 1998-05-14
JPH10140017A (ja) 1998-05-26

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