CA2086023A1 - Laser-inscribable plastic molding composition, process for the preparation thereof, and the use thereof - Google Patents
Laser-inscribable plastic molding composition, process for the preparation thereof, and the use thereofInfo
- Publication number
- CA2086023A1 CA2086023A1 CA002086023A CA2086023A CA2086023A1 CA 2086023 A1 CA2086023 A1 CA 2086023A1 CA 002086023 A CA002086023 A CA 002086023A CA 2086023 A CA2086023 A CA 2086023A CA 2086023 A1 CA2086023 A1 CA 2086023A1
- Authority
- CA
- Canada
- Prior art keywords
- molding composition
- plastic molding
- pigment
- laser
- excimer laser
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- 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
- C08K3/013—Fillers, pigments or reinforcing additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Abstract of the disclosure Laser-inscribable plastic molding composition, process for the preparation thereof, and the use thereof A laser-inscribable plastic molding composition comprises an organic polymer, preferably a polyacetal, an in-organic, photoactive white pigment and, if desired, a further additive. Moldings produced therefrom are pro-vided with an abrasion-resistant and permanent dark inscription, preferably a black coloration, by irradia-tion by means of an excimer laser.
Description
HOECHST AKTIENGESELLSCHAFT HOE 91/F 41~ Dr.K/sch Laser-inscribable plastic molding composition, process for the preparakion thereof, and the use thereof Description The invention relates to a plastic molding composition which comprises a polyacetal material and at least one white pigment, to a process for the preparation of the inscribed molding composition, and to the use of a plastic molding composition of this type as the starting material for the production of shaped articles which can be provided with s~nbols with the aid of excimer laser radiation.
It is known that plastic articles can be provided with symbols if the plastic contains a ~iller which discolors when the surface of the articles is exposed to energy radiation (DE-C 29 36 926). The plastic material used is polyacetal, to which carbon black or graphite is added as filler, preferably in a concentration of from 0.08 to 0.125 percent. The pigment can also be admixed with an optical brightener which is not destroyed by the action of the laser (DE-C 30 4~ 722). The contrast effect is achieved by a foam-like melting zone on a black back-ground. The energy radiation mentioned in both applica-tions is a deflectable, focusable energy beam, preferably a laser beam, but a more detailed specification is not given.
Also known is a process for inscribing hi.gh-molecular-weight material w~ich contains at least one radiation-sensitive additive which causes discoloration, in which the energy radiation used is laser light, for example solid-state pulse lasers, pulse-modi~ied continuous-wave lasers, metal vapor lasers and semiconductor lasers, and the additive used is at least one inorganic and/or 2086~
organic pigment and/or a polymer-soluble dye (EP-A 0 190 997). However, excimer lasers are not used.
Also known is a process for the laser inscription of high-molecular-weight organic material which contains at least one radiation-sensitive, bleachable additive and at least one less radiation-sensitive, non-bleachable compound. The pulsed laser light source used here is, in addition to an excimer laser, in particular a frequency-doubled Nd:YAG laser (wavelength 532 nm) (EP-A 0 327 508). However, only pale or colored symbols can be obtained by means of this process.
The object of the invention is to provide a pigment-containing plastic molding composition, preferably a pol~acetal molding composition, which does not have said disadvantages.
The invention relates to laser-inscribable plastic molding compositions comprising at least one organic polymer and at least one pigment, wherein (a) the polymer is a polyacetal, (b) the pigment is an inorganic photo-active white pigment and (c) the molding composition maycontain at least one further additive.
The invention furthermore relates to a process by means of which a plastic molding composition (a), preferably a polyacetal polymer as polymer component, which contains (b) a photoactive white pigment and, if desired, (c) a further additive, is irradiated with an excimer laser at wavelengths of from 200 to 550 nm, preferably from 240 to 360 nm, in particular from 248 to 351 nm. The plastic molding composition is used as a thermoplastic material for the production of shaped articles which can be provided with symbols with the aid of excimer laser radiation.
3~6~3 The plastic molding composition is provided with a dark inscription or dark symbols, preferably a bl~ck colora-tion, by the excimer laser radiation, roughening or foaming being avoided at the point at which the laser beam hits the material. This enables permanent and abrasion-resistant labeling of moldings.
In order to achieve the most abrasion-resistant and black inscription on a pale background, titanium dioxide, for example, is suitable as the photoactive white pigment.
Furthermore, the use of an excimer laser is necessary, since a black coloration of photoactive white pigments can be achieved with its wavelengths (i.e. ~he corres-ponding photon energies). In order that the surface is not effected by the interaction of the laser beam with the plastic molding composition, the absorption of the excimer laser radiation must be virtually zero or very small, which is why polyacetals, in particular, are suitable plastics. This type of labeling therefore ensures that all important applicational material proper-ties are fully retained even after inscription. Further-more, the resolution of the symbols is better than when CO2 or Nd:YAG lasers are used, so that even very small inscriptions are still readily legible. The process indicated according to the invention also makes very clear labeling possible, since the absence of thermal effects during inscription means that leading of ~he edge zones of the symbols does not occur. The absence of thermal effects in the indicated process also allows dimension- and distortion-free inscription, for example on very thin moldings.
The base polymers (a) employed are generally known polyoxymethylenes, as described, for example, in DE-A
29 47 490. These are unbranched linear polymers which generally contain at least 80 ~ by weight, preferably at least 90 ~ by weight, of~ oxymethylene units (-CH2O-). The term polyoxymethylenes here covers both homopolymers of ~6~23 formaldehyde or its cyclic oligomers such as trioxane or tetroxane, and corresponding copolymers.
Homopolymers of formaldehyde or trioxane are polymers whose hydroxyl end groups have been chemically stabilized against degradation in a known manner, for example by esterification or etherification.
Copolymers are polymers of formaldehyde or its cyclic oligomers, in particular trioxane, and cyclic ethers, cyclic acetals and/or linear polyacetals.
Suitable comonomers are ~) cyclic ethers having 3, 4 or 5, preferably 3, ring members, ~) c~clic acetals, other than trioxane, having 5 to 11, preferably 5, 6, 7 or 8 ring members and ~) linear polyacetals, in each case in amounts from 0.1 to 20 % by weight, preferably from 0.5 to 10 ~ by weight. Most suitable are copolymers compris-ing 99.5 to 95 % by weight of trioxane and from 0.5 to 5 % by weight of one of the abovementioned co-components.
The polyacetal polymers employed generally have a melt flow index (MFI 190/2.16 value) of from 2 to 50 (DIN 53 735)-The pigment (b) is a photoactive white pigment which changes color under the influence of W light. Parti-cularly suitable for this purpose is titanium dioxide, which causes a color change from white to black. Antimony trioxide, zinc oxide and zinc sulfide have likewise proven to be photoactive, i.eO change in color from pale to dark under the influence of W light. The proportion of the white pigment in the plastic molding composition is from 0.001 to 20 percent by weight, preferably from 0.01 to 10 percent by weight; a proportion of from 0.1 to 5 percent by weight, in each case based on the plastic molding composition, is particularly advantageous.
It is known that plastic articles can be provided with symbols if the plastic contains a ~iller which discolors when the surface of the articles is exposed to energy radiation (DE-C 29 36 926). The plastic material used is polyacetal, to which carbon black or graphite is added as filler, preferably in a concentration of from 0.08 to 0.125 percent. The pigment can also be admixed with an optical brightener which is not destroyed by the action of the laser (DE-C 30 4~ 722). The contrast effect is achieved by a foam-like melting zone on a black back-ground. The energy radiation mentioned in both applica-tions is a deflectable, focusable energy beam, preferably a laser beam, but a more detailed specification is not given.
Also known is a process for inscribing hi.gh-molecular-weight material w~ich contains at least one radiation-sensitive additive which causes discoloration, in which the energy radiation used is laser light, for example solid-state pulse lasers, pulse-modi~ied continuous-wave lasers, metal vapor lasers and semiconductor lasers, and the additive used is at least one inorganic and/or 2086~
organic pigment and/or a polymer-soluble dye (EP-A 0 190 997). However, excimer lasers are not used.
Also known is a process for the laser inscription of high-molecular-weight organic material which contains at least one radiation-sensitive, bleachable additive and at least one less radiation-sensitive, non-bleachable compound. The pulsed laser light source used here is, in addition to an excimer laser, in particular a frequency-doubled Nd:YAG laser (wavelength 532 nm) (EP-A 0 327 508). However, only pale or colored symbols can be obtained by means of this process.
The object of the invention is to provide a pigment-containing plastic molding composition, preferably a pol~acetal molding composition, which does not have said disadvantages.
The invention relates to laser-inscribable plastic molding compositions comprising at least one organic polymer and at least one pigment, wherein (a) the polymer is a polyacetal, (b) the pigment is an inorganic photo-active white pigment and (c) the molding composition maycontain at least one further additive.
The invention furthermore relates to a process by means of which a plastic molding composition (a), preferably a polyacetal polymer as polymer component, which contains (b) a photoactive white pigment and, if desired, (c) a further additive, is irradiated with an excimer laser at wavelengths of from 200 to 550 nm, preferably from 240 to 360 nm, in particular from 248 to 351 nm. The plastic molding composition is used as a thermoplastic material for the production of shaped articles which can be provided with symbols with the aid of excimer laser radiation.
3~6~3 The plastic molding composition is provided with a dark inscription or dark symbols, preferably a bl~ck colora-tion, by the excimer laser radiation, roughening or foaming being avoided at the point at which the laser beam hits the material. This enables permanent and abrasion-resistant labeling of moldings.
In order to achieve the most abrasion-resistant and black inscription on a pale background, titanium dioxide, for example, is suitable as the photoactive white pigment.
Furthermore, the use of an excimer laser is necessary, since a black coloration of photoactive white pigments can be achieved with its wavelengths (i.e. ~he corres-ponding photon energies). In order that the surface is not effected by the interaction of the laser beam with the plastic molding composition, the absorption of the excimer laser radiation must be virtually zero or very small, which is why polyacetals, in particular, are suitable plastics. This type of labeling therefore ensures that all important applicational material proper-ties are fully retained even after inscription. Further-more, the resolution of the symbols is better than when CO2 or Nd:YAG lasers are used, so that even very small inscriptions are still readily legible. The process indicated according to the invention also makes very clear labeling possible, since the absence of thermal effects during inscription means that leading of ~he edge zones of the symbols does not occur. The absence of thermal effects in the indicated process also allows dimension- and distortion-free inscription, for example on very thin moldings.
The base polymers (a) employed are generally known polyoxymethylenes, as described, for example, in DE-A
29 47 490. These are unbranched linear polymers which generally contain at least 80 ~ by weight, preferably at least 90 ~ by weight, of~ oxymethylene units (-CH2O-). The term polyoxymethylenes here covers both homopolymers of ~6~23 formaldehyde or its cyclic oligomers such as trioxane or tetroxane, and corresponding copolymers.
Homopolymers of formaldehyde or trioxane are polymers whose hydroxyl end groups have been chemically stabilized against degradation in a known manner, for example by esterification or etherification.
Copolymers are polymers of formaldehyde or its cyclic oligomers, in particular trioxane, and cyclic ethers, cyclic acetals and/or linear polyacetals.
Suitable comonomers are ~) cyclic ethers having 3, 4 or 5, preferably 3, ring members, ~) c~clic acetals, other than trioxane, having 5 to 11, preferably 5, 6, 7 or 8 ring members and ~) linear polyacetals, in each case in amounts from 0.1 to 20 % by weight, preferably from 0.5 to 10 ~ by weight. Most suitable are copolymers compris-ing 99.5 to 95 % by weight of trioxane and from 0.5 to 5 % by weight of one of the abovementioned co-components.
The polyacetal polymers employed generally have a melt flow index (MFI 190/2.16 value) of from 2 to 50 (DIN 53 735)-The pigment (b) is a photoactive white pigment which changes color under the influence of W light. Parti-cularly suitable for this purpose is titanium dioxide, which causes a color change from white to black. Antimony trioxide, zinc oxide and zinc sulfide have likewise proven to be photoactive, i.eO change in color from pale to dark under the influence of W light. The proportion of the white pigment in the plastic molding composition is from 0.001 to 20 percent by weight, preferably from 0.01 to 10 percent by weight; a proportion of from 0.1 to 5 percent by weight, in each case based on the plastic molding composition, is particularly advantageous.
2~D~3 The plastic molding composition according to -the inven-tion may also contain at least one further additive (c).
This additive is generally a further pigmenk; black and colored pigments are particularly suitable. The additive is present in the plastic molding composition in an amount of up to 5 percent by weight, preferably from 0.01 to 2 percent by weight.
Depending on the application, further substances, for example fillers such as chalk, mica, talc, feldspar, wollastonite and aluminum silicate, furthermore antioxi-dants, light stabilizers, flame proofing agents, heat stabilizers, reinforcing agents, such as glass fibers, or processing aids, which are customary in the processing of plastics, may be added to the molding composition.
The molding composition according to the invention can be prepared by conventional processes. Thus, for example, the white pigment component b) and, if used, component (c) are admixed with the plastic material using extru-ders, mixers or grinding units. The resultant mixture is then converted into the desired final form by processes Xnown per se, such as press molding, casting, calender-ing, extrusion or injection molding.
Inscription by means of the excimer laser using ultra-violet light is possible by means of the following processes:
(a) Using the mask technique, the symbol is imaged on the molding through a mask and a focusing line. This enables very high inscription rates, depending on the pulse rate of the laser. 0 (b) If the test specimen is passed under the beam of the excimer laser on a computer-controlled X/Y stage, the sample can be inscribed with any desired symbols. In this case, the inscription rate depends on the speed at which the X/Y stage is moved.
2 ~
The excimer laser can preferabl~ be opera-ted with -the filling gases KrF (wavelength 248 nm), XeCl (308 nm) and XeF (351 nm).
The plas-tic molding composition according to the inven-tion can be used to inscribe or mark polyacetal moldings, for example in the electronics and motor vehicle industries, for example in the labeling of keys, casings and individual parts. These shaped articles can then easily be provided with symbols with the aid o~ excimer laser radiation.
Examples 1. A homogeneous mixture of 99 parts by weight of a polyacetal (copolymer made from 98 percent b~ weight of oxymethylene units and 2 percent by weight of oxyethylene units and having a melt flow index (MFI 190/2.16) of 9 g/10 min (DIN 53 735) and a crystallite melting range of from 164 to 167C) and 1 part by weight of a white pigment (titanium dioxide, Pigment White 6, C.I. 77 891) was prepared in an extruder (ZSK 28, Werner und Pfleiderer, Stuttgart, Germany).
The resultant molding composition was used to produce plate-like test specimens (120 mm * 80 mm *
2 mm) by injection molding. The test specimens were exposed to the radiation of an excimer laser under the following conditions:
a) the wavelength was 248 nm (KrF), b) the pulse energies were between 0.1 Jcm~2 and 2.0 Jcm~2, c) the pulse length was 30 nsec and the pulse rate was 30 Hz.
A symbol was imaged on the test specimen through a mask. Blackening occurred at the point at which the laser hit the sample without any roughening of the surface being observable. Comparison of the depth profiles of inscribed and uninscribed areas showed no differences within an accuracy of + 1 ~m.
2. Example 1 was repeated, but in addition 0.1 part by weight of Pigment Blac~ 7, C.I. 77 266, was mixed into the molding composition. A black coloration of the script was obtained without surface roughening.
This additive is generally a further pigmenk; black and colored pigments are particularly suitable. The additive is present in the plastic molding composition in an amount of up to 5 percent by weight, preferably from 0.01 to 2 percent by weight.
Depending on the application, further substances, for example fillers such as chalk, mica, talc, feldspar, wollastonite and aluminum silicate, furthermore antioxi-dants, light stabilizers, flame proofing agents, heat stabilizers, reinforcing agents, such as glass fibers, or processing aids, which are customary in the processing of plastics, may be added to the molding composition.
The molding composition according to the invention can be prepared by conventional processes. Thus, for example, the white pigment component b) and, if used, component (c) are admixed with the plastic material using extru-ders, mixers or grinding units. The resultant mixture is then converted into the desired final form by processes Xnown per se, such as press molding, casting, calender-ing, extrusion or injection molding.
Inscription by means of the excimer laser using ultra-violet light is possible by means of the following processes:
(a) Using the mask technique, the symbol is imaged on the molding through a mask and a focusing line. This enables very high inscription rates, depending on the pulse rate of the laser. 0 (b) If the test specimen is passed under the beam of the excimer laser on a computer-controlled X/Y stage, the sample can be inscribed with any desired symbols. In this case, the inscription rate depends on the speed at which the X/Y stage is moved.
2 ~
The excimer laser can preferabl~ be opera-ted with -the filling gases KrF (wavelength 248 nm), XeCl (308 nm) and XeF (351 nm).
The plas-tic molding composition according to the inven-tion can be used to inscribe or mark polyacetal moldings, for example in the electronics and motor vehicle industries, for example in the labeling of keys, casings and individual parts. These shaped articles can then easily be provided with symbols with the aid o~ excimer laser radiation.
Examples 1. A homogeneous mixture of 99 parts by weight of a polyacetal (copolymer made from 98 percent b~ weight of oxymethylene units and 2 percent by weight of oxyethylene units and having a melt flow index (MFI 190/2.16) of 9 g/10 min (DIN 53 735) and a crystallite melting range of from 164 to 167C) and 1 part by weight of a white pigment (titanium dioxide, Pigment White 6, C.I. 77 891) was prepared in an extruder (ZSK 28, Werner und Pfleiderer, Stuttgart, Germany).
The resultant molding composition was used to produce plate-like test specimens (120 mm * 80 mm *
2 mm) by injection molding. The test specimens were exposed to the radiation of an excimer laser under the following conditions:
a) the wavelength was 248 nm (KrF), b) the pulse energies were between 0.1 Jcm~2 and 2.0 Jcm~2, c) the pulse length was 30 nsec and the pulse rate was 30 Hz.
A symbol was imaged on the test specimen through a mask. Blackening occurred at the point at which the laser hit the sample without any roughening of the surface being observable. Comparison of the depth profiles of inscribed and uninscribed areas showed no differences within an accuracy of + 1 ~m.
2. Example 1 was repeated, but in addition 0.1 part by weight of Pigment Blac~ 7, C.I. 77 266, was mixed into the molding composition. A black coloration of the script was obtained without surface roughening.
3. A mixture of 0.1 part by weight of Pigment White 6 and 0.2 part by weight of Pigment Black 7 was prepared analogously to Example 1 and inscribed by means of the excimer laser. A black coloring of the script was obtained without surface roughening.
. A mixture of 0A7 part by weight of Pigment White 6 and 0.2 part by weight of Pigmen-t Brown 24 C.I.
77 310, was prepared analogously to Example 1 and inscribed by means of the excimer laser. A black coloration of the script was obtained without surface roughening.
5. Example 1 was repeated, but 1 part by weight of zinc sulfide (Pigment White 7, C.I. No. 77 975) was mixed into the molding composition instead of Pigment White 6. A black coloration of the script was obtained without surface roughening.
. A mixture of 0A7 part by weight of Pigment White 6 and 0.2 part by weight of Pigmen-t Brown 24 C.I.
77 310, was prepared analogously to Example 1 and inscribed by means of the excimer laser. A black coloration of the script was obtained without surface roughening.
5. Example 1 was repeated, but 1 part by weight of zinc sulfide (Pigment White 7, C.I. No. 77 975) was mixed into the molding composition instead of Pigment White 6. A black coloration of the script was obtained without surface roughening.
Claims (10)
1. A laser-inscribable plastic molding composition comprising at least one organic polymer and at least one pigment, wherein (a) the polymer is a polyacetal, (b) the pigment is an inorganic, photoactive white pigment, and (c) the molding composition may contain at least one further additive.
2. A plastic molding composition as claimed in claim 1, wherein the amount of pigment (b) is from 0.001 to 20 percent by weight, based on the plastic molding composition.
3. The plastic molding composition as claimed in claim 1, wherein the white pigment is titanium dioxide.
4. A plastic molding composition as claimed in claim 1 or 2 or 3, wherein pigment (b) is mixed with a black or colored pigment.
5. A plastic molding composition as claimed in claim 1 or 2 or 3, wherein the polyacetal has a melt flow index (MFI 190/2.16) of from 2 to 50.
6. A process for the preparation of an inscribed plastic molding composition, which comprises irradiating a plastic molding composition comprising a) a polyacetal, b) a photoactive white pigment and, if desired, c) a further additive with an excimer laser at a wavelength in the ultraviolet range from 200 to 550 nm.
7. The process as claimed in claim 6, wherein the excimer laser is operated with the filling gases KrF (wavelength 248 nm), XeCI (308 nm) or XeF
(351 nm), and wherein the irradiation by means of the excimer laser is carried out using the mask technique through a mask and a focusing line or on a computer-controlled X/Y stage.
(351 nm), and wherein the irradiation by means of the excimer laser is carried out using the mask technique through a mask and a focusing line or on a computer-controlled X/Y stage.
8. Shaped articles produced of the plastic molding composition as claimed in claim 1 which are provided with symbols with the aid of laser radiation.
9. Shaped articles as claimed in claim 8 for the electronics and motor vehicle industries.
10. Shaped articles as claimed in claim 8 or 9 in the form of keys, casings and individual parts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4143258.4 | 1991-12-31 | ||
| DE4143258A DE4143258A1 (en) | 1991-12-31 | 1991-12-31 | LASER-WRITABLE PLASTIC MOLDING METHOD, METHOD FOR THEIR PRODUCTION AND USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2086023A1 true CA2086023A1 (en) | 1993-07-01 |
Family
ID=6448284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002086023A Abandoned CA2086023A1 (en) | 1991-12-31 | 1992-12-22 | Laser-inscribable plastic molding composition, process for the preparation thereof, and the use thereof |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0550032A3 (en) |
| JP (1) | JPH05247319A (en) |
| KR (1) | KR930012963A (en) |
| BR (1) | BR9205192A (en) |
| CA (1) | CA2086023A1 (en) |
| DE (1) | DE4143258A1 (en) |
| MX (1) | MX9207672A (en) |
| TW (1) | TW249814B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8975323B2 (en) | 2010-02-22 | 2015-03-10 | Polyone Corporation | UV laser markable thermoplastic elastomer compound |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3419885B2 (en) * | 1994-05-25 | 2003-06-23 | 帝人株式会社 | Thermoplastic resin composition |
| DE19620993A1 (en) * | 1996-05-24 | 1997-11-27 | Bayer Ag | Laser-inscribable polymer molding compounds |
| JP3413329B2 (en) * | 1996-06-28 | 2003-06-03 | ポリプラスチックス株式会社 | Laser marking method and laser-marked molded product |
| US5977514A (en) * | 1997-06-13 | 1999-11-02 | M.A. Hannacolor | Controlled color laser marking of plastics |
| AT406476B (en) | 1999-01-25 | 2000-05-25 | P1 Handels Gmbh | PLUGS FROM FOAMED THERMOPLASTIC PLASTIC |
| NL1012476C2 (en) * | 1999-06-30 | 2001-01-03 | Dsm Nv | Laser writable polymer composition. |
| GB2352824A (en) * | 1999-07-30 | 2001-02-07 | Nokia Mobile Phones Ltd | Laser markable material comprising TiO2 pigmented thermoplstic elastomer |
| AT412710B (en) * | 2002-07-17 | 2005-06-27 | P1 Handels Gmbh | GRAVES OF DUSTED, THERMOPLASTIC PLASTIC |
| NL1027217C2 (en) | 2004-10-11 | 2006-04-18 | Klinipath B V | Tissue holder, and device and method for providing such a tissue holder with data. |
| WO2021235556A1 (en) * | 2020-05-22 | 2021-11-25 | 王子ホールディングス株式会社 | Printed material, method for producing printed material and printing medium for laser printing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55125148A (en) * | 1979-03-22 | 1980-09-26 | Asahi Chem Ind Co Ltd | Polyoxymethylene composition and preparation thereof |
| TW267182B (en) * | 1991-06-29 | 1996-01-01 | Hoechst Ag |
-
1991
- 1991-12-31 DE DE4143258A patent/DE4143258A1/en not_active Withdrawn
-
1992
- 1992-11-24 TW TW081109414A patent/TW249814B/zh active
- 1992-12-22 CA CA002086023A patent/CA2086023A1/en not_active Abandoned
- 1992-12-24 EP EP19920121987 patent/EP0550032A3/en not_active Withdrawn
- 1992-12-28 JP JP4349043A patent/JPH05247319A/en not_active Withdrawn
- 1992-12-29 KR KR1019920025973A patent/KR930012963A/en not_active Application Discontinuation
- 1992-12-30 MX MX9207672A patent/MX9207672A/en unknown
- 1992-12-30 BR BR9205192A patent/BR9205192A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8975323B2 (en) | 2010-02-22 | 2015-03-10 | Polyone Corporation | UV laser markable thermoplastic elastomer compound |
Also Published As
| Publication number | Publication date |
|---|---|
| TW249814B (en) | 1995-06-21 |
| EP0550032A2 (en) | 1993-07-07 |
| DE4143258A1 (en) | 1993-07-01 |
| JPH05247319A (en) | 1993-09-24 |
| KR930012963A (en) | 1993-07-21 |
| EP0550032A3 (en) | 1993-11-03 |
| BR9205192A (en) | 1993-07-06 |
| MX9207672A (en) | 1994-05-31 |
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