DE4319190A1 - Polymer mixts. for prodn. of laser-inscribed mouldings - contain polyoxymethylene homo- or copolymer, polycarbonate, opt. impact-modifying polymer and opt. fillers - Google Patents

Abstract

The use of polymer mixt. (I) for the prodn. of moulded prods. which are inscribed with the aid of high-energy radiation is claimed. (I) contains (A) 40-99 wt.% polyoxymethylene homo- or co-polymer, (B) 1-30 wt.% polycarbonate, (C) 0-50 wt.% impact-modifying polymer and (D) 0-50 wt.% fibrous and/or particulate fillers. The prodn. of moulded prods. with markings, comprises exposing a moulded prod. made from (I) to high-energy radiation. Also claimed are moulde prods. with markings obtd. by this process. The markings are made with laser radiation pref. using a Nd/YAG laser. USE/ADVANTAGE - The polyoxymethylene-based mouldings have a good surface structure and good contrast between markings and background.

Description

The present invention relates to the use of poly mixtures, containing

• A) 40-99 wt .-% of a Polyoxymethylenhomo- or Copolyme risats
• B) 1-30 wt .-% of a polycarbonate
• C) 0-50 wt .-% of an impact modifying polymer and
• D) 0-50 wt .-% fibrous and / or particulate fillers for producing by means of high-energy radiation provided with a label shaped bodies.

Mixtures of polyoxymethylene polymers and polycarbons th are known per se and for example in the DE-A 27 54 600, US-A 3,646,159, EP-A 122 560 and the EP-A 338 303. In none of these writings will However, the application for the production of means of energy egg mentioned ment radiation-writable moldings.

In DE-A 29 36 926 and DE-A 30 44 722 (addition to DE-A 29 36 926) are methods for producing ver with ver various signs provided similar plastic parts described after which the plastic of the base material a discolourable on exposure to energy radiation Filler added, from the mixture Herge a molding and then this from high-energy radiation is set.

As shown in DE-A 30 44 722 is as filler carbon black or Graphite used and it is the base plastic preferably a polyoxymethylene polymer.  

It is easy to understand that when using carbon black as filler only black moldings can be labeled NEN; it creates a bright (the natural color of the base art corresponding text) on black background.

The mechanism of this inscription is based on the combus tion of carbon in carbon black or graphite to CO ₂ , which escapes as gas, creating a foam-like melting zone in the form of the character to be transmitted, in which there are no more soot particles.

In many cases, however, it is desirable to use bright Formkör to be provided with a dark lettering. This is in principle possible by means of the energierei radiation burns the plastic itself or ver kohlt. Shaped bodies of polyoxymethylene polymers without addition however, only labels are used in this procedure with low, generally unsatisfactory Kon contrast.

The present invention was therefore based on the object Polyoxymethylene molding compounds that are particularly good label with high-energy radiation.

This object is achieved by the use of polymer blends gene solved according to claim 1.

The polymer mixtures to be used according to the invention ent hold as component A 40 to 99, preferably 60-98 and in particular 70 to 98 wt .-%, based on the total weight the components A-D, a polyoxymethylene homo- or co polymer.

Such polymers are known per se to the person skilled in the art and described in the literature.

In general, these polymers have at least 50 mole percent of recurring units -CH ₂ O- in the polymer backbone.

The homopolymers are generally polymerized of formaldehyde or trioxane, preferably in the presence of suitable catalysts.

In the context of the invention, preference is given to polyoxymethylene copolymers as component A, in particular those which, in addition to the repeating units -CH ₂ O-, also contain up to 50, preferably from 0.1 to 20, and in particular from 0.3 to 10, mol% of recurring units

wherein R ¹ to R ^{4 are} independently a hydrogen atom, a C 1 to C ₄ alkyl group or a halogen-substituted alkyl group having 1 to 4 carbon atoms and R 5 is a -CH ₂ -, -CH ₂ O-, a C ₁ - to C ₄ alkyl or C ₁ - to C ₄ haloalkyl substituted te methylene group or a corresponding oxymethylene group and n has a value in the range of 0 to 3. Before geous enough, these groups can be introduced by ring opening of cyclic ethers in the copolymers. Preferred cyclic ethers are those of the formula

wherein R ¹ to R ⁵ and n have the abovementioned meaning. For example, ethylene oxide, 1,2-propylene oxide, 1,2-Bu tylenoxid, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane and 1,3-dioxepane called cyclic ethers and linear oligo- or Polyformals such as polydioxolane or polydioxepan called Co monomers.

Also suitable as component A) are oxymethylene ethers polymers which, for example, by reaction of tri oxane, one of the cyclic ethers described above with a third monomer, preferably a bifunktio nelle compound of the formula

wherein Z is a chemical bond, -O-, -ORO- (R = C ₁ - to C ₈ - alkylene or C ₂ - to C ₈ -cycloalkylene), who made the.

Preferred monomers of this type are ethylene diglycide, diglyme cidyl ether and diether from glycidylene and formaldehyde, Dio xan or trioxane in the molar ratio 2: 1 and diether from 2 mol glycidyl compound and 1 mol of an aliphatic diol with 2 to 8 carbon atoms such as the diglycidyl ethers of ethylene glycol, 1,4-butanediol, 1,3-butanediol, cyclobu tan-1,3-diol, 1,2-propanediol and cyclohexane-1,4-diol to only to give some examples.

Process for the preparation of the above-described homo and copolymers are known in the art and in the Li described, so that here more details erübri gene.

The preferred polyoxymethylene copolymers have melting point of at least 150 ° C and molecular weights (wt Mw) in the range of 5000 to 200,000, preferably from 7,000 to 150,000.

Endgruppenstabilisierte Polyoxymethylenpolymerisate, the the chain ends have C-C bonds become especially prefers.  

As component A) in particular products can be be set, which still has a relatively high proportion (in gen. <0.1% by weight) of thermally unstable portions.

As component B) include the invention to verwen denden molding compounds 1-30, preferably 2-15 and in particular Other 2 to 12 wt .-%, of a polycarbonate.

Suitable, thermoplastic, preferably halogen-free aro matic polycarbonates according to component A) are those on Base of the diphenols of the formula (I)

wherein A is a single bond, a C ₁ -C ₃ alkylene, C ₂ -C ₃ alkylidene, a C ₃ -C ₆ cycloalkylidene group, -S- or -SO ₂ -.

Suitable polycarbonates are both homopolycarbonates as also copolycarbonates.

The diphenols of the formula (I) are either known from the literature or preparable by literature methods.

The preparation of the suitable polycarbonates B is litera turbite and can, for example, with Phosgen after the Pha interfacial or phosgene method in homogeneous phase (the so-called pyridine method) suc in which the respective molecular weight to be set in known manner by an appropriate amount of known Chain breakers is achieved. (Regarding polydiorganosilo xan-containing polycarbonates see, for example DE-A 33 34 782.)

Suitable chain terminators are, for example, phenol, p- tert-butylphenol but also long-chain alkylphenols such as 4- (1,1,3,3-tetramethyl-butyl) -phenol according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 C atoms in the alkyl substituents according to the German patent application 35 06 472, such as p-nonyl  phenyl 3,5-di-tert-butylphenol, p-tert-octylphenol, p-Do decylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3,5-dime thylheptyl) phenol.

The polycarbonates generally have relative viscosities η _{rel of} from 1.10 to 1.50, in particular from 1.25 to 1.40 ml / g. This corresponds to average molecular weights (Mw) of 10,000 to 200,000, preferably 20,000 to 80,000.

Suitable diphenols of the formula (I) are, for example, Hy drochinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hy droxyphenyl) -propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane and 1,1-bis (4-hydroxyphenyl) cyclohexane.

Preferred diphenols of the formula (I) are 2,2-bis (4-hydroxy phenyl) -propane (bisphenol A) and 1, 1-bis (4-hydroxyphe phenyl) -cyclohexane.

The polycarbonates can also be branched in a known manner be, preferably by the incorporation of 0.05 bis 2.0 mol%, based on the sum of the diphenols used, tri- or more than trifunctional compounds, at For example, those with three or more than three phenolic OH groups.

Preferred polycarbonates are in addition to the bisphenol A homopo lymerisat the copolycarbonates of bisphenol A.

As component C) thermopla according to the invention Stical molding compositions 0 to 50, preferably 0 to 40 wt .-% an impact-modifying polymer (hereinafter also denoted as elastomeric polymer or elastomer net).

Preferred types of such elastomers are the so-called Ethy len-propylene (EPM) and ethylene-propylene-diene (EPDM) -Kau tschuke.

EPM rubbers generally have virtually no double bonds more, while EPDM rubbers 1 to 20 doublebin can have / 100 C atoms.  

As diene monomers for EPDM rubbers are, for example conjugated dienes like isoprene and butadiene, non-conjugal te Dienes with 5 to 25 carbon atoms such as penta-1,4-diene, He xa-1,4-diene, hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene and Octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohe xadiene, cyclooctadienes and dicyclopentadiene and alkenyl norbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-nor bornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltri-cyclo (5.2.1.0.2.6) -3,8- called decadiene or mixtures thereof. Preference is given to He xa-1,5-diene-5-ethylidene-norbornene and dicyclopentadiene. The Diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the Gesamtge weight of the rubber.

Another group of preferred rubbers are copolymers of ethylene with esters of (meth) acrylic acid. additionally For example, the rubbers may still contain epoxy groups. These Epoxy group-containing monomers are preferably by adding monomers containing epoxy groups general formulas II or III to the monomer mixture in the Rubber incorporated:

where R6-R10 is hydrogen or alkyl groups having 1 to 6 carbon atoms represent and m is an integer from 0 to 20, g a integer from 0 to 10 and p an integer from 0 to 5 is.

Preferably, the radicals R6 to R8 hydrogen, wherein m is 0 or 1 and g is 1. The corresponding verbin allyl glycidyl ether and vinyl glycidyl ether.  

Preferred compounds of formula III are epoxy groups containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate and glycidyl methacrylate.

Advantageously, the copolymers consist of 50 to 98 wt .-% Ethylene, 0.1 to 20 wt .-% of epoxy groups-containing monomials ren and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of
50 to 98, in particular 55 to 95 wt .-% ethylene,
0.1 to 40, in particular 0.3 to 20% by weight of glycidyl acrylate lat and / or glycidyl methacrylate, and
1 to 45, in particular 10 to 40 wt .-% n-butyl acrylate and / or 2-ethylhexyl acrylate.

Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.

In addition, vinyl esters and vinyl ethers may also be used as comonomers be used.

The ethylene copolymers described above can after be prepared per se known methods, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are general known.

Preferred elastomers are also emulsion polymers whose Production z. As in Blackley in the monograph "Emulsion Polymerization. "The usable emulsifier ren and catalysts are known per se.

Basically, homogeneously constructed elastomers or those with a shell structure are used. The sha This type of construction is followed by the addition of rows determined individual monomers; also the morphology of the polyme It is influenced by this order of addition.  

Only representative are here as monomers for the manufacturer Development of the rubber part of the elastomers acrylates such. B. n-butyl acrylate and 2-ethylhexyl acrylate, corresponding metha crylate, butadiene and isoprene and mixtures thereof Nannt. These monomers can be reacted with other monomers such as z. As styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, Ethyl acrylate and propyl acrylate are copolymerized.

The soft or rubber phase (with a Glasübergangstem temperature of below 0 ° C) of the elastomers may be the core, the outer shell or a middle shell (in elastomers with more than bivalve structure); in multi-shelled Elastomers can also have multiple shells of a rubber phase exist.

Are next to the rubber phase still one or more hard components (with glass transition temperatures of more than 20 ° C) involved in the construction of the elastomer, so they are generally by polymerization of styrene, acrylonitrile, Methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyla crylate and methyl methacrylate produced as major monomers. In addition, smaller shares in other Como can also be used here nomeren be used.

In some cases it has turned out to be advantageous to use emulsion polymers which are at the top surface have reactive groups. Such groups are z. As epoxy, amino or amide groups and functional Groups, by the concomitant use of monomers of the general NEN formula IV

can be introduced, wherein the substituents may have the following meaning:
R ^{15 is} hydrogen or a C ₁ - to C ₄ -alkyl group,
R ^{16 is} hydrogen, a C ₁ - to C ₈ -alkyl group or an aryl group, in particular phenyl,
R ^{17 is} hydrogen, a C ₁ - to C ₁₀ -alkyl, a C ₆ - to C ₁₂ -aryl group or -OR ¹⁸ ,
R ^{18 is} a C ₁ - to C ₈ -alkyl or C ₆ - to C ₁₂ -aryl group, which may optionally be substituted with groups containing O or N,
X is a chemical bond, a C ₁ - to C ₁₀ -alkylene or

Y OZ or NH Z and
Z is a C ₁ - to C ₁₀ -alkylene or C ₆ - to C ₁₂ -arylene group.

Also, the graft monomers described in EP-A 208 187 are used to introduce reactive groups on the surface suitable.

As further examples may be acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (N-t-butylamino) ethyl methacrylate, (N, N-dimethylamino no) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N- Diethylamino) ethyl acrylate.

Furthermore, the particles of the rubber phase can also ver be wet. As a crosslinking monomers acting example Buta-1,3-diene, divinylbenzene, diallyl phthalate and di hydrodicyclopentadienyl acrylate and those in EP-A 50 265 described compounds.

Furthermore, so-called graft-crosslinking monomers (graft-linking monomers) are used, d. H. Monomers with two or more polymerizable double bonds, at the polymerization at different speeds  react. Preferably, such compounds will be used det, in which at least one reactive group with approximately the same same speed as the other monomers polymeri while the other reactive group (or reactive Groups) z. B. polymerized much slower (polymerisie ren). The different polymerization rates bring a certain amount of unsaturated doublebin in rubber. Will then be on a such gum grafted another phase, so rea the double bonds present in the rubber gase in at least partially with the graft monomers under formation of chemical bonds, d. H. the grafted phase is closed at least partially via chemical bonds with the graft basis.

Examples of such graftlinking monomers are allyl containing groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, Al lylmethacrylate, diallyl maleate, diallyl fumarate, diallylitaco nat or the corresponding Monoallylverbindungen this Di carboxylic acids. There are a lot of other suitable neter graft-curing monomer; for details For example, reference is made here to US Pat. No. 4,148,846.

In general, the proportion of this crosslinking mono mers to the component C) up to 5 wt .-%, preferably not more than 3% by weight, based on C).

Below are some preferred emulsion polymers listed. First, here are graft polymers with a To name the core and at least one outer shell, the fol have the following structure:

Monomers for the core Monomers for the shell Buta-1,3-diene, isoprene, n-butyl acrylate, ethylene hexyl acrylate or mixtures thereof, optionally together with crosslinking monomers Styrene, acrylonitrile, (meth) acrylates optionally with reactive groups as described herein

Instead of graft polymers with a mehrschaligen Construction can also be homogeneous, d. H. single-shell elastomers Buta-1,3-diene, isoprene and n-butyl acrylate or their copoly  meren be used. Also these products can by Concomitant use of crosslinking monomers or monomers with reactive groups are produced.

The described elastomers C) can also after other üb method, z. B. by suspension polymerization ago be put.

Further preferred rubbers are polyurethanes as in the EP-A 115 846, EP-A 115 847, EP-A 116 456, EP-A 117 664 and EP-A 327 384 are described. Commercially available are such products z. B. under the names Desmopan® (Bayer AG) or Elastollan® (Elastogran Polyurethane GmbH) available.

Of course, mixtures of the above listed rubber types are used.

As component D) can be used according to the invention Molding compounds 0 to 50, preferably 5 to 40 wt .-% of a fa ser- or particulate filler or mixtures thereof contain.

Examples of reinforcing fillers are Ka lithium titanate whisker, carbon and preferably glass called fibers, wherein the glass fibers z. B. in the form of Glasge weaving, mats, nonwovens and / or glass silk rovings or ge cut glass silk from low-alkali E-glass with a Diameter of 5 to 200 microns, preferably 8 to 50 microns can be used, wherein the fibrous fillers after their incorporation, preferably a mean length of 0.05 to 1 mm, in particular 0.1 to 0.5 mm.

Other suitable fillers are, for example, wollastonite, Calcium carbonate, glass beads, quartz powder, Si and boron nitride or mixtures of these fillers.

In addition to the components A) and B) and optionally C and D) can the molding compositions to be used according to the invention are still conventional Additives and processing aids. Just Examples include additives for trapping formaldehyde (Formaldehyde scavenger), plasticizer, lubricant, anti oxidants, adhesion promoters, light stabilizers and pigments  called. The proportion of such additives is generally in the Range from 0.001 to 5 wt .-% (stabilizers, pigments and Lubricant).

Corresponding compounds are known to the person skilled in the art and For example, in EP-A 327 384 described.

By the concomitant use of a polycondensation product 2,2-di (4-hydroxyphenyl) propane (bisphenol A) and epichlorohy in it (component C)) can verwen the dispersibility The polyamides can be improved. In addition, such show Products a lighter intrinsic color and less specks and Streaks as products containing only polyamide.

Such condensation products are used in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 and in particular from 0.1 to 3 wt .-% used.

Also the condensation products of epichlorohydrin and bisp henol A are commercially available. Process for their preparation position are also known to those skilled in the art. Handelsbe Drawings of the polycondensates are Phenoxy® (the Union Car bide Corporation) or Epikote® (Shell). The molecular weight of the polycondensates can vary within wide limits; In principle, the commercially available types are all suitable.

According to the invention the Formmas described above for the production of high-energy radiation use moldings provided with a lettering det.

The production of the moldings to be inscribed is not Object of the invention; appropriate procedures are the Professional known from the literature. Only as an example is as preferred method is the mixing of the components in the Melt on an extruder and subsequent processing of the obtained granules by injection molding.

As high-energy radiation in the Ver invention can z. B. electron or laser radiation used be laser radiation is preferably used. Be Nd: YAG solid-state lasers are particularly preferably used.  

To be inscribed moldings may, for. B. via an ent speaking mask corresponding to the desired label which are exposed to radiation, the control of the But electron or laser beam can also with the help of a Computer done.

The intensity and duration of the exposure influence Kon trast, penetration depth and surface structure of the molded article Pers. More detailed statements about this can be found at For example, in two relevant publications in Plastics 81 (1991), No. 4, pages 341ff and in art 78 (1988), No. 8, pages 688ff, which deals with La serbeschriftung of moldings of thermoplastic art dealing with substances. Furthermore, DE-A 39 36 926, DE 36 19 670, DE 30 44 722 and EP-A 190 997 called. According to the inventive method for the preparation of be written moldings based on Polyoxymethylenho Mono- or copolymers become moldings from a Mi from components A and B described above, and optionally C and D high-energy radiation, preferably Electron or laser radiation exposed, in particular preferably Nd: YAG laser can be used.

Obtainable by the process according to the invention be written form bodies are characterized by a good con trast between caption and background, at the same time good surface texture.

Examples

In the following examples, the captions were printed with a Nd: YAG laser performed in the IR range at a Wavelength of 1.064 microns emitted.

The laser beam was, as described in EP-A 330 689, by two computer-controlled rotating mirrors according to the contour to be written over the surface in focus guided. Further information on the aperture diameter, the select th lamp current intensity and the pulse frequency are the Ta 2 (the indicated values were in each case determined as optimal for the corresponding plastic).  

The contrast also shown in Table 2 was determined by determining the ratio of background and luminance sign at a uniform illuminance of 500 cd / m ² .

In the visual assessment, scores of 1 (very good) awarded to 6 (very bad).

The following components were used
A / 1: Polyoxymethylene copolymer, prepared from a mixture of 97.3% by weight of trioxane and 2.7% by weight of butanediol formally, which contains about 3% by weight of unreacted trioxane and 5% by weight of thermally unstable adduct contained. After degradation of the thermally unstable fractions and removal of the liberated trioxane and formaldehyde, the Co polymer has a melt index of 9 g / 10 min (2.16 kg at 190 ° C load according to DIN 53 735).

The crude polymer contained 0.4% by weight Irganox®245 (Ciba Geigy) and 0.2% by weight of a melamine formaldehyde condensate Sats according to Ex. 1 of DE-A 25 40 207 and 0.05% by weight of a synthetic Mg silicate (Ambosol®, Soc. Soc. Nobel Bozel).

A / V1 polycaprolactam having a viscosity number (measured 0.5% in 96% strength by weight H ₂ SO ₄ at 25 ° C. according to DIN 42 727) of 190 ml / g (Ultramid® B35 from BASF Aktiengesellschaft) A / V2 Homopolypropylene having a melt index of 11 g / 10 min (2.16 kg / 230 ° C according to DIN 53 735), available under the name Novolen®1100 N from BASF Aktiengesellschaft).

A / V3 copolymer of 99% by weight of methyl methacrylate and 1% by weight Methyl acrylate having a molecular weight (wt value) of 110,000 g / mol (Lucryl® G 88 from BASF Aktien society).

A / V4 polybutylene terephthalate having a viscosity number (0.5%) in phenol / o-dichlorobenzene 1: 1 (weight ratio) at 25 ° C) of 130 ml / g (Ultradur® B 4500 from BASF Aktiengesellschaft).  

B: Bisphenol A-based polycarbonate with a viscous (0.5% in chloroform at 25 ° C) of 61.5 ml / g (Panlite®RC 1225 from Teÿin).

In addition, the following components were used in some examples:
E / 1 carbon black with an average particle size of 14 nm (Prin tex®90 from Degussa).
E / 2 TiO ₂ (Kronos® 2200 from Bayer).
E / 3 polyamide having a number average molecular weight of 5000, prepared from 37 wt .-% ε-caprolactam and 63 wt .-% of an equimolar mixture of adipic acid and hexamethylenediamine using propionic acid as a molecular weight regulator.
E / 4 polycondensation product of 2,2-di- (4-hydrophenyl) per pan and epichlorohydrin (Phenoxy® PKHH from Union Carbide).

The components described above were heated at 23 ° C in mixed in a dry mixer, in a twin-screw extruder (ZSK 28 from Werner & Pfleiderer) dosed, plasticized and extruded. The throughput was 6 kg / h at one turn 150 min.

From the granules thus obtained were circular discs with 60 mm Diameter and 2 mm thickness sprayed, the be as introductory be written, labeled.

The composition of the molding compositions is Table 1, the results The measurements can be found in Tab. 2 and 3.  

Table 1

Composition of the molding compounds

Table 3

Surface of the circular

Claims (8)

1. Use of polymer blends containing

• A) 40-99 wt .-% of a Polyoxymethylenhomo- or Copo lymerisats
• B) 1-30 wt .-% of a polycarbonate
• C) 0-50 wt .-% of an impact modifying Polymerme ren and
• D) 0-50 wt .-% fibrous and / or particulate filling materials

for producing by means of high-energy radiation ment provided with a lettering moldings. 2. Use according to claim 1 wherein as the radiation source a laser is used for the high-energy radiation becomes. 3. A process for the preparation of labeled moldings based on Polyoxymethylenhomo- or Copolymeri saten, characterized in that comprising a molding of a mixture containing

• A) 40-99 wt .-% of a Polyoxymethylenhomo- or Copo lymerisats
• B) 1-30 wt .-% of a polycarbonate
• C) 0-50 wt .-% of an impact modifying Polymerme ren and
• D) 0-50 wt .-% fibrous and / or particulate filling materials

exposed to high-energy radiation. 4. The method according to claim 3, characterized in that one uses laser radiation as high-energy radiation det. 5. The method according to claim 4, characterized in that one generates the laser radiation with a Nd / YAG laser. 6. Labeled moldings obtainable according to the method of claims 3 to 5.