WO1990006966A1 - Agents de photodegradation et de thermocollage pour materiaux de matrices polymeres - Google Patents

Agents de photodegradation et de thermocollage pour materiaux de matrices polymeres Download PDF

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Publication number
WO1990006966A1
WO1990006966A1 PCT/US1989/005749 US8905749W WO9006966A1 WO 1990006966 A1 WO1990006966 A1 WO 1990006966A1 US 8905749 W US8905749 W US 8905749W WO 9006966 A1 WO9006966 A1 WO 9006966A1
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WO
WIPO (PCT)
Prior art keywords
polymer
photodegradation
tiθ2
composition
matrix material
Prior art date
Application number
PCT/US1989/005749
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English (en)
Inventor
Ronald P. Markovich
Dallas C. Pichnic
B. Alam Sham
Gerald M. Lancaster
Original Assignee
The Dow Chemical Company
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 The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to KR1019900701819A priority Critical patent/KR910700301A/ko
Publication of WO1990006966A1 publication Critical patent/WO1990006966A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/012—Additives activating the degradation of the macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the photodegradability and/or heat-seal range of polymeric matrix materials is controllably enhanced by incorporating therein Ti ⁇ 2 and ethylene copolymers which have pendent carbonyl groups along the copolymer chain.
  • Photodegradation is the process whereby the ultraviolet radiation in sunlight attacks the chemical bonds in a chemical structure, such as plastics and polymers, thereby breaking the structure into smaller segments. This causes the structure to lose its physical strength, especially its ability to flex or stretch. The degradation process can continue the embrittlement and produce smaller and smaller pieces.
  • the ethylene/carbon monoxide copolymers include those which have other copolymerizable monomers contained in the polymer, such as acrylic acid, methacrylic acid, vinyl alkylates, alkyl acrylates, and even minor amounts of lower olefins, such as propylene or butylene.
  • Patents showing the preferred method of making CO-containing ethylene copolymers include U.S. Patent 4,600,614 and U.S. Patent 4,601,948.
  • a European Patent Application published July 29, 1987 as European Patent No. 0230143 discloses that a photodegrading agent comprising a heavy metal dithiocarbamate or heavy metal dithiophosphate together with an ethylene/carbon monoxide polymer is useful for enhancing the photodegradation of an ethylene polymer, such as a linear low density polymer.
  • copolymer which has carbonyl oxygen groups is one prepared by copolymerizing ethylene with an alkyl vinyl ketone, such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, or an alkyl isopropenyl ketone and the like; these copolymers have the carbonyl groups pendent from one of the carbons of the vinyl group which is directly in the polymer "backbone" chain.
  • alkyl vinyl ketone such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, or an alkyl isopropenyl ketone and the like.
  • n is a plural number
  • R' is hydrogen or alkyl group
  • Ti ⁇ 2 will accelerate the photodegradation of polyethylene and polypropylene.
  • the rutile form of Ti ⁇ 2 is relatively inactive with respect to the photodegradation of polymers to which it may be added, but it may be employed for other purposes, such as for pigmentation or thermal activity.
  • a first aspect of the invention is a photodegrading agent comprising a blend of anatase Ti ⁇ 2 and at least one photodegrading polymer containing carbonyl CO groups along the polymer chain.
  • a second aspect of the invention is a process of synergistically enhancing the photodegradation rate of photodegradation polymers containing carbonyl groups along the polymer chain; the said process comprising incorporating the anatase form of Ti ⁇ 2 therein.
  • An ethylene copolymer containing copolymerized carbon monoxide (CO) in the polymer chain backbone is the preferred type of 5 CO-containing polymer.
  • a process of accelerating the photodegrada ⁇ tion rate of a matrix resin comprising incorporating into the matrix resin a photodegrading composition (or "agent") comprising anatase Ti ⁇ 2 and at least one CO-containing polymer.
  • a photodegrading composition or "agent” comprising anatase Ti ⁇ 2 and at least one CO-containing polymer.
  • a process of providing a predetermined regulated rate of photodegradation to a matrix resin comprising blending the matrix resin with predetermined amounts of anatase Ti ⁇ 2, at least one CO- containing polymer and optionally rutile Ti ⁇ 2, and/or a UV stabilizer.
  • the photodegradation rate of CO-containing polymers is synergistically accelerated by the addition thereto of the anatase form of Ti ⁇ 2 and is not merely a numerically additive effect of the two ingredients. That, in itself, is Deneficial in the preparation of articles which can be made directly from an anatase Ti ⁇ 2/polymer blend and relatively fast photodegradation is desirably obtained.
  • the mixture of anatase Ti ⁇ 2/CO-containing polymer is also used as an agent to provide a faster photodegradation rate to articles such as resin films, filaments, fibers, sheets, slabs, containers or other configurations prepared from matrix resins.
  • the agent may, as a "masterbatch" of Ti02/C0-containing polymer, be blended with the matrix resin in which the accelerated rate of photodegradation is desired.
  • the carbo ⁇ yl-containing polymer and the Ti ⁇ 2 can be added separately to the matrix resin, but are beneficially and preferably mixed together to form a photodegrading agent which is then added to the resin.
  • additives and/or degradation accelerators and/or photostabilizers and/or photosensitizers may also be employed along with the agent of this invention either by way of having the photodegradation agent added to matrix resins which contain the said optional ingredients, or by way of adding the optional additives to matrix resins which contain the photodegradation agents, or by adding them to the matrix resin at substantially the same time.
  • the matrix resins to which a photodegrading property are desired to be imparted or accelerated may be resins which are used in making packaging materials, especially those which are usually intended to be discarded after their first use.
  • matrix resins are polyolefins, polyesters, polyurethanes, polyamides, polyepoxides, polyacrylates and plolycarbonates.
  • Such articles as garbage bags, grocery bags, tampon-type applicators, wipe-cloths, hygiene products, disposable diapers, sanitary napkins, food-wrapping, food cartons, can holders, beverage overwraps, beverage containers, beer can "loop carriers", and the like, often comprise or include resins which can be caused to be more rapidly photodegraded by sunlight.
  • Resins prepared from olefin monomers and/or vinyl monomers such as ethylene, propylene, butene, styrene, vinyl acetate, vinyl halide, and derivatives of these or other such monomers which are used in making plastics and which are often used as discardable packaging materials.
  • Resins prepared from olefins and mixtures of olefins such as low density branched polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density linear polyethylene (HDPE) as well as styrene polymers and copolymers are of particular interest as the matrix resins in this invention.
  • LLDPE resins are of special interest considering, among other things, the strength and- impact resistance they exhibit which makes them popular in the making of garbage bags and trash bags.
  • Compositions comprising HDPE are particularly useful for preparing discardable molded articles.
  • Compositions comprising LLDPE or LDPE are particularly useful for preparing discardable melt-extruded films.
  • Compositions comprising styrenic polymers or copolymers are particularly useful for preparing discardable foams.
  • the titanium oxide, Ti ⁇ 2, which exhibits a synergistic effect when combined with CO-containing polymers is of the crystalline form known as anatase. Throughout this disclosure the Ti ⁇ 2 is the anatase form unless stated otherwise.
  • the CO-containing polymer used as a photodegrading agent, in conjunction with the Ti ⁇ 2 may be any thermoplastic polymer which has carbonyl groups along the polymer chain and which is either compatible with, or can be compatibilized with, the resin into which it is to be blended. Compatibilizing may be accomplished, e.g., by the addition of a compatibilizer or by special blending techniques while the polymers/resins are in solution or are molten.
  • the CO-containing polymer is an ethylene copolymer, especially a binary or ternary polymer, which is prepared using carbon monoxide as one of the monomers. The preparation of such ethylene/carbon monoxide polymers is known in the art of making ethylene copolymers. Less preferred are those polymers wherein the carbonyl groups are supplied to the polymer chain by the presence of an alkyl vinyl ketone polymerized into the chain.
  • the amount of the CO-containing polymer used in the matrix resin usually is an amount in the range of 0.05 percent to 50 percent of the total weight of the 5 formulation.
  • the amount of the anatase Ti ⁇ 2 used in the matrix resin usually is an amount in the range of 0.05 percent to 25 percent of the total weight of the formulation.
  • the ratio of the CO- containing polymer to the anatase Ti ⁇ 2 usually is in the 0 range of 99.9/0.1 to 0.3/99.7, preferably in the range of 99.8/0.2 to 0.5/99.5, most preferably in the range of 99.7/0.3 to 1/99.
  • slip agents such as erucylamides or oleamides, or antioxidants or UV stabilizers, such as compounds sold under the following names (some of which are proprietary formulations) :
  • Irganox 1010 Tetrakis [methylene 2-(3' ,5 ! -di-tert- butyl-4'hydroxylphenol) propionate] methane,
  • Irganox 1076 Octadecyl 3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate or Octadecyl 3,5-di-t-butyl-4- hydroxyhydrocinnamate
  • Tinuvin 770 hindered piperidines
  • Tinuvin 328 a benzotriazole
  • UV stabilizers Some compounds or families of UV stabilizers are, e.g., as follows:
  • Dithiolate metal complexes e.g. Ni, Co, Cu
  • foaming agents to cause foaming of the matrix resin and produce lightweight articles, and/or add other polymers to the CO-containing polymer/Ti ⁇ 2 compositions, thus preparing an appreciable variety of final products having an enhanced tendency to degrade under the influence of actinic radiation, especially UV.
  • LLDPE linear low density polyethylene which is actually an ethylene/1-alkene copolymer prepared by using a coordination catalyst, such as a Ziegler catalyst or the like.
  • MFR melt flow rate
  • MI melt index
  • LLDPE-2 Ethylene/octene copolymer, density of 0.920 g/cc and MFR of 10 g/10 min.
  • LDPE-1 Branched homopolymer of ethylene, 0.922 g/cc density, MI of 20 g/10 min.
  • Ti ⁇ 2 Titanium oxide indicated as the anatase crystal form or the rutile crystal form, or in some instances it can be either one,
  • Concentrate #1 Equal parts of ECO-1 and anatase Ti ⁇ 2, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
  • Concentrate #3 Equal parts of LDPE and rutile Ti ⁇ 2, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
  • Concentrate #4 Equal parts of LDPE and anatase Ti02, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
  • a composite blend is prepared by blending 9.9 parts of LLDPE-1, 0.3 parts of LLDPE-2, and 4.8 parts of Concentrate #1. The components are tumble dry blended prior to being fabricated into cast film at 550°F (288°C) of 1.2 mil (30 micrometers) thickness. Strips of film, 1-inch by 8-inch (2.5 cm by 20 cm) are cut from the cast film and subjected to outside weathering in accordance with ASTM D-1435-85. By analyses of the parameters of interest, average tensile, average yield and percent elongation at break are determined and analyzed in accordance with ASTM D-882. The brittle point is determined to be that point where the tensile at break and yield strength values were identical and the film samples demonstrated brittleness when handled. The data for the outside weathering are shown in TABLE I.
  • Example 2 In similar manner to Example 1 , a composite blend is prepared consisting of 9.9 parts of LLDPE-1,
  • Hot tack tests are performed on a "Pack Forsk” instrument which is fully automated and is equipped with an Instron type seal strength testing device.
  • the dwell time is set at 0.5 seconds.
  • the delay time (between the formation of. seal and the strength) is set at 0.2 seconds.
  • the film samples are 1-inch (2.5 cm) wide strips of uniform thickness. Each data point is calculated from an average of at least 3 measurements.
  • the tear resistance is measured by Elmendorf tear test type B, which is ASTM # D-1922. Each data point is an average of four measurements.
  • Films from which testing samples are taken are prepared by dry blending the components for 1 hour and then extruding the well-mixed ingredients through a 1-inch (2.5 cm) 24/1 L/D MPM extruder and fabricated into cast film (film gauge of 2.5 to 2.7 mils, i.e. about 63 to 69 micrometers, under the following conditions:
  • a typical prior art composite contains about 73 percent LLDPE, about 25 percent LDPE, and about 2 percent Ti0 2 .
  • the heat seal temperature range and the tear strength of this currently used composite when fabricated into a cast film without the Ti0 2 , are 225°F to 275°F (107°C to 135°C) and 200 grams, respectively.
  • the heat seal temperature range and tear strength With the Ti0 2 added to the LDPE/LLDPE formulation, the heat seal temperature range and tear strength become reduced to 230°F to 265°F (110°C to 129°C) and 146 grams, respectively.
  • the heat seal temperature range and tear resistance is 225°F to 28 ⁇ °F and 592 grams, respectively.
  • Ti0 2 is added to the LLDPE/EC0 blend
  • the heat seal temperature and tear strength is 235°F to 295°F and 606 grams, respectively.
  • T1O2 acidic surface
  • ECO basic carbonyl
  • EC0/Ti0 2 in place of LDPE/Ti0 2 is found to result in widening the heat seal temperature range of a wide variety of polymers into which the ECO/Ti ⁇ 2 is incorporated, especially olefin polymers and copolymers such as LLDPE, HDPE, and LDPE and the like.
  • olefin polymers and copolymers such as LLDPE, HDPE, and LDPE and the like.
  • the benefits of the ECO/Ti ⁇ 2 additives are found in blown films as well as cast films.
  • the ECO copolymer usually contains 1 to 50 weight percent CO.
  • the LLDPE usually contain any one or more alkene comonomers in the C -C-J Q range.

Abstract

Un mélange de la forme anatasique de TiO2 et d'un polymère photodégradable contenant des groupes carbonyle le long de la chaîne polymère (notamment un copolymère d'éthylène) augmente de manière synergique le taux de photodégradation de matériaux de matrices polymères. D'autres additifs tels que le rutile TiO2 et/ou d'autres matériaux sensibles aux UV, absorbant les UV ou stabilisant les UV peuvent être inclus afin de régler le taux de photodégradation. En outre, la présence de TiO2, qui présente une surface acide, et dudit polymère contenant du CO augmente la plage des températures de thermocollage des matériaux de matrices polymères thermocollables.
PCT/US1989/005749 1988-12-22 1989-12-18 Agents de photodegradation et de thermocollage pour materiaux de matrices polymeres WO1990006966A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019900701819A KR910700301A (ko) 1988-12-22 1989-12-18 중합체성 매트릭스 물질용 광분해제 및 열-접착제

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28908088A 1988-12-22 1988-12-22
US289,080 1988-12-22

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AU (1) AU4849890A (fr)
CA (1) CA2006376A1 (fr)
WO (1) WO1990006966A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0486524A1 (fr) * 1990-05-18 1992-05-27 The Dow Chemical Company Agents de photodegradation et de thermosoudage pour materiaux matriciels polymeres
EP0529696A1 (fr) * 1991-07-31 1993-03-03 Shell Internationale Researchmaatschappij B.V. Compositions de polymères de monoxyde de carbone et de composés oléfiniques non-saturés
FR2692583A1 (fr) * 1992-05-29 1993-12-24 Mezza Michel Mise en application d'une réaction photochimique sur divers produits en polypropylène, copolymère ou homogène et polyéthylène haute ou basse densité.
CN1034737C (zh) * 1994-05-13 1997-04-30 梅秀泉 可控光·生物降解聚苯乙烯泡沫塑料及其制备方法
GB2352824A (en) * 1999-07-30 2001-02-07 Nokia Mobile Phones Ltd Laser markable material comprising TiO2 pigmented thermoplstic elastomer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676401A (en) * 1964-11-16 1972-07-11 Eastman Kodak Co Environmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator
US3860538A (en) * 1972-04-07 1975-01-14 James Edwin Guillet Photodegradable polymer masterbatches
US3981856A (en) * 1974-03-07 1976-09-21 Princeton Polymer Laboratories, Incorporated Degradable hydrocarbon polymers containing a metal compound and a benzotriazole
CA1073581A (fr) * 1974-01-25 1980-03-11 Canadian Titanium Pigments Ltd. Matiere aux polyolefines photodegradables
US4476255A (en) * 1971-11-01 1984-10-09 Owens-Illinois, Inc. Photoreactive plastic composition and articles degradable by ultraviolet radiation and a process for their manufacture
US4883857A (en) * 1987-09-30 1989-11-28 Ecoplastics Limited Production of photodegradable polyester plastics

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676401A (en) * 1964-11-16 1972-07-11 Eastman Kodak Co Environmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator
US4476255A (en) * 1971-11-01 1984-10-09 Owens-Illinois, Inc. Photoreactive plastic composition and articles degradable by ultraviolet radiation and a process for their manufacture
US3860538A (en) * 1972-04-07 1975-01-14 James Edwin Guillet Photodegradable polymer masterbatches
CA1073581A (fr) * 1974-01-25 1980-03-11 Canadian Titanium Pigments Ltd. Matiere aux polyolefines photodegradables
US3981856A (en) * 1974-03-07 1976-09-21 Princeton Polymer Laboratories, Incorporated Degradable hydrocarbon polymers containing a metal compound and a benzotriazole
US4883857A (en) * 1987-09-30 1989-11-28 Ecoplastics Limited Production of photodegradable polyester plastics

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0486524A1 (fr) * 1990-05-18 1992-05-27 The Dow Chemical Company Agents de photodegradation et de thermosoudage pour materiaux matriciels polymeres
EP0486524A4 (en) * 1990-05-18 1992-12-09 The Dow Chemical Company Photodegradation and heat-seal agents for polymeric matrix materials
EP0529696A1 (fr) * 1991-07-31 1993-03-03 Shell Internationale Researchmaatschappij B.V. Compositions de polymères de monoxyde de carbone et de composés oléfiniques non-saturés
FR2692583A1 (fr) * 1992-05-29 1993-12-24 Mezza Michel Mise en application d'une réaction photochimique sur divers produits en polypropylène, copolymère ou homogène et polyéthylène haute ou basse densité.
CN1034737C (zh) * 1994-05-13 1997-04-30 梅秀泉 可控光·生物降解聚苯乙烯泡沫塑料及其制备方法
GB2352824A (en) * 1999-07-30 2001-02-07 Nokia Mobile Phones Ltd Laser markable material comprising TiO2 pigmented thermoplstic elastomer

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KR910700301A (ko) 1991-03-14
AU4849890A (en) 1990-07-10
CA2006376A1 (fr) 1990-06-22

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