JPH10138293A - Polymer molding composition to which laser marking can be applied - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded item which gives one or multiple colors onto a dark background after marking, and obtain various lightness grades and color tones by a method wherein marking is formed by giving various pigments to a polymer to vary laser energy, laser frequency, and marking speed. SOLUTION: Polymer or copolymer suitable as a polymer matrix, e.g. polyalkylene terephthalate, is a reaction product of aromatic dicarboxylic acid or reactive derivative thereof and aliphatic, cyclic aliphatic or aromatic aliphatic diol and a mixture of these reaction products. Polydiorganosiloxane- polycarbonate block copolymer contains, firstly, an aromatic carbonate structure unit represented by the formula I in a polymer chain and contains, secondly, polyorganosiloxane having aryloxy end group represented by the formula II. In the formulae, Ar denotes the same or different aryl group from diphenol, and R and R' denote the same or different straight-chain alkyl, branched-chain alkyl, alkenyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the production of a molded article having a dark marbled or colored marbled surface, or having a colored lacquer superimposed thereon, which shows high contrast 2- or multi-color mottle marks after laser engraving. For
It relates to the use of at least two differently colored polymer molding compositions.

[0002] It has become increasingly important to apply designs, letters, numbers and / or images using laser beam printers to mark and decorate molded articles made of plastic. Apart from its cost-efficiency compared to conventional stamping methods, laser marking provides significant flexibility with regard to the stamp type, stamp dimensions and stamp design regardless of batch size. The marking of electrical / electronic components, keyboard key covers, casings and identification cards is a classic use of laser engraving.

[0003] The following options are known for marking plastics using laser engraving: Dark symbol on light background Colors the polymer matrix with a light colorant-pigment or dye. Laser engraved polymer matrix /
The colorant is partially carbonized for absorption of laser energy. This results in a dark coloration of the light polymer matrix. This behavior is restricted to polymers that tend to carbonize.

[0004] The contrast ratios which can be achieved thereby are unsatisfactory for many applications.

The addition of colorants whose color changes due to absorption of laser energy is described, for example, in EP-A 019
0 997. Thus, polybutylene terephthalate is colored red using, for example, iron oxide.
Laser engraving produces a dark symbol on a red background. The contrast ratio has proven to be unsatisfactory.

[0006] 2. Light symbols on dark background: polymers, which tend to foam due to the absorption of laser energy
Colorants or additives have proven to be useful in this type of imprinting. Foaming produces a light imprint on a dark background. The contrast ratios that can be achieved are unsatisfactory for many application areas.

[0007] By adding various pigments to the polymer, after laser engraving, 2- or poly- on a dark background.
It has been found that molded articles giving color marks can be produced. By varying the laser energy, the laser frequency and / or the marking speed, different lightness steps and shades can be obtained.

The present invention relates to a thermoplastic molding composition in the form of at least two differently colored, preferably granular materials, which is at least two-colored in the laser-marked position after laser engraving. It relates to the use for the production of molded articles.

The present invention further provides the above-described use by two- or multi-component injection molding of a two- or multi-color granular material to form a molded article and for the production of molded articles by hot pressing. Here, the two- or multi-color moldings can optionally be overlaid with suitable colored lacquers or films, the lacquers or films being removed at the locations marked by laser engraving, whereby the lacquer coat or Film layer (background)
Various colors of the lower background with excellent contrast with respect to are obtained.

[0010] The present invention provides for a light-to-white imprint in combination with a mono- or multi-color or dark-to-black imprint at the location where the variously colored components are marked after the laser imprint, or A dark to black imprint, optionally combined with a single or multi-color imprint, is provided with a colored, optionally black-and-white marble, optionally black and colored marble, optionally white and colored marble, The invention also relates to a process as described above for the production by 2- or multi-component injection-molding or hot-pressing of moldings which optionally exhibit a good contrast on a dark or optionally monochromatic light background.

[0011] Two- or multi-component injection molding techniques are known per se in the art. In the course of this process, two or more differently colored thermoplastic granular materials are separated from one another and, as such, using injection molding parameters known in the art, using a two- or multi-component injection molding machine. To form a molded product. Processing is generally carried out at a temperature in the range from 100 to 400C, preferably from 130 to 380C, especially from 150 to 350C, depending on the thermoplastic material used. Thereby, a transition phase is obtained in the interfacial region of the two or more thermoplastic moldings being processed; however, here the components themselves are not otherwise mixed. A juxtaposed 2- or multi-phase structure in the thermoplastic molding is thus obtained.

In the case of hot pressing, two or more differently colored granular materials are first mechanically mixed. These are then introduced into a mold and heated to bring the thermoplastic molding composition almost into a molten state. For hot pressing, 70 to 70, depending on the thermoplastic material used
350 ° C, preferably 90 to 300 ° C, especially 100 to 2
A temperature of 60 ° C. is generally used. These mixed granular materials are then pressed into the final shape by the action of pressure. When cooled below the melting temperature range, the molded article transitions to its solid state and can be removed from the mold.

The moldings produced in this way can optionally be coated and subsequently marked with a laser beam in the manner described above.

[0014] A commercially available laser system, preferably a Nd-YAG solid state laser, is used as the energy source. The wavelength can be between 193 and 10,600 nm, preferably between 532 and 1064 nm.

The molding composition used in accordance with the present invention provides visual information in the form of designs, graphics, numbers, letters, symbols, images (eg, passport photographs, portraits, photographs), etc., by means of laser energy, eg, laser energy. Can be used to apply by beam printing machine.

Thus, for example, a photographic image can be transferred to a molding composition used according to the invention.

The thermoplastic molding compositions are, for example: A) 99.9999-30, preferably 99.9995
To 35, especially 99.9990 to 40 parts by weight of a thermoplastic polymer; B) 0.0001 to 10.00 parts by weight of pigment, preferably 0.0005 to 8.00 parts by weight, most preferably 0.1 to 0.5 parts by weight.
0010 to 6.00 parts by weight of pigment, C) 0 to 50 parts by weight of filler and reinforcement, D) 0 to 60 parts by weight of flame retardant, E) 0 to 30 parts by weight of elastomer modifier, F) It may contain from 0 to 8 parts by weight of antimony trioxide.

Examples of polymers or copolymers suitable as Component A polymer matrices include polyalkylene terephthalates, aromatic polyesters, polyamides, polycarbonates, polyacrylates, polymethacrylates, ABS graft polymers, polyolefins such as polyethylene or polypropylene, polystyrene, poly Includes those based on vinyl chloride, polyoxymethylene, polyimide, polyether and polyetherketone, which can be used individually or as a blend of various polymers.

Polyalkylene terephthalates in the sense of the present invention are the reaction products of aromatic dicarboxylic acids or their reactive derivatives (eg dimethyl esters or anhydrides) with aliphatic, cycloaliphatic or aromatic aliphatic diols, Is a mixture of the reaction products of

A preferred polyalkylene terephthalate is terephthalic acid (or a reactive derivative thereof) and has 2 to 2 carbon atoms.
It can be produced from 10 aliphatic or cycloaliphatic diols by known methods (Kunststoff-
Handbuch, Volume VIII, p. 695 et seq., Karl-Hanser-Verlag, Mun.
ich 1973).

Preferred polyalkylene terephthalates have at least 80, preferably 90 mole% terephthalic acid residues with respect to the dicarboxylic acid and at least 80, preferably at least 90 mole% with respect to the diol component.
Of ethylene glycol and / or 1,4-butanediol.

Preferred polyalkylene terephthalates are, in addition to terephthalic acid residues, up to 20 mol% of other aromatic dicarboxylic acids having from 8 to 14 carbon atoms or from 4 to 1 carbon atoms.
Residues of two aliphatic dicarboxylic acids, such as phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,
It may contain residues of 4'-diphenyldicarboxylic acid, succinic acid, adipic acid or sebacic acid, azelaic acid or cyclohexanediacetic acid.

Preferred polyalkylene terephthalates are, in addition to ethylene glycol or 1,4-butanediol residues, up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cyclic fatty acids having 6 to 21 carbon atoms. Group diols such as 1,3-propanediol, 2-ethylpropanediol-1,3, neopentyl glycol,
5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, 3-methylpentanediol-2,4,2-methyl-pentanediol-2,4,2,2,4-trimethylpentane Diol-
1,3 and -1,6,2-ethylhexanediol-
1,3,2,2-diethylpropanediol-1,3,
2,5-hexanediol, 1,4-di- (b-hydroxyethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3 -Tetramethyl-cyclobutane,
It can contain 2,2-bis- (3-b-hydroxy-ethoxyphenyl) -propane, as well as 2,2-bis- (4-hydroxypropoxyphenyl) -propane (DE-OS 24 07 674, 24 07
776, 27 15 932).

The polyalkylene terephthalate can be used in relatively small amounts of trihydric or tetrahydric alcohols or 3- or 4-basic carboxylic acids such as DE-OS 1900 270
And by adding those as described in U.S. Pat. No. 3,692,744. Examples of preferred branching agents include trimesic acid, trimellitic acid, trimethylolethane and -propane, and pentaerythritol.

It is preferable to use 1 mol% or less of a branching agent with respect to the acid component.

Particularly preferred polyalkylene terephthalates are those prepared exclusively from terephthalic acid and its reactive derivatives (eg its dialkyl esters) and ethylene glycol and / or 1,4-butanediol (polyethylene and polybutylene terephthalate); And mixtures of these polyalkylene terephthalates.

Preferred polyalkylene terephthalates also include copolyesters made from at least two of the above acid components and / or from at least two of the above alcohol components; particularly preferred copolyesters are poly- (ethylene glycol / 1,4-butanediol)
Terephthalate.

The polyalkylene terephthalates which are preferably used as component A generally have in each case about 0.4 to 1.5 dl, measured at 25 ° C. in phenol / o-dichlorobenzene (1: 1 parts by weight). /
g, preferably 0.5 to 1.3 dl / g.

Aromatic polycarbonates in the sense of the invention are understood to mean homopolycarbonates and mixtures of these polycarbonates, which are based, for example, on at least one of the following diphenols: hydroquinone, resorcinol, dihydroxydiphenyl, bis -(Hydroxyphenyl) -alkane, bis-
(Hydroxyphenyl) -cycloalkane, bis- (hydroxyphenyl) -sulfide, bis- (hydroxyphenyl) -ether, bis- (hydroxyphenyl)
-Ketone, bis- (hydroxyphenyl) -sulfone,
Bis- (hydroxyphenyl) -sulfoxide, α,
α'-Bis- (hydroxyphenyl) -diisopropylbenzene, and derivatives thereof containing alkylated or halogenated nuclei.

These and other suitable diphenols are described, for example, in US Pat. No. 3,028,365, 2999.
835, 3 148 172, 2 275 601,
2991 283, 3271 367, 3062
781, 2 970 131 and 2 999 846
DE-OS 1 570 703, 2 06305
0, 2 063 052, 2 211 956, 22
11 957, French Patent Specification 1 561 5
18, and H.R. Monograph by Schnell:
“Chemistry and Physics of
Polycarbonates ”, Intersci
ence Publishers, New York
1964.

Examples of preferred diphenols are: 2,2-
Bis- (4-hydroxyphenyl) -propane, 1,1
-Bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) ) -Propane, 2,2
-Bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, bis- (4-hydroxyphenyl) -sulfide, 1,1- Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane is included.

The diphenols can be used individually or as a mixture. A particularly preferred aromatic polycarbonate is 2,2-bis- (4-hydroxyphenyl)
-Polycarbonates based on propane and / or based on one of the diphenols mentioned above as being preferred. Particularly preferred diphenols are 2,2-bis-
(4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane or 1,1-bis- (4-hydroxyphenyl)
Based on -3,3,5-trimethylcyclohexane, or 2,2-bis- (4-hydroxyphenyl) -propane and 1,1-bis- (4-hydroxyphenyl)-
Based on a mixture of 3,3,5-trimethylcyclohexane.

Aromatic polycarbonates can be prepared in a known manner, for example by transesterification of the corresponding bisphenol with diphenyl carbonate in the molten state, and in solution from bisphenol and phosgene. The solution can be homogeneous (pyridine method) or heterogeneous (2-
Phase boundary method) (H. Schnell,
“Chemistry and Physics of
"Polycarbonates", Polymer
Reviews, Vol. IX, page 33 and below, Inte
rsscience Publ. 1964).

[0034] Aromatic polycarbonates are generally about 1
0000-200,000, preferably 20,000
Having an average molecular weight M _W of ～80,000 (determined by gel chromatography after preliminary calibration).

The copolycarbonates in the sense of the present invention have in particular an average molecular weight M _w of about 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after pre-calibration). About 75 to 97.5% by weight, preferably 8%
Polydiorganosiloxane-polycarbonate having a content of aromatic carbonate structural units of 5 to 97% by weight and a content of polydiorganosiloxane structural units of about 25 to 2.5% by weight, preferably 15 to 3% by weight Block copolymers, where the block copolymers contain a, w-bishydroxyaryloxy end groups and are prepared starting from polydiorganosiloxanes having a degree of polymerization _Pn of 5 to 100, preferably 20 to 80. .

The polydiorganosiloxane-polycarbonate block polymer can also be a mixture of a conventional polydiorganosiloxane-polycarbonate block copolymer and a conventional polysiloxane-free thermoplastic polycarbonate, wherein the polydiorganosiloxane in this mixture is used. Total content of structural units is about 2.5-2
5% by weight.

Polydiorganosiloxane-polycarbonate block copolymers such as these comprise polydiorganosiloxanes which initially contain aromatic carbonate structural units (1) in their polymer chains and secondly have aryloxy end groups. It is characterized by containing 2).

[0038]

Embedded image

Wherein Ar is the same or different aryl group from diphenol, R and R ¹ are the same or different and are linear alkyl, branched alkyl, alkenyl,
Represents a halogenated linear alkyl, a halogenated branched alkyl, an aryl or an aryl halide, preferably represents methyl, and the number of diorganosiloxy units n = a
+ B + c = 5 to 100, preferably 20 to 80.

In the above formula (2), alkyl represents, for example, C ₁ -C ₂₀ alkyl, alkenyl in the above formula (2) represents, for example, C ₂ -C ₆ alkenyl; aryl in the above formula (2) Represents C ₆ -C ₁₄ aryl. The expression "halogenated" in the above formula means partially or completely chlorinated, fluorinated or brominated.

Examples of alkyl, alkenyl, aryl, alkyl halide and aryl halide include methyl,
Ethyl, propyl, n-butyl, tert. -Butyl,
Includes vinyl, phenyl, naphthyl, chloromethyl, perfluorobutyl, perfluorooctyl and chlorophenyl.

Polydiorganosiloxane-polycarbonate block copolymers of this type are described, for example, in US-PS
3 189 662, US-PS 3 821 325
And U.S. Pat. No. 3,382,419.

Preferred polydiorganosiloxane-polycarbonate block copolymers are those of a di-organosiloxane containing a, w-bishydroxyaryloxy end groups and other diphenols optionally used in combination with conventional amounts of branching agents. For example, by a reaction according to the two-phase boundary method (in this connection,
H. Schnell, Chemistry and P
physics of Polycarbonates, P
polymer Rev. Vol. IX, p. 27 or less; I
nterscience Publishers Ne
w York 1964), where the proportions of the bifunctional phenolic reactants are chosen in each case such that the content according to the invention of aromatic carbonate structural units and diorganosiloxy units results therefrom. .

Polydiorganosilanes of this type containing a, w-bishydroxyaryloxy end groups are known, for example, from US Pat. No. 3,419,634.

ABS graft polymers in the sense of the present invention include: 1) 5 to 95, preferably 30 to 80 parts by weight of A. 1.1) 50 to 95 parts by weight of styrene, a- methylstyrene, halogen - or methyl - styrenes including substituted nucleus, C ₁ -C ₈ alkyl methacrylates, in particular methyl methacrylate, C ₁ -C ₈ alkyl acrylate, in particular methyl Acrylates or mixtures of these compounds; 1.2) 5 to 50 parts by weight of acrylonitrile, methyl acrylonitrile, C ₁ -C ₈ alkyl methacrylates, in particular methyl methacrylate, C ₁ -C ₈ alkyl acrylate, in particular methyl acrylate, maleic anhydride,
A mixture of C ₁ -C ₄ alkyl- or phenyl-N-substituted maleimides, or a mixture of these compounds, was prepared according to 2) 5 to 95, preferably 20 to 70 parts by weight of butadiene, polybutadiene or butadiene / styrene copolymer having a glass transition temperature of less than 10C.

Graft polymers such as these are, for example, DE-OS 2 035 390 (= US-PS 3
644 574) or DE-OS 2 248 242
(= GB-PS 1 409 275).

As is known, in a grafting reaction, a copolymer is formed from the grafted monomer because the grafted monomer is not exactly and completely grafted onto the graft base. The term "ABS graft polymer" should be understood to include these copolymers.

The average particle size d ₅₀ of the ABS graft polymer is generally 0.5 to 5 nm, preferably 0.1 to 2 nm. The average particle size d ₅₀ is above and below 5
0% by weight is the particle size present. It can be determined using ultracentrifugation measurements (W. Scholtan,
H. Lange, Kolloid, Z .; Polymer
e 250 (1972), 782-796).

The polyolefins are polyethylene, polypropylene, poly-1-butene and polymethylpentene, which may also contain small amounts of non-conjugated dienes which have been polymerized. These polymers are known and are disclosed in Roempp's Chemielexikon,
8th Edition 1987, Volume
5, page 3307 and the references cited therein. Polypropylene is preferred.

In the thermoplastic polyamide molding composition, an aliphatic polyamide or a polyamide having a predominantly aliphatic content is generally used as the polyamide. Preferred polyamides are polyamide 6 or polyamide 66, or polyamide 6 and a diamine (preferably C ₄ -C ₁₆
-, in particular C ₄ -C ₈ - alkylene - diamine) and dicarboxylic acids (preferably C ₄ -C ₁₂ -, in particular C ₄ -C ₈ - alkylene - copolyamides of the dicarboxylic acid), or at most is comonomer content 20% by weight of polyamide 66
It is.

Component B Both organic and inorganic pigments and / or dyes are suitable as pigments. Optionally, carbon black or graphite can also be added. Pigments / pigments and / or carbon black and graphite can optionally be used as batches.

Examples of inorganic pigments which can be used as additive materials for coloring include 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 Prussian blue, lead chromate, lead sulfochromate, chromium antimony titanate, chromium oxide, iron oxide, cobalt blue, cobalt chrome blue, Cobalt nickel gray, manganese blue, manganese violet, molybdate red,
Nickel antimony titanate, ultramarine blue,
And metal sulfides such as arsenic disulfide, antimony trisulfide, cadmium sulfide, cadmium sulfoselenide, and zirconium silicates such as zirconium vanadium blue or zirconium praseodymium yellow.

Examples of the organic pigment used as an additive material for coloring include anthraquinone, azo, izometin, benzanthrone, quinacridone, quinophthalone,
Metal complexes of dioxazine, flavanthrone, indanthrone, isoindoline, isoindolinone, methine, perinone, perylene, phthalocyanine, pyranthrone, pyrrolopyrrole or thioindigo pigments, and metal complexes of azo, azomethine or methine dyes, including metal salts of azo compounds It is.

Examples of suitable polymer-soluble dyes include disperse dyes, for example dyes of the anthraquinone series, such as alkylamino, amino, arylamino, cyclohexylamino, hydroxy, hydroxyamino or phenylmercaptoanthraquinone, and metal azo dyes. Complexes, in particular 1: 2 chromium or cobalt complexes of monoazo dyes, and also fluorescent dyes, for example dyes of the benzthiazole, coumarin, oxaline or thiazine series, are included.

The polymer-soluble dyes are preferably used in combination with fillers and / or pigments, especially with inorganic pigments such as titanium dioxide.

The pigments or polymer-soluble dyes can be used with or without the pigments according to the invention. In this case, it must only be ensured that they are compatible with the thermoplastic polymers used according to the invention and that they do not impair their mechanical or other properties.

Examples of suitable pigment additives include fatty acids having at least 12 carbon atoms, such as behenic acid or stearic acid, or amides, salts or esters thereof, such as aluminum stearate, magnesium stearate, zinc stearate or behenate. magnesium acid, and quaternary ammonium compounds, such as tri - (C ₁ -C ₄₎ - alkyl benzyl ammonium salts, waxes such as polyethylene waxes, resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin, C _{12- C18} paraffin-disulfonic acids or alkyl phenols are included.

According to the invention, preference is given to inorganic pigments, in particular metal-containing pigments such as titanium dioxide and metal complexes of azo, azomethine or methine dyes.

Also preferred pigments are anthraquinone,
Azo, azomethine, quinacridone, dioxazine, isoindoline, isoindolinone, methine, perylene, phthalocyanine, pyrrolopyrrole or thioindigo pigments are included.

Metal-containing inorganic pigments such as phthalocyanine-metal complexes, copper-phthalocyanines, monoazo-
1: 2-Chromium complexes, azo-metal complexes and bismuth vanadate are particularly preferred.

The pigment carbon black and titanium dioxide are also particularly preferred.

Component C Glass fibers, glass spheres, mica, silicates, quartz, French chalk, titanium dioxide, wollastonite, etc. can be used as fillers and reinforcements; these must be surface-treated. Can also. Preferred reinforcements are commercially available glass fibers. Generally 8-14m
Glass fibers having a fiber diameter of m can be used as continuous fibers or as chopped or milled glass fibers, and the fibers can be treated with a suitable sizing system and with a silane-based fixer or fixer system. It is preferred to add from 8 to 45, especially from 10 to 40, parts by weight of fillers and reinforcements to the mixture.

Commercially available organic or halogenated compounds having a component D synergist, or commercially available organic nitrogen compounds or organic / inorganic phosphorus compounds are suitable as flame retardants. Inorganic flame retardants such as Mg hydroxide or hydrated Ca-Mg carbonate can also be used.

The molding composition according to the invention comprises up to 20, preferably 3 to 18, in particular 6 to 15 parts by weight of halogenated compound and up to 8, preferably 2 to 6 parts by weight of antimony compound, in particular antimony trioxide. Alternatively, it can contain antimony pentoxide.

The following compounds are mentioned as examples of halogen-containing organic compounds, in particular brominated and chlorinated organic compounds: ethylene-1,2-bis-tetrabromophthalimide, epoxidized tetrabromobisphenol A resin,
Tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, pentabromopolyacrylate, brominated polystyrene.

Poly (pentabromobenzyl acrylate) generally has an average molecular weight M _w (weight average) of 10,000 to 200,000; brominated polystyrene generally has an average molecular weight of 10,000 to 500,000.

It is preferred to use epoxidized tetrabromobisphenol A and tetrabromobisphenol A oligocarbonate.

The epoxidized tetrabromobisphenol A has a molecular weight of about 350-2100, preferably 360-200.
1,000, most preferably 370 to 400, known diepoxide resins, consisting essentially of at least one condensation product of bisphenol A and epihalohydrin;

[0069]

Embedded image

Wherein X represents hydrogen or bromine, and n represents 0
~ Average number less than 2.3] (see e.g. EP-A 180 471).

Tetrabromobisphenol A oligocarbonate or tetrachlorobisphenol A oligocarbonate is represented by formula (II), wherein the oligomer is phenol or tribromophenol or trichlorophenol terminated:

[0072]

Embedded image

Where R =

[0074]

Embedded image

Wherein X represents hydrogen, bromine or chlorine;
n is an average number of 4 to 7.

Tetrabromo (chloro) bisphenol A
Oligocarbonates are known and can be produced by known methods.

EP-A 345 522 (US-PS
061, 745) or DE-OS 43 28 656.
According to No. 9, the amounts of phosphorus compounds described there, such as triphenyl phosphate, oligomeric phosphate, resorcinol diphosphate or mixtures thereof, are suitable as organic phosphorus compounds.

Component E Suitable elastomer modifiers include commercially available EP
(D) M rubbers, graft rubbers based on butadiene, styrene and acrylonitrile (see, for example, ABS graft polymers above), acrylate rubbers, thermoplastic polyurethanes, or with or without functional coupling groups EVA copolymers are included.

Component F Antimony trioxide is generally known and includes, for example, Campi
commercially available from Ne.

The molding composition of the present invention may contain usual additives such as a releasing and removing agent, a nucleating agent, an antistatic agent and a stabilizer.

The molding compositions according to the invention, which comprise the respective components and, if appropriate, other known additives, such as stabilizers, demolding and demolding agents, reinforcing agents, nucleating agents and antistatic agents, comprise the respective components. Is mixed with the thermoplastic polymer in a known manner, optionally in the form of a masterbatch,
At an internal kneader, extruder or 2
-Can be produced by compounding or extruding the melt in a conventional device such as a shaft endless screw device. The resulting material is then converted to 2 using known methods.
-Or multi-component injection molding to the desired final form.

The resulting material may optionally be processed by injection molding to form a molded article, in which case it must be ensured that at least two differently colored thermoplastic molded articles are not homogeneously mixed. .

The two- or multi-color thermoplastic moldings obtained in this way can be provided in accordance with the invention with what is preferably a laminated lacquer, wherein the lacquer is marked by laser engraving. It is removed at the location, thereby creating various colors of the background that show a high contrast to the lacquer coat.

As lacquer resins for the process according to the invention, use can be made, for example, of saturated and unsaturated polyesters. Alkyd resins are examples of suitable saturated polyesters, and maleic resins are examples of suitable unsaturated polyesters.

The high molecular weight organic materials in dissolved form can also be used for the process according to the invention as film-forming agents or as binder vehicles for lacquers or printing inks.

Thus, for example, acrylic resins, alkyd resins, urea-formamide resins, melamine resins, boiled linseed oil, nitrocellulose or phenol resins can be used.

For the process according to the invention, 2- or poly-
A suitable colored film can also be overlaid on the color thermoplastic molding, where the film is removed at the location marked by laser engraving, thereby providing a high contrast to the film layer (background) on the lower background. Various colors are created.

A high-energy source such as a laser is used for imprinting the thermoplastic molding. In the course of this method, the energetic radiation is directed and possibly focused corresponding to the shape of the symbol to be applied to the surface of the material to be marked, so as to give a coloring effect at the illuminated location .

Examples of such sources are solid state pulsed lasers, such as ruby lasers or frequency-multiplexed (fre
quency-multiplied Nd: YAG lasers, the pulsed lasers being pulsed dye lasers or Raman shifters, and also pulse modified (pu)
1se modification) (Q-switch,
Continuous-wave lasers with a mode locker, such as a frequency multiplexer
rs) based on CW Nd: YAG lasers or CW ion lasers (Ar, Kr), as well as pulsed metal vapor lasers, such as Cu or Au vapor lasers or, if necessary, such as high-power pulsed semiconductor lasers. The device is also included.

Depending on the laser system used, pulse energies up to a few joules, energy densities up to 4 watts per cm ² , pulse widths up to a few femtoseconds and repetition rates up to 1 gigahertz are possible. The advantageous performance parameters that are used, 1 microjoule-Joules pulse energy, 1 cm energy density of ² per one kilowatt 1 cm ² per 100 MW, microseconds to picoseconds pulse width and 1 Hz to 2
Repetition rate of 50 MHz.

It is preferable to use a laser containing pulsed light. Pulse or pulse-modify, frequency-duplex (fre
Q-doubled Nd-YAG laser or metal vapor laser, such as Au- or especially Cu
Steam lasers are particularly preferred.

A laser whose parameters, such as the pulse energy, for example, can be adjusted to a high degree with the duration of action, allows an optimal adaptation to the requirements of the material to be imprinted.

There are three methods for laser engraving: the mask method, the linear engraving and the dot-matrix method. In the case of the last two types of imprints (dynamic beam guidance),
The laser is combined with a laser engraving system such that any desired figure, letter and special symbol, such as programmed into a computer, can be imprinted on the high molecular weight organic material at the point of incidence of the laser beam. preferable.

The choice of the laser system with regard to its power and repetition rate basically depends on the marking method to be used. For mask exposure, it is preferable to use high power and low repetition rates as obtained from a solid state pulsed laser. For imprints requiring dynamic beam guidance, it is preferable to use medium to low power and fast repetition rates obtained from pulsed metal vapor lasers or from continuous wave lasers with pulse correction. For example, an electroreflector (elect
tro-reflectors) or a polygon scanner (polygon scanners).
Beam variation optically or holographically
Deviation) can be performed. Dynamic beam guidance allows imprinting or marking that can be performed very flexibly, since the symbols can be created electronically.

A wide variety of types of inscriptions can be obtained with the method of the invention. Examples include: variable text programming of numbers by text entry using a VDU terminal, standard or special symbols such as frequently repeated characteristic names, publisher symbols or data test programs, sequential part numbering, Includes input of measured variables, input of stored programs, linear imprints, or even decoration.

The method according to the invention makes it possible to use laser beams to mark pieces, sheets, tubes and sections, keys on keyboards, and plastic-clad electronic components.

Typical examples of applications include circuits, printed circuit boards, printed circuits, active and dynamic electronic components, encapsulated high-voltage transformers, socket outlets, casings, precision engineering And mechanical parts, vehicle parts, keyboards, electronic parts, cables, pipes, lacquers, wrapping films, and the imprints of bank notes and securities from the watchmaking industry.

The method according to the invention makes it possible to give marks which are not soilable and therefore resistant to abrasion and scratches. Furthermore, the marks obtained according to the invention are corrosion-resistant, dimensionally stable, not subject to deformation, light-resistant, heat-resistant and weather-resistant; they read well in clean edge zones. be able to. Furthermore, the mechanical and physical properties of the material imprinted in this way are not actually impaired. The depth of penetration of the mark depends on the material to be imprinted. It is about 1mm
Range. Thereby, the high molecular weight organic material is very strongly protected. Inscriptions are thus possible that do not cause a noticeable loss of surface gloss.

The method of the present invention results in a color transition with significant contrast at the illuminated location of the material.

[0100]

EXAMPLES Example 1 Granular material 1 0.006 parts by weight of Bayertitan rutile KB2
(Titanium dioxide, BAYER AG), 0.006 parts by weight of Printex 300 (pigment carbon black,
Degussa AG) and 0.012 parts by weight of Hel
iogenblau K 6911 D (copper phthalocyanine, BASF AG) was added to 97.976 parts by weight of Du.
retan B 31 SK (polyamide, BAYE
RAG) and a formulation containing 2.00 parts by weight of stabilizer and nucleating agent, followed by compounding using an extruder.

Granular material 2 0.006 parts by weight of Bayertitan rutile KB2
(Titanium dioxide, BAYER AG), 0.006 parts by weight of Printex 300 (pigment carbon black,
Degussa AG) and 0.012 parts by weight of Hel
iogenguen K 8730 (phthalocyanine-
Metal complex, BASF AG), was mixed with 97.976 parts by weight of Durethane B 31 SK (polyamide, BA
YER AG) and a formulation containing 2.00 parts by weight of stabilizer and nucleating agent, and were subsequently compounded using an extruder.

The granular materials 1 and 2 were prepared under the usual manufacturing conditions described in the text in a two-component Engel injection molding machine using known injection molding methods at a material temperature of 260 ° C. It was processed by injection molding to form a molded product.

Example 2 Granular material 3 0.006 parts by weight of Bayertitan rutile KB2
(Titanium dioxide, BAYER AG), 0.006 parts by weight of Printex 300 (pigment carbon black,
Degussa AG) and 0.012 parts by weight of Fil
amidgelb R (monoazo-1: 2-chromium complex, Ciba Geigy GmbH) was converted to 97.97.
It was physically mixed with a formulation comprising 6 parts by weight of Durthan B 31 SK (polyamide, BAYER AG) and 2.00 parts by weight of stabilizer and nucleating agent, and subsequently compounded using an extruder.

Granular material 4 0.006 parts by weight of Bayertitan rutile KB2
(Titanium dioxide, BAYER AG), 0.006 parts by weight of Printex 300 (pigment carbon black,
Degussa AG) and 0.012 parts by weight of Ora
sol-Orange 8730 (azo-metal complex, C
iba Geigy GmbH) was combined with 97.976 parts by weight of Durethane B 31 SK (polyamide,
BAYER AG) and a formulation containing 2.00 parts by weight of stabilizer and nucleating agent, and subsequently compounded using an extruder.

The granular materials 3 and 4 were processed by two-component injection molding according to the data in Example 1 to form molded articles.

Example 3 Granular materials 1 and 4 were processed by two-component injection molding according to the data in Example 1 to form molded articles.

Example 4 Granular material 5 0.006 parts by weight of Bayertitan rutile KB2
(Titanium dioxide, BAYER AG), 0.006 parts by weight of Printex 300 (pigment carbon black,
Degussa AG) and 0.012 parts by weight of Irg
colorgelb 2GTM (bismuth vanadate, Ciba Geigy GmbH) was added to 97.97.
It was physically mixed with a formulation comprising 6 parts by weight of Durthan B 31 SK (polyamide, BAYER AG) and 2.00 parts by weight of stabilizer and nucleating agent, and subsequently compounded using an extruder.

The granulated materials 1 and 5 were processed by two-component injection molding according to the data in Example 1 to form molded articles.

Example 5 Granular materials 2 and 5 were processed by two-component injection molding according to the data in Example 1 to form molded articles.

EXAMPLE 6 Granular materials 3 and 5 were processed by two-component injection molding according to the data in Example 1 to form molded articles.

Example 7 Granular materials 4 and 5 were processed by two-component injection molding according to the data in Example 1 to form molded articles.

The molded product was produced at a material temperature of 260 ° C. using a known injection molding method in a two-component Engel injection molding machine.

[0113]

[Table 1]

Example 8 Granular materials 1 and 2 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

Example 9 Granular materials 3 and 4 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

Example 10 Granular materials 1 and 4 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

EXAMPLE 11 Granular materials 1 and 5 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

Example 12 Granular materials 2 and 5 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

[0119] The molded product is obtained by a Lauffer press.
It was manufactured using a known pressing method.

[0120]

[Table 2]

Example 13 Granular materials 3 and 5 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

EXAMPLE 14 Granular materials 4 and 5 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

Example 15 Granular material 6 0.1 part by weight of Printex 300 (pigmented carbon black, supplied by Degussa) was charged with 97.9 parts by weight of Durethane B 31 SK (polyamide, BAYERAG) and 2.0 parts by weight Was physically mixed with a formulation containing the following stabilizers and nucleating agents and subsequently compounded using an extruder.

The granular materials 1 and 6 are subjected to pressure and about 220
It was pressed under the action of a temperature of ° C. to form a molded article.

Example 16 Granular materials 2 and 6 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

Example 17 Granular materials 3 and 6 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

[0127] The molded product is obtained by a Lauffer press.
It was manufactured using a known pressing method.

[0128]

[Table 3]

Example 18 Granular materials 4 and 6 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

Example 19 Granular materials 1 and 3 and 6 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

Example 20 Granular materials 1, 4 and 6 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

Example 21 Granular materials 1 and 2 and 3 and 6 were subjected to pressure and about 220
It was pressed under the action of a temperature of ° C. to form a molded article.

Example 22 Granular materials 1 and 2 and 3 and 4 and 6 were pressed under the action of pressure and a temperature of about 220 ° C. to form molded articles.

[0134] The molded product is obtained by a Lauffer press.
It was manufactured using a known pressing method.

[0135]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/00 C08L 101/00 // B29K 101: 12

Claims (7)

[Claims] 1. A molded article which is at least 2-colored at the laser-marked position after laser-engraving,
Use of at least two differently colored thermoplastic molding compositions for the production by -or multi-component injection molding or by hot pressing. 2. The method according to claim 1, wherein the molding composition is used in the form of its granular material. 3. Polyalkylene terephthalate, aromatic polyester, polyamide, polycarbonate, polyacrylate, polymethacrylate, ABS graft polymer, polyolefins such as polyethylene or polypropylene, polystyrene, polyvinyl chloride, polyoxymethylene, polyimide, polyether and 2. The process according to claim 1, wherein polymers or copolymers based on polyetherketone are used, alone or as a blend of different polymers. 4. An organic and / or inorganic pigment and / or dye is added as a pigment, and optionally carbon black and / or dye.
Or the method of claim 1, wherein graphite is added. 5. The method according to claim 1, wherein the thermoplastic molding is provided with a lacquer or a film. 6. The two or more differently colored thermoplastic granules produced by two- or multi-component injection molding of at least two differently colored granular materials according to claim 1. A method for the production of a molded article in which the shaped materials are separately processed directly in a two- or multi-component injection molding machine to form a molded article. 7. The hot pressing of at least two differently colored granular materials according to claim 1,
First, they are mechanically mixed, they are subsequently introduced into a mold and heated to bring the thermoplastic molding composition almost into a molten state, and these mixed granular materials are brought to their final state under the action of pressure. A method for the production of molded articles that are pressed into shapes.