DE10054859A1 - Process for joining molded parts - Google Patents

Abstract

The invention relates to a method for connecting a moulded part (I) consisting of a thermoplastic polymer A containing colouring agents to a moulded part (II) consisting of a thermoplastic polymer B containing colouring agents by means of laser radiation. According to said method, 1) the laser radiation passes through moulded part (I) at the point to be connected and strikes moulded part (II), 2) moulded part (I) contains at least one colouring agent which absorbs selectively in the visible range of the electromagnetic spectrum, 3) the colouring agents contained in moulded part (I) and the concentrations thereof are chosen in such a way that moulded part (I) is permeable to laser radiation at the point to be connected, 4) the colouring agents contained in moulded part (II) and the concentrations thereof are chosen in such a way that moulded part (II) absorbs the laser radiation at the point to be connected and 5) the colouring agents contained in the two moulded parts (I) and (II) and the proportions thereof are chosen in such a way that moulded parts (I) and (II) are perceived by the human eye as having essentially the same colour.

Description

The invention relates to a method for connecting a molded part I made of a colorant-containing thermoplastic polymer A with a molded part II made of a colorant-containing thermoplastic polymer B by laser radiation, in which

• 1. the laser radiation at the point to be connected through the Molding I passes through and meets the molding II,
• 2. the molded part I contains at least one colorant which is im selectively visible part of the electromagnetic spectrum absorbed,
• 3. the colorants contained in the molding I and their concentration functions are selected such that the molded part I at the to connecting point for the laser radiation is permeable,
• 4. the colorants contained in the molding II and their con centrations are selected such that the molded part II to the point to be connected absorbs the laser radiation,
• 5. the colorants contained in both moldings I and II and their proportions are selected so that the shape share I and II essentially one for the human eye have the same color impression.

The invention also relates to the use of this method for the production of composite moldings III, the up builds are made up of two or more individual molded parts I and II, and finally assembled molded parts III, which are built up from two or more individual molded parts I and II, obtainable according to the procedure mentioned.

Plastic molded parts, z. B. those with complex or demanding geometry several individual molded parts (also called joining parts) together set, whereby the individual molded parts by various Ver driving, including also welding, can be joined together. Examples of plastic welding processes are the heating element welding, vibration welding, rotational friction welding, ultra sonic welding, high frequency welding and laser beam welding.

The invention relates to laser beam welding according to the principle transmission welding (also called lap welding). The welding process is based on the absorption of laser radiation the place to be connected and the formation of a locally limited Melt. Choosing a suitable combination of materials is important Basic requirement for transmission welding: The first joint part (molded part I within the meaning of the invention) is for the laser beam treatment permeable (transmissive, laser-transparent) due to the small absorption constant. It absorbs the laser radiation so not or only to a minor extent. The second join part (molded part II within the meaning of the invention) is due to the high Absorption constant impermeable or only slightly permeable to the laser radiation and absorbs it (laser-absorbing). the The absorption constant of the parts to be joined depends on the type and waves length of the laser radiation used usually by adding from additives, such as colorants, to the polymer from which the respective part to be joined is set. These additives absorb ren the laser radiation.

In the case of transmission welding, the parts to be joined are usually in contact the point to be connected, the later weld seam who or are otherwise in contact with each other; it is also a small gap (mostly in the µm range) possible. The lasers Radiation is directed onto the first part to be joined and penetrates it unhindered or almost unhindered and meets the second joint part on. There the laser radiation is absorbed and converted into heat converted. With increasing energy input from the laser beam ment becomes the second part to be joined in the area of the absorption volume heated and melted with volume expansion. The bil The melt leads to intimate contact and heat transition between the two parts to be joined. Through this heat conduction the laser-transparent first joining part is also heated and melted under volume expansion. By mixing the Melting (diffusion processes and change of place processes in the Melting) occurs after cooling and solidification of the melt zen a permanently firm and tight connection of both parts to be joined, the weld.

D. Hänsch et al., Kunststoffe 88 (1998), 210-212 describes this Welding of thermoplastic elastomers (TPE) with thermo plastics such as polyamide, polyolefins, polyesters and styrene copoly using a diode laser. More information about additives or coloring agents are not made by Hänsch.

H. Potente et al., Plastverarbeiter 46 (1995) No. 10, 58-64 be writes the transmission method in general form and he suggests that PA6, POM, PP and PMMA are suitable. Potent power no information on additives or colorants.

DE-A 14 79 239 discloses a method for connecting Fo lien made of thermoplastics by laser or other electromagnetic radiation and is named as an absorbing additive generally dyes or color pigments and especially carbon black.

EP-A 126 787 teaches a method for butt seam welding _{of plastic foils and mentions SiO 2} , TiO _{2 , CaCO 3} , Al ₂ O ₃ and carbon black in amounts of 1% by weight each as absorbent additives.

DE-A 195 42 328 discloses a method for producing Bodies made of layers or fo lien and names PE, SB / PS and Plexiglas as transparent joining parts as well as black colored PE as absorbent joining parts, black colored ABS and black colored PS. Absorbance rend additives are not mentioned.

EP-A 159 169 teaches a method for joining two pieces of art material parts by means of transmission laser welding. As a transparent one Plastics are PP, PA6, PA66 and SAN, all each without starting sorbent additives, called. As absorbent plastics who called the PP and SAN, which contain an absorbent additive, in particular 0.1% by weight of carbon black.

DE-A 198 14 298 discloses a method for producing a plastic fuel tank in which at least two part bodies are welded by means of laser radiation. A Teilkör is laser-transparent and the other is laser-absorbing by adding fillers such as carbon black or SiO ₂ .

The methods described have the disadvantage that the finished, welded workpiece from two or more parts with difference lighter color. The visual impression of the finished work piece is therefore inhomogeneous in color. This is mostly un desires, since the consumer is more aesthetically pleasing, monochromatic Plastic items preferred.

DE-A 195 10 493 describes a workpiece, which by Ver welding two workpiece parts made of thermoplastic material how SAN or PA is produced using laser radiation. Included the absorption coefficient of the workpiece parts is given by the An partly adjusted to additives such as glass fibers or color pigments. The laser-absorbing workpiece contains 1-2% by weight of dyes.

So that the reflectivity of the two workpiece parts for the Spek spectrum of visible light is essentially the same (thus both parts have a similar or the same color), contains the laser-transparent workpiece a "lower pigmentation", ie a lesser amount of the same dye, nothing to the amount it is said. The only color pigments used are “black color Substance pigments "called, so colorants that the entire view absorb the range of the electromagnetic spectrum.

This approach has the disadvantage that large amounts of soot or whose absorbent black additives must be added in order to to make one workpiece laser-absorbent. High additive con centrations often make the workpiece more expensive and are problematic when incorporated into the polymer and deteriorate in many Cases the mechanical and other performance characteristics of the Workpiece. In addition, only black and not colored Manufacture (colored) workpieces.

The task was to remedy the disadvantages outlined. In particular, the object was to provide a method for connecting Provide molded parts by laser radiation, in which only ge A small amount of colorant can be used. Besides, that should finished, composite molding no significant color underlay show differences, d. H. the individual molded parts that make it up The set-up molded part should be roughly the same color be. Accordingly, the method with low colorant con centrations and still come together homogeneously in terms of color set moldings result.

In addition, colored (colored, so not black) composite molded parts read sen.

We have found that this object is achieved by the process defined at the outset. White thereafter have been using this method of manufacture of composite molded parts III, which are composed of two or more individual moldings I and II, and finally together set molded parts III, which are composed of two or more individual molded parts I and II, obtainable according to the above-mentioned Ver drive, found.

A molded part within the meaning of the invention is, for example, an injection molding molded part or a deep-drawn molded part, and includes foils, Semi-finished products (sheets, tubes, plates, rods, etc.). Are z. B. two or more foils with the method according to the invention connected to one another, then the process product, namely that together Mixed molded part, a multilayer film.

i) Polymers A and B

The individual molded parts I are made of thermoplastic polymers A, and the individual molded parts II made of thermoplastic polymers B, built up.

All thermoplastic polymers can be used as polymers A or B Consideration. Such polymers are used, for example, in plastics Paperback, Ed. Saechtling, 25th edition, Hanser-Verlag Munich 1992, especially chap. 4, and in the Kunststoff-Handbuch, ed. G. Becker and D. Braun, volumes 1 to 11, Hanser-Verlag Munich 1966-1996. In Saechtling's plastic paperback are also called sources of supply.

The polymers A and B can be identical or different. After Some preferred polymers A and B are shown below purifies.

1. Polyoxymethylene homo- or copolymers (polyoxymethylene, POM)

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

Quite generally, these polymers have at least 50 mol% of recurring —CH ₂ O— units in the main polymer chain. The homopolymers are generally prepared by polymerizing formaldehyde or trioxane, preferably in the presence of suitable catalysts.

In the context of the invention, polyoxymethylene copolymers are given before given, in particular those which, in addition to the recurring units -CH ₂ O-, have up to 50, preferably 0.1 to 20 and in particular 0.3 to 10 mol% of recurring units

contain, where R ¹ to R ^{4 are} independently a hydrogen atom, a C ₁ - to C ₄ alkyl group or a halogen-substituted alkyl group with 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 methyl groups or a corresponding oxymethylene group and n has a value in the range from 0 to 3. These groups can advantageously be introduced into the copolymers by ring opening of cyclic ethers. Preferred cyclic ethers are those of the formula

where R ¹ to R ⁵ and n have the meaning given above. Ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane and 1,3-dioxepane as cyclic ethers and linear oligo- or may be mentioned only as examples Polyformals such as polydioxolane or polydioxepane are called comonomers.

Also suitable are oxymethylene terpolymers which are prepared, for example, by reacting trioxane, one of the cyclic ethers described above, with a third monomer, preferably a bifunctional compound of the formula

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

Preferred monomers of this type are ethylene diglycid and diglycidyl ethers and diethers from glycidyls and formaldehyde, dioxane or Trioxane in a molar ratio of 2: 1 and diether from 2 mol glycidyl compound and 1 mol of an aliphatic diol with 2 to 8 C- Atoms such as the diglycidyl ethers of ethylene glycol, 1,4-butanediol, 1,3-butanediol, cyclobutane-1,3-diol, 1,2-propanediol and cyclohexane-1,4-diol, to name just a few examples.

Process for the preparation of the above-described homo- and Copolymers are known to the person skilled in the art and be in the literature so that further details are not necessary here.

The preferred polyoxymethylene copolymers have melting points of at least 150 ° C and molecular weights (weight average) Mw im Range from 5,000 to 200,000, preferably from 7,000 to 150,000.

End group-stabilized polyoxymethylene polymers which are attached to the Chain ends having C-C bonds are particularly preferred.

2. Polycarbonate (PC) and polyester

Suitable polycarbonates are known per se. You are e.g. B. ent speaking the method of DE-B-13 00 266 through interfaces polycondensation or according to the method of DE-A-14 95 730 obtainable by reacting biphenyl carbonate with bisphenols. The preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, in general common - as also in the following - referred to as bisphenol A.

Instead of bisphenol A, other aromatic dihy Hydroxy compounds are used, in particular 2,2-di (4-hydro xyphenyl) pentane, 2,6-dihydroxynapthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sul fit, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane or 4,4-dihydroxydiphenyl and mixtures of the aforementioned Dihydroxy compounds.

Particularly preferred polycarbonates are those based on Bisphenol A or bisphenol A together with up to 30 mol% of the the aforesaid aromatic dihydroxy compounds.

The relative viscosity of these polycarbonates is in general in the range from 1.1 to 1.5, in particular 1.28 to 1.4 (measured at 25 ° C in a 0.5 wt .-% solution in dichloromethane).

Suitable polyesters are also known per se and are described in the literature. They contain an aromatic ring in the main chain, which is derived from an aromatic dicarboxylic acid. The aromatic ring can also be substituted, e.g. B. by halogen such as chlorine and bromine or by C ₁ -C ₄ alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or tert-butyl groups.

The polyesters can be made by reacting aromatic dicarbon acids, their esters or other ester-forming derivatives of the same ben with aliphatic dihydroxy compounds in known per se Way to be made.

Preferred dicarboxylic acids are naphthalenedicarboxylic acid, Terephthalic acid and isophthalic acid or mixtures thereof to name. Up to 10 mol% of the aromatic dicarboxylic acids can by aliphatic or cycloaliphatic dicarboxylic acids such as Adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and Cyclohexanedicarboxylic acids are replaced.

Of the aliphatic dihydroxy compounds, diols with 2 up to 6 carbon atoms, in particular 1,2-ethanediol, 1,4-butane diol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, and neo pentyl glycol or mixtures thereof are preferred.

Particularly preferred polyesters are polyalkylene terephthalates, which are derived from alkanediols with 2 to 6 carbon atoms, to NEN nen. Of these, polyethylene terephthalate in particular is used (PET), polyethylene naphthalate and polybutylene terephthalate. (PBT) preferred.

The viscosity number of the polyesters is generally in the range from 60 to 200 ml / g (measured in a 0.5% by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C)).

3. polyolefins

In general, polyethylene and polypropylene and co polymers based on ethylene or propylene, possibly also to mention with higher α-olefins. Corresponding products are un available under the trade names Lupolen® or Novolen®. Under Polyolefins are also said to be ethylene-propylene elastomers and ethylene Propylene terpolymers are understood.

4. Polyacrylates and polymethacrylates

These include, in particular, polymethyl methacrylate (PMMA) as well Copolymers based on methyl methacrylate with up to 40 % By weight of other copolymerizable monomers called, like them for example under the names Lucryl® or Plexiglas® are available.

5. polyamides (PA)

Polyamides with aliphatic, partially crystalline or are suitable partially aromatic as well as amorphous structure of any kind and their Blends including polyether amides such as polyether block amides. For the purposes of the present invention, polyamides should include all known polyamides are understood.

Such polyamides generally have a viscosity number of 90 to 350, preferably 110 to 240 ml / g determined in one 0.5% by weight solution in 96% by weight sulfuric acid at 25 ° C according to ISO 307.

Semi-crystalline or amorphous resins with a molecular weight (Weight average) of at least 5,000, as z. Tie American patents 2,071,250, 2,071,251, 2,130,523, 2 130 948, 2 241 322, 2 312 966, 2 512 606 and 3 393 210 be are preferred. Examples are poly amides derived from lactams with 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, as well Polyamides made by reacting dicarboxylic acids with diamines can be obtained.

As dicarboxylic acids are alkanedicarboxylic acids with 6 to 12, esp special 6 to 10 carbon atoms and aromatic dicarboxylic acids applicable. Here are adipic acid, azelaic acid, sebacic acid, Dodecanedioic acid (= decanedicarboxylic acid) and terephthalic and / or Isophthalic acid called as acids.

Alkanediamines with 6 to 12 ins are particularly suitable as diamines special 6 to 8 carbon atoms and m-xylylenediamine, Di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) methane, 2,2-di- (4-aminophenyl) -propane or 2,2-di- (4-aminocyclohe xyl) propane.

Preferred polyamides are polyhexamethylene adipamide (PA 66) and polyhexamethylene sebacic acid amide (PA 610), polycaprolactam (PA 6) and copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units. PA 6, PA 66 and Co polyamides 6/66 are particularly preferred.

In addition, polyamides should also be mentioned, the z. B. by Condensation of 1,4-diaminobutane with adipic acid under increased Temperature are available (polyamide-4,6). production method for polyamides of this structure are z. B. in EP-A 38 094, EP-A 38 582 and EP-A 39 524 are described.

Other examples are polyamides, which are produced by copolymerization two or more of the aforementioned monomers are available, or mixtures of several polyamides are suitable, the mixture ratio is arbitrary.

Furthermore, such partially aromatic copolyamides as PA 6 / 6T and PA 66 / 6T proved to be particularly advantageous, their Triamine content less than 0.5, preferably less than 0.3% by weight (see EP-A 299 444). The manufacture of the partially aromatic copolyamides with a low triamine content according to the processes described in EP-A 129 195 and 129 196 take place.

The following non-exhaustive list contains the named, as well as other polyamides within the meaning of the invention (the monomers are given in brackets):
PA 46 (tetramethylenediamine, adipic acid)
PA 66 (hexamethylenediamine, adipic acid)
PA 69 (hexamethylenediamine, azelaic acid)
PA 610 (hexamethylenediamine, sebacic acid)
PA 612 (hexamethylenediamine, decanedicarboxylic acid)
PA 613 (hexamethylenediamine, undecanedicarboxylic acid)
PA 1212 (1,12-dodecanediamine, decanedicarboxylic acid)
PA 1313 (1,13-diaminotridecane, undecanedicarboxylic acid)
PA MXD6 (m-xylylenediamine, adipic acid)
PA TMDT (trimethylhexamethylenediamine, terephthalic acid)
PA 4 (pyrrolidone)
PA 6 (ε-caprolactam)
PA 7 (ethanolactam)
PA 8 (caprylic lactam)
PA 9 (9-aminopelargonic acid)
PA 11 (11-aminoundecanoic acid) PA 12 (laurolactam)

These polyamides and their production are known. details the person skilled in the art will find information on their preparation in Ullmanns Encyklopadie der Technischen Chemie, 4th edition, Vol. 19, pp. 39-54, publisher Chemie, Weinheim 1980, and Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21, pp. 179-206, VCH Verlag, Weinheim 1992, and Stoeckhert, Kunststofflexikon, 8th edition, pp. 425-428, Hanser Verlag Munich 1992 (keyword "polyamides" and the following).

On the production of the preferred polyamides PA6, PA 66 and Co polyamide 6/66 is briefly discussed below.

The polymerization or polycondensation of the starting monomers is preferably carried out according to the usual procedures. So the polymerization of caprolactam can, for example, according to the Continuous described in DE-A 14 95 198 and DE-A 25 58 480 formal procedures. The polymerization of AH salt for Production of PA 66 can be carried out according to the usual discontinuous Process (see: Polymerization Processes pp. 424-467, esp dere pp. 444-446, Interscience, New York, 1977) or according to one continuous process, e.g. B. in accordance with EP-A 129 196.

Conventional chain regulators can also be used in the polymerization. Suitable chain regulators are, for. B. Triacetondiamine connections (see WO-A 95/28443), monocarboxylic acids such as acetic acid, propionic acid and benzoic acid, and bases such as hexamethylenediamine, benzylamine and 1,4-cyclohexyldiamine. Also C ₄ -C ₁₀ dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid; C ₅ -C ₈ cycloalkanedicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid; Benzene and naphthalenedicarboxylic acids such as isophthalic acid, terephthalic acid and naphthalene-2,6-dicarboxylic acid are suitable as chain regulators.

The polymer melt obtained is discharged from the reactor, cooled and granulated. The granules obtained are subjected to post-polymerization. This is done in a manner known per se by heating the granulate to a temperature T below half the melting temperature T _s or crystallite _{melting temperature T k of} the polyamide. The final molecular weight of the polyamide (measurable as viscosity number VN, see information on VN above) is established by post-polymerization. The post-polymerization usually lasts from 2 to 24 hours, in particular from 12 to 24 hours. When the desired molecular weight has been reached, the granules are cooled in the usual way.

Corresponding polyamides are available under the trade name Ultramid® from BASF available.

6. Vinyl aromatic polymers

The molecular weight of these known per se and in the trade he available polymers is generally in the range of 1,500 to 2,000,000, preferably in the range from 70,000 to 1,000,000.

Vinyl aromatic polymers are only representative here Called styrene, chlorostyrene, α-methylstyrene and p-methylstyrene; in minor proportions (preferably not more than 20, ins not more than 8% by weight), comonomers such as (Meth) acrylonitrile or (meth) acrylic acid ester involved in the structure be. Particularly preferred vinyl aromatic polymers are poly styrene, styrene-acrylonitrile copolymers (SAN) and impact modified Decorated polystyrene (HIPS = High Impact Polystyrene). It understands that mixtures of these polymers can also be used nen. The production is preferably carried out according to the Methods described in EP-A-302 485.

Furthermore, ASA, ABS and AES polymers (ASA = Acrylni tril-styrene-acrylic ester, ABS = acrylonitrile-butadiene-styrene, AES = Acrylonitrile-EPDM-rubber-styrene) is particularly preferred. These impact-resistant vinyl aromatic polymers are detailed below described.

The impact-resistant vinyl aromatic polymers contain at least one rubber-elastic graft polymer A and one thermoplastic polymer B (matrix polymer). Preference is given to using graft polymers A, which are used as rubber

• - A diene rubber based on dienes, such as. B. butadiene or isoprene,
• - An alkyl acrylate rubber based on alkyl esters of Acrylic acid, such as n-butyl acrylate and 2-ethylhexyl acrylate,
• - an EPDM rubber based on ethylene, propylene and a service,

or mixtures of these rubbers or rubber monomers ent keep.

Preferred graft polymers A contain, based on A),

• 1. 30 to 95, preferably 40 to 90 and particularly preferably 40 to 85% by weight of a rubber-elastic basic stage, based on a1)
  • 1. 50 to 100, preferably 60 to 100 and particularly preferably 70 to 100% by weight of a (C ₁ -C ₁₀ -alkyl) ester of acrylic acid,
  • 2. 0 to 10, preferably 0 to 5 and particularly preferably 0 to 2% by weight of a polyfunctional, crosslinking monomer,
  • 3. 0 to 40, preferably 0 to 30 and particularly preferably 0 to 20% by weight of one or more further mono-ethylenically unsaturated monomers,
    or off
  • 4. a11 *) 50 to 100, preferably 60 to 100 and particularly preferably 65 to 100% by weight of a diene with conjugated double bonds,
  • 5. a12 *) 0 to 50, preferably 0 to 40 and particularly preferably 0 to 35% by weight of one or more monoethylenically unsaturated monomers,
    or off
  • 6. a11 **) 50 to 100, preferably 60 to 100 and particularly preferably 65 to 100% by weight of a mixture of ethylene, propylene and a diene,
  • 7. a12 **) 0 to 50, preferably 0 to 40 and particularly preferably 0 to 35 wt .-% of one or more further mono-ethylenically unsaturated monomers,
• 2. 5 to 70, preferably 10 to 60 and particularly preferably 15 to 60% by weight of a graft stage, based on a2),
  • 1. 50 to 100, preferably 60 to 100 and particularly preferably 65 to 100% by weight of a styrene compound of the general formula
    in which R ¹ and R ^{2 are} hydrogen or C ₁ -C ₈ -alkyl,
  • 2. 0 to 40, preferably 0 to 38 and particularly preferably 0 to 35% by weight of acrylonitrile or methacrylonitrile or mixtures thereof,
  • 3. 0 to 40, preferably 0 to 30 and particularly preferably 0 to 20% by weight of one or more further mono-ethylenically unsaturated monomers.

Particularly suitable (C ₁ -C ₁₀ -alkyl) esters of acrylic acid, component a11), are ethyl acrylate, 2-ethylhexyl acrylate and n-butyl acrylate. 2-Ethylhexyl acrylate and n-butyl acrylate are preferred, and n-butyl acrylate is very particularly preferred. It is also possible to use mixtures of different alkyl acrylates which differ in their alkyl radical.

Crosslinking monomers a12) are bifunctional or polyfunctional comono mers with at least two olefinic double bonds, for example wise butadiene and isoprene, divinyl esters of dicarboxylic acids such as of succinic acid and adipic acid, diallyl and divinyl ethers bi functional alcohols such as ethylene glycol and butane 1,4-diols, diesters of acrylic acid and methacrylic acid with the ge named bifunctional alcohols, 1,4-divinylbenzene and Trial lylcyanurate. The acrylic acid esters are particularly preferred Tricyclodecenyl alcohol (see DE-OS 12 60 135), including under the Name dihydrodicyclopentadienyl acrylate is known, as well as the Allyl esters of acrylic acid and methacrylic acid.

Crosslinking monomers a12) can be used in the molding compositions, depending on the type the molding compounds to be produced, in particular depending on the ge desired properties of the molding compositions, or not. If crosslinking monomers a12) are contained in the molding compositions th, the amounts are 0.01 to 10, preferably 0.3 to 8 and particularly preferably 1 to 5% by weight, based on a1).

The other monoethylenically unsaturated monomers a13) which can be contained in the graft core a1) at the expense of the monomers a11) and a12) are, for example:
vinyl aromatic monomers such as styrene, styrene derivatives of the general formula

in which R ¹ and R ^{2 are} hydrogen or C ₁ - to C ₈ -alkyl;
Acrylonitrile, methacrylonitrile;
C ₁ - to C ₄ -alkyl esters of methacrylic acid such as methyl methacrylate, and also the glycidyl esters, glycidyl acrylate and methacrylate;
N-substituted maleimides such as N-methyl, N-phenyl and N-cyclo hexyl maleimide;
Acrylic acid, methacrylic acid, furthermore dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their anhydrides such as maleic anhydride;
Nitrogen-functional monomers such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone, vinyl caprolactam, vinylcarbazole, vinylaniline, acrylamide and methacrylamide;
aromatic and araliphatic esters of acrylic acid and methacrylic acid such as phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate;
unsaturated ethers such as vinyl methyl ether,
and mixtures of these monomers.

Preferred monomers a13) are styrene, acrylonitrile, methyl meth acrylate, glycidyl acrylate and methacrylate, acrylamide and meth acrylamide.

Instead of the basic stage monomers a11) to a13), the basic stage a1) also be built up from the monomers a11 *) and a12 *). Buta are used as dienes with conjugated double bonds, a11 *) diene, isoprene, norbornene, and their halogen-substituted Deri vate, such as chloroprene, into consideration. Butadiene and are preferred Isoprene, especially butadiene.

As further monoethylenically unsaturated monomers a12 *) can the monomers are also used, as they are for the monomers a13) have already been mentioned.

Preferred monomers a12 *) are styrene, acrylonitrile, methyl meth acrylate, glycidyl acrylate and methacrylate, acrylamide and meth acrylamide.

The graft core a1) can also consist of a mixture of the mono mers a11) to a13), and a11 *) to a12 *).

Instead of the basic level monomers a11) to a13) or a11 *) and a12 *) the basic level a1) can also be made from the monomers a11 **) and a12 **). As diene in the monomer mixture a11 **), which is used in a mixture with ethylene and propylene in particular ethylidene norbornene and dicyclopentadiene are suitable.

As further monoethylenically unsaturated monomers a12 **) can the monomers mentioned for a13) are also used.

The graft core can also consist of a mixture of the monomers a11) to a13) and a11 **) to a12 **), or from a mixture of the mono meren a11 *) to a12 *) and a11 **) to a12 **), or from a Mixture of monomers a11) to a13), a11 *) to a12 *) and a11 **) to a12 **).

If the graft core contains the monomers a11) to a13), the result is after mixing with a thermoplastic polymer B) Styrene and acrylonitrile (SAN), so-called ASA molding compounds (Acrylni tril-styrene-alkyl acrylate). If the graft core contains the monomials ren a11 *) to a12 *), after mixing with an ether thermoplastic polymer B) made of styrene and acrylonitrile (SAN) Molding compounds of the ABS type (acrylonitrile-butadiene-styrene). Contains the The graft core is formed by the monomers a11 **) to a12 **) according to Ab mixture with a thermoplastic polymer B) made of styrene and Acrylonitrile (SAN) molding compounds of the AES type (Acrylonitrile-EPDM-Sty rol). In a preferred embodiment it is according to the polymers A to ASA graft polymers or to ABS graft polymers or AES graft polymers, or around Mixed types of ASA, ABS and AES.

Regarding the monomers a21) and a23), please refer to the explanations refer to the components b1) and b3) below. Therefore can the graft shell a2) at the expense of the monomers a21) more Monomers a22), or a23), or mixtures thereof, contain. Be The graft shell a2) is preferably composed of polymers such as see them below as preferred embodiments B / 1 to B / 4 das Matrix polymers B were named.

The preparation of the graft stage a2) can be carried out under the same conditions conditions such as the preparation of the basic level a1) take place, whereby the graft stage a2) in one or more process steps can produce. The monomers a21), a22) and a23) be added individually or in a mixture with one another. The monome The ratio of the mixture can be constant over time or a graph serves to be. Combinations of these procedures are also possible lich. For example, you can start with styrene alone, and then a mixture of styrene and acrylonitrile, on basic level a2) polymerize. The gross composition remains of the mentioned th refinements of the method are unaffected.

Furthermore, graft polymers with several "white" are also suitable chen "and" hard "levels, e.g. of the structure a1) -a2) -a1) -a2) or a2) -a1) -a2), especially in the case of larger particles.

As far as non-grafted polymers from the mono during the grafting meren a2) arise, these quantities, which are usually below 10% by weight of a2) are assigned to the mass of component A.

The preparation of the graft polymers A can be carried out in various ways Way to be carried out, especially in emulsion, in micro emulsion, in miniemulsion, in suspension, in microsuspension, in Minisuspension, as precipitation polymerization, in bulk or in Solution, or as a combination of two methods such. B. Mass / Solution, solution / precipitation, mass / suspension and mass / emulsion. the Processes can be carried out continuously or batchwise are and are known to the person skilled in the art. Details of the named th polymerization process and the necessary auxiliaries such as emulsifiers, initiators, etc. are for example the DE-A 197 52 394 can be found.

Furthermore, the impact-resistant vinyl aromatic polymers contain at least one thermoplastic polymer B (Matrixpolymeri sat). Preferred polymers B are obtained by polymerizing a monomer mixture from, based on B),

• 1. 50 to 100, preferably 60 to 95 and particularly preferably 60 to 90% by weight of a styrene compound of the general formula I
  in which R ¹ and R ^{2 are} hydrogen or C ₁ - to C ₈ -alkyl
  or a (C ₁ -C ₈ -alkyl) ester of acrylic acid or methacrylic acid,
  or mixtures of the styrene compound and the (C ₁ -C ₈ -alkyl) ester of acrylic acid or methacrylic acid,
• 2. 0 to 40, preferably 5 to 38 wt .-% acrylonitrile or Methacrylonitrile or mixtures thereof, and
• 3. 0 to 40, preferably 0 to 30 weight percent of one or more ren further monoethylenically unsaturated, different from b2) those monomers.

Component B preferably has a glass transition temperature T _g of 50 ° C. or above. B is therefore a hard polymer.

The styrene compound of the general formula (I) (component b1)) is preferably styrene, α-methylstyrene and also _{styrenes alkylated in the ring with C 2} -C ₈ -alkyl, such as p-methylstyrene or tert-butylstyrene. Styrene is particularly preferred. It is also possible to use mixtures of the styrenes mentioned, in particular of styrene and α-methylstyrene.

Instead of the styrene compounds or as a mixture with them, C ₁ - to C ₈ -alkyl esters of acrylic acid and / or methacrylic acid come into consideration, especially those which are derived from methanol, ethanol, n- and iso-propanol, sec.-, tert.- and isobutanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol and n-butanol derived. Methyl methacrylate is particularly preferred.

Furthermore, at the expense of monomers b1) and b2), component B can contain one or more further monoethylenically unsaturated monomers b3) which vary the mechanical and thermal properties of B within a certain range. Examples of such comonomers are:
N-substituted maleimides such as N-methyl, N-phenyl and N-cyclo hexyl maleimide;
Acrylic acid, methacrylic acid, furthermore dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their anhydrides such as maleic anhydride;
Nitrogen-functional monomers such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone, vinyl caprolactam, vinylcarbazole, vinylaniline, acrylamide and methacrylamide;
aromatic and araliphatic esters of acrylic acid and meth acrylic acid such as phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate;
unsaturated ethers such as vinyl methyl ether,
and mixtures of these monomers.

Preferred components B are, for example, polystyrene, and the like polymers of styrene and / or α-methylstyrene and one or more reren of the other monomers mentioned under b1) to b3). Before methyl methacrylate, N-phenylmaleimide and maleic are given acid anhydride and acrylonitrile, particularly preferably methyl meth acrylate and acrylonitrile.

Examples of preferred components B include:
B / 1: polystyrene
B / 2: copolymer of styrene and acrylonitrile,
B / 3: Copolymer of a-methylstyrene and acrylonitrile,
B / 4: copolymer of styrene and methyl methacrylate.

The proportion of styrene or α-methyl is particularly preferred styrene, or the proportion of the sum of styrene and α-methylstyrene, at least 40% by weight, based on component B.

If component B preferably contains styrene and acrylonitrile, then so the well-known commercially available SAN copolymers are produced. You ha usually have a viscosity number VZ (determined according to DIN 53 726 at 25 ° C, 0.5% by weight in dimethylformamide) from 40 to 160 ml / g, corresponding to an average molar mass of about 40,000 up to 2,000,000 (weight average).

Component B can be used in a manner known per se, for. B. by Substance, solution, suspension, precipitation or emulsion polymers receive rization. Details of these procedures are e.g. B. in Kunststoff Handbuch, Ed. Vieweg and Daumiller, Carl-Hanser-Verlag Munich, Vol. 1 (1973), pp. 37 to 42 and Vol. 5 (1969), pp. 118 to 130, as well as in Ullmann's Encyclopedia of Technical Chemistry, 4th ed., Verlag Chemie Weinheim, Vol. 19, pp. 107 to 158 "Polyme risationstechnik ", described.

Typically the high impact vinyl aromatic poly contain mers 5 to 80, preferably 10 to 70 and particularly preferably 15 to 60 wt .-% of the rubber-elastic graft polymer A and ent Speaking 20 to 95, preferably 30 to 90 and particularly preferred 40 to 85% by weight of the thermoplastic polymer B.

7. polyarylene ethers

Polyarylene ethers are preferably to be understood as meaning both polyarylene ethers per se, polyarylene ether sulfides, polyarylene ether sulfones or poly arylene ether ketones. Their arylene groups can be the same or different and, independently of one another, denote an aromatic radical having 6 to 18 carbon atoms. Examples of suitable arylene radicals are phenylene, bisphenylene, terphenylene, 1,5-naphthylene, 1,6-naphthylene, 1,5-anthrylene, 9,10-anthrylene or 2,6-anthrylene. Among these, 1,4-phenylene and 4,4'-biphenylene are given before. These aromatic radicals are preferably unsubstituted. However, you can carry one or more substituents. Suitable substituents are, for example, alkyl, arylalkyl, aryl, nitro, cyano or alkoxy groups and heteroaromas such as pyridine and halogen atoms. The preferred substituents include alkyl radicals with up to 10 carbon atoms such as methyl, ethyl, i-propyl, n-hexyl, i-hexyl, C ₁ - to C ₁₀ -alkoxy radicals such as methoxy, ethoxy, n-propoxy, n-butoxy , Aryl radicals with up to 20 carbon atoms such as phenyl or naphthyl as well as fluorine and chlorine. These can in addition to -O-, z. B. be linked to one another via -S-, -SO-, -SO ₂ -, -CO-, -N = N-, -COO-, an alkylene radical or a chemical bond. In the polyarylene ethers, the arylene groups can also be linked to one another via different groups.

The preferred polyarylene ethers include those with recurring units of the general formula

Their ring-substituted derivatives can also be used. Preferred substituents are C ₁ -C ₆ -alkyl, such as methyl, ethyl or t-butyl, C ₁ -C ₆ -alkoxy, such as methoxy or ethoxy, aryl, in particular phenyl, chlorine or fluorine. The variable X can be -SO ₂ -, -SO-, -S-, -O-, CO, -N = N-, -RC = CR ^a -, -CR ^b R ^c - or a chemical bond. The variable Z can be for -SO ₂ -. -SO-, -CO-, -O-, -N = N- or -RC = CR ^a . Here, R and R ^a each represent hydrogen, C ₁ -C ₆ -alkyl, e.g. B. methyl, n-propyl or n-hexyl, C ₁ -C ₆ alkoxy, including methoxy, ethoxy or butoxy or aryl, in particular phenyl. The radicals R ^b and R ^c can each hydrogen or a C ₁ - to C ₆ -alkyl group, in particular methyl, represent. However, they can also _{be linked to one another to form a C 4} to C ₁₀ cycloalkyl ring, preferably cyclopentyl or cyclohexyl ring, which in turn can be substituted with one or more alkyl groups, preferably methyl. In addition, R ^b and R ^{c can} also be a C ₁ - to C ₆ alkoxy group, e.g. B. methoxy or ethoxy or an aryl group, especially phenyl. The aforementioned groups can in turn each be substituted with chlorine or fluorine.

The polyarylene ethers can also be copolymers or block copolymers, in which polyarylene ether segments and segments from other thermopla synthetic polymers such as polyamides, polyesters, aromatic poly carbonates, polyester carbonates, polysiloxanes, polyimides or Polyetherimides are present. The molecular weights of the blocks or the graft arms in the copolymers are usually in the range from 1000 to 30,000 g / mol. The blocks of different structure can be arranged alternately or statistically. Of the Percentage by weight of the polyarylene ether segments in the Co or block copolymers is generally at least 3, preferably at least 10% by weight. The weight fraction of the polyarylene ethers sulfones or ketones can be up to 97% by weight. Preferred are copolymers or block copolymers with a weight fraction of poly arylene ether segments with up to 90% by weight. Particularly preferred are copolymers or block copolymers with 20 to 80 wt .-% polyarylene ether segments.

In general, the polyarylene ethers have an average molecular weight weight Mn (number average) in the range from 10,000 to 60,000 g / mol and viscosity numbers from 30 to 150 ml / g. The viscosity numbers are either in, depending on the solubility of the polyarylene ethers 1% strength by weight N-methylpyrrolidone solution, in mixtures of phenol and o-dichlorobenzene or in 96% sulfuric acid at each Measured at 20 ° C or 25 ° C.

The polyarylene ethers are known per se or can be per se known methods are produced.

For example, polyphenylene ethers can be oxidative Produce coupling of phenols. Polyarylene ether sulfones or ketones arise z. B. by condensation of aromatic bis-halogen compounds and the alkali double salts of aromatic bisphenols. You can, for example, by self-condensation of Alkali salts of aromatic halophenols in the presence of a Catalyst are produced.

Preferred process conditions for the synthesis of polyarylenes thersulfones or ketones are for example in the EP-A-113 112 and 135 130 are described.

The preferred polyarylene ethers usually have a Melting point of at least 320 ° C (polyarylene ether sulfones) or of at least 370 ° C (polyarylene ether ketones).

According to the invention, the molding compositions can be polyary as component A) contain lenethersulfones or ketones that are produced by reacting a Polyarylene ether sulfone or ketone A1) with a reactive Ver binding are available. The reactive compounds contain ne beneath a C, C double or triple bond one or more car carbonyl, carboxylic acid, carboxylate, acid anhydride, acid imide, Carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline, ure than, urea, lactam or halobenzyl group (s).

Typically suitable compounds are, for example, maleic acid, methyl maleic acid, itaconic acid, tetrahydrophthalic acid, their hydrides and imides, fumaric acid, the mono- and diesters of these acids, eg. B. of C ₁ -C ₁₈ alkanols, the mono- or diamides of these acids such as N-phenylmaleimide, maleic acid hydrazide.

Modified polyarylene ether sulfones or ketones are preferred used, the conversion of 80 to 99.9 wt .-%, in particular 90 to 99% by weight of the unmodified polyarylene ether sulfones or ketones, with 0.1 to 20% by weight, in particular 1 to 10 Wt .-% of the reactive compound have been obtained.

The radical starters can usually be found in the specialist literature (e.g., J.K. Kochi, "Free Radicals", J. Wiley, New York, 1973) be written connections are used.

Usually the free radical initiators are used in amounts of about 0.01 up to about 1% by weight, based on the polyarylene ethers used sulfones or ketones are used. Of course you can too Mixtures of different free radical initiators are used.

Correspondingly modified polyphenylene ethers are inter alia. from the WO 87/00540 known, which is preferably with polyamides as Blendkompo be mixed.

8. Polyurethanes, polyisocyanurates and polyureas

Soft, semi-hard or hard, thermoplastic or cross-linked Polyisocyanate polyaddition products, for example polyurethanes, Polyisocyanurates and / or polyureas, especially polyure thane, are well known. Their production is varied and is usually carried out by reacting (a) Isocyanates with (b) isocyanate-reactive compounds under well-known conditions. The implementation is preferred in the presence of (c) catalysts and / or (d) auxiliaries carried out. When it comes to foamed polyisocyanate polyaddi tion products, they are in the presence of usual Propellants (e) produced.

As isocyanates (a) come the known aromatic, arylaliphatic, aliphatic and / or cycloaliphatic or Chemical isocyanates, preferably diisocyanates, are possible.

As isocyanate-reactive compounds (b) can be for example, well-known compounds with a molecular weight from 60 to 10000 and functionality compared to Iso cyanates from 1 to 8, preferably 2 to 6 are used (im In the case of thermoplastic polyurethanes, TPU functionality approx. 2), for example polyols with a molecular weight of 500 to 10,000, e.g. B. polyether polyols, polyester polyols, polyether polyols sterpolyols, and / or diols, triols and / or polyols with molecules larweights less than 500.

As catalysts (c) for the production of the products can be given Generally known compounds are used, wel the reaction of isocyanates with that of isocyanates highly accelerate reactive compounds, being preferred a total catalyst content of 0.001 to 15% by weight, in particular 0.05 to 6 wt .-%, based on the weight of the total incorporated put isocyanate-reactive compounds (b), use is det, for example tertiary amines and / or metal salts, for example, inorganic and / or organic compounds of the Iron, lead, zinc and / or tin in the usual oxidation states of the metal.

Customary substances can optionally be used as auxiliaries (d) be turned. Surface-active substances may be mentioned, for example Substances, fillers, dyes, pigments, flame retardants, Anti-hydrolysis, fungistatic and bacteriostatic like kekende substances as well as UV stabilizers and antioxidants.

Details on polyurethanes, polyisocyanurates and polyurates The specialist will find materials in the plastics manual, 3rd edition, Volume 7 "Polyurethane", Hanser Verlag, Munich 1993.

9. Polylactides

Polylactides, that is to say polymers of lactic acid, are known per se or can be produced by processes known per se. In addition to polylactide, copolymers or block copolymers based on lactic acid and other monomers can also be used. Mostly linear polylactides are used. However, branched lactic acid polymers can also be used. As a branch z. B. polyfunctional acids or alcohols are used. For example, polylactides can be mentioned, consisting essentially of lactic acid or its C ₁ - to C ₄ -alkyl esters or mixtures thereof and at least one aliphatic C ₄ - to C ₁₀ -dicarboxylic acid and at least one C ₃ - to C ₁₀ -alkanol with three to five hydroxy groups are available.

10. Thermoplastic elastomers (TPE)

Thermoplastic elastomers (TPE) can be used like thermoplastics process, but have rubber-elastic properties. It are TPE block polymers, TPE graft polymers and segmented TPE Copolymers of two or more monomer units are suitable. Special Another suitable TPE are thermoplastic polyurethane elastomers (TPE-U or TPU), styrene oligoblock copolymers (TPE-S) such as SBS (Styrene-butadiene-styrene block copolymer) and SEBS (styrene-ethylene Butylene-styrene block copolymer obtainable by hydrogenating SBS), thermoplastic polyolefin elastomers (TPE-O), thermpla elastic polyester elastomers (TPE-E), thermoplastic polyamide Elastomers (TPE-A) and especially thermoplastic vulcanizates (TPE-V). The latter contain z. B. a thermoplastic and one in a small amount of vulcanized rubber. Exemplary for TPE-V is a blend of polypropylene and slightly vulcanized EPDM (Ethylene-propylene-diene rubber) called.

The person skilled in the art can find details on TPE in G. Holden et al., Thermoplastic Elastomers, 2nd edition, Hanser Verlag, Munich 1996.

11. Halogen-containing polymers

Particularly noteworthy here are polymers of vinyl chloride, in particular polyvinyl chloride (PVC) such as rigid PVC and soft PVC, and copolymers of vinyl chloride such as PVC-U molding compounds.

Fluorine-containing polymers are also suitable, in particular Polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoropropylene Copolymers (FEP), copolymers of tetrafluoroethylene with Per fluoroalkyl vinyl ethers, ethylene-tetrafluoroethylene copolymers (ETFE) polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), Polychlorotrifluoroethylene (PCTFE), and ethylene-chlorotrifluoroethy len copolymers (ECTFE).

12. Polymers containing imide groups

Polymers containing imide groups are, in particular, polyimides, poly etherimide, and polyamideimide.

13. Cellulose esters

Suitable cellulose esters are, for example, cellulose acetate and Celluloseace tobutyrat, and cellulose propionate.

14. Silicone Polymers

Silicone rubbers are particularly suitable. That’s what it’s about are usually polyorganosiloxanes, which react to crosslinking have groups capable of action. Such polymers are used in for example in Römpp Chemie Lexikon, CD-ROM Version 1.0, Thieme Verlag Stuttgart 1995, described.

In addition to the polymers mentioned under No. 1 to 14, other polymers A and B can be used, as e.g. Tie books by Saechtling and Becker and Braun mentioned at the beginning to be discribed.

A mixture of different polymers can also be used as polymer A. or polymer B are used, d. H. the molding I or the Molded part II or both moldings can be made from various mixtures which polymers are made, e.g. B. from single or multiphase polymer blends which contain at least two of the aforementioned polymers ten. Such blends are known to the person skilled in the art.

The polymer A or the polymer B or both polymers can be in addition to the usual additives and processing aids ent keep. Here are the additives and processing aids to be selected according to type and amount in such a way that the molded part I is not changes laser-transparent and molding II unchanged is sorbent. This is particularly important in the selection and dosage of additives and processing aids, note that these must not make the molded part I laser-absorbing.

Suitable additives and processing aids are, for. B. Lubricants or mold release agents, rubbers, antioxidants, stabilizers lizers against the effects of light, antistatic agents, flame retardants, or fibrous and powdery fillers or reinforcing agents, see above like other additives, or their mixtures.

Suitable lubricants and mold release agents are, for. B. stearic acids, Stearyl alcohol, stearic acid esters or amides, silicone oils, Metal stearates, montan waxes and those based on polyethylene and polypropylene.

Suitable antioxidants (heat stabilizers) are about steric hindered phenols, hydroquinones, arylamines, phosphites, various dene substituted representatives of this group, as well as their mixtures gen. They are about as Topanol®, Irgafos®, Irganox® or Naugard® available in stores.

Suitable stabilizers against the action of light are, for. B. ver various substituted resorcinols, salicylates, benzotriazoles, Benzophenones, HALS (Hindered Amine Light Stabilizers), like them z. B. are commercially available as Tinuvin®.

Suitable antistatic agents are, for example, amine derivatives such as N, N- Bis (hydroxyalkyl) alkylamines or alkyleneamines, polyethylene glycol colesters or glycerol mono- and distearates, as well as their mixtures gene.

Suitable flame retardants are z. B. those known to the person skilled in the art halogen-containing or phosphorus-containing compounds, magnesium hy droxide, red phosphorus, as well as other common compounds or their mixtures.

As examples of fibrous or powdery filling and Ver Reinforcement materials are carbon or glass fibers in the form of Glass fabrics, glass mats or glass silk rovings, cut glass, Glass balls and wollastonite are called, particularly preferred glass fiber sern. When using fiberglass, these can be used for the better Compatibility with the blend components with a size and be equipped with an adhesion promoter. Incorporation of the glass fibers can be in the form of short glass fibers as well as in the form of endless strands (rovings).

Suitable particulate fillers are, for. B. Soot, amorphous grit Selsic acid, magnesium carbonate (chalk), powdered quartz, mica, Mica, bentonite, talc, feldspar or especially calcium silicate kate like wollastonite and kaolin.

The fibrous, powdery or particulate filling and reinforcing substances are usually used in amounts of 1 to 60, preferably 10 up to 50% by weight, based on the molded part I or II, is used.

Especially with fillers and reinforcing materials, flame retardants materials, titanium dioxide, and minerals such as wollastonite, should be noted th that these substances affect the extent of laser absorption or trans mission can change significantly. Your quantities must correspond be chosen accordingly.

The individual additives are, taking into account the the above-mentioned limitations with regard to laser absorption, used in the usual amounts, so that closer to gave this superfluous.

The production of molding compounds from polymer A or B and additional or processing aids can be mixed according to a known per se process take place, for example with melting in one Extruder, Banbury mixer, kneader, roller frame or calender. the However, components can also be used "cold" and that powdery or granular mixture is only used in the Processing melted and homogenized.

The components, if appropriate with those mentioned, are preferred th additives, in an extruder or other mixing process direction at temperatures of 100 to 320 ° C with melting of the thermoplastic polymers mixed, and discharged. The Ver Use of an extruder is particularly preferred, especially ei nes co-rotating, tightly intermeshing twin-screw extrusion that.

Molded parts (including semi-finished products) of all can be made from the molding compounds Kind produce, which then with the method according to the invention with be connected to each other. Is molded part within the meaning of the invention z. B. an injection molding or a deep-drawn molding, and includes foils, semi-finished products (sheets, tubes, plates, rods, etc.) a. Are z. B. two or more films with the inventive Processes are linked to one another, the product of the process is namely the composite molded part, a multilayer film.

ii) The laser radiation

The laser radiation used in the method according to the invention generally has a wavelength in the range from 150 to 11000, preferably in the range from 700 to 2000, in particular 800 to 1100 nm.

In principle, all conventional lasers are suitable, for example gas lasers and solid-state lasers. Gas lasers are z. B. (the typical wavelength of the emitted radiation is given in brackets):
CO ₂ laser (10600 nm = 10.6 µm)
Argon gas laser (488 nm and 514.5 nm)
Helium-neon gas laser (543 nm, 632.8 nm, 1150 nm)
Krypton gas laser (330 to 360 nm, 420 to 800 nm)
Hydrogen gas laser (2600 to 3000 nm)
Nitrogen gas laser (337 nm)

Solid-state lasers are z. B. (in brackets the typical wavelength of the emitted radiation):
Nd: YAG laser (Nd ³⁺ : Y ₃ Al ₅ O ₁₂ ) (1064 nm)
High-power diode laser (800 to 1000 nm)
Ruby laser (694 nm)
F ₂ excimer laser (157 nm)
ArF excimer laser (193 nm)
KrCl excimer laser (222 nm)
KrF excimer laser (248 nm)
XeCl excimer laser (308 nm)
XeF excimer laser (351 nm)
as well as frequency-multiplied Nd: YAG lasers with wavelengths of 532 nm (frequency doubled), 355 nm (frequency tripled) or 266 nm (frequency quadrupled).

The lasers used are usually used at powers of 1 up to 200, preferably 5 to 100 and in particular 10 to 50 watts be drove.

The energy densities of the lasers used are usually given in the literature as so-called "line energies" and in the present invention are generally in the range from 0.1 to 50 J / mm. The actual energy density is defined as
input power / generated welding area.

That value is the ratio
Energy per unit length / width of the weld seam produced
equate. The actual energy densities of the lasers used are usually 0.01 to 25 J / mm ² .

The energy density to be selected depends, among other things, on depends on whether the ver binding moldings I and II fillers or reinforcing materials or contain other strongly laser-absorbing substances. For polymers A or B, which contain no fillers or reinforcing materials, betra gen the energy densities usually 1 to 20, in particular 3 to 10 J / mm. For polymers A or B, the fillers or reinforcing materials contain, they are usually 3 to 50, in particular 5 up to 20 J / mm.

Corresponding lasers that are incorporated in the method according to the invention are commercially available.

Excimer lasers are particularly suitable for projection (Mas method). But it is also possible to move the beam with mirroring (scanning). With a homogeneous beam cross cut the irradiation of a mask of about 2 cm × 2 cm is possible lich. By using suitable optics, the beam can cross cut but also further expanded.

Particularly preferred lasers emit in the short-wave infrared range. Such particularly preferred lasers are solid-state lasers, in particular the Nd: YAG laser (Nd ³⁺ : Y ₃ Al ₅ O ₁₂ ) (1064 nm), and high-power diode lasers (800 to 1000 nm). The Nd: YAG laser, the high-power diode laser and the CO ₂ laser are particularly preferred. The CO ₂ laser is particularly suitable for joining foils. The Nd: YAG laser and the diode laser are preferably used for joining other molded parts.

The laser radiation can be stationary (unmoved) and the to ver binding moldings can move past the laser radiation will. The molded parts can also be stationary (stationary) and the laser radiation can be moved past the molded parts. The laser radiation can be moved by moving the laser as a whole, only the laser head, or only the emitted from the laser tending laser radiation via optical or opto-mechanical pre moving directions. Such devices can e.g. B. Lentils, Mirrors, light-conducting cables, in particular fiber optic cables, and other devices commonly used in laser technology, as well as Combinations of the devices mentioned. It is also possible Lich that move both laser radiation and molded parts.

Regardless of the aforementioned embodiments, the relative speed of movement (hereinafter referred to as "speed speed ") of the laser radiation to the molded parts usually 1 to 1000 mm / s, preferably 5 to 200 and in particular 10 to 200 mm / s.

According to the invention, the path of the laser radiation and the ver binding moldings so arranged to each other that the laser radiation at the point to be connected initially on the (laser transparent) molding I meets, it penetrates and finally impinges on the (laser-absorbing) molded part II.

The thickness of the molded part I to be connected is at the ver binding site usually from 0.0005 to 10, preferably from 0.25 to 5 and in particular 0.5 to 3 mm. The thickness of the to be joined Part II can usually be selected as desired.

Regarding the laser power and the speed result the upper and lower limits mentioned, among other things, by the fact that if the laser power is too high or the speed is too low the polymer material at the point of the molded parts to be connected decomposes (thermal damage), and that if the laser is too low performance or too high speed not high quality term (i.e. permanently firm and tight) weld seam is more possible is because the diffusion processes required for welding require a certain temperature exposure time.

The selection of the suitable process parameters for welding ßen, especially the laser, the wavelength, the laser power and the speed, of course, depends on the Thickness of the molded part I also according to the chemical composition of molded parts I and II, in particular after polymers A and B, and after the colorants contained in the moldings I and II th are. It should be noted that some polymers per se la are transparent, while other polymers are inherently transparent There was a certain amount of queuing without the addition of laser-absorbing additives absorb part of the laser radiation. Molded parts I made from lasertran sparing polymers or containing weakly laser-absorbing polymers or additives present in small amounts usually allow a lower laser power or a higher feed rate as molded parts I made of laser-absorbing in the natural state Polymers or containing strongly laser-absorbing or large Amount of additives present.

It has proven advantageous to shape the shape to be connected parts I and II to dry before laser welding to sweat avoid seam defects caused by evaporating water. The drying can for example by storing the molded parts at increased Temperature, in particular 40 to 100 ° C, take place. Particularly good can be the molded parts at elevated temperature in a vacuum dry.

Radiation laser welding can be carried out in various forms. The most important are mentioned as examples:
Contour welding: is a sequential welding process in which the laser beam is guided along a freely programmable seam contour or the component is moved relative to the fixed laser. The weld seam width can be varied greatly depending on the laser type and optics and is typically in the range from 0.6 to 5 mm.
Simultaneous welding: the linearly emitted radiation from individual high-performance diodes is arranged along the seam contour to be welded. The melting and welding of the entire contour thus takes place at the same time (simultaneously).
Quasi-simultaneous or scan (scanning) welding: is a combination of contour and simultaneous welding. The laser beam is guided back and forth along the weld seam contour at high speed using a galvanometric mirror (scanner). As a result, the area to be joined gradually heats up and melts.
Mask welding: a linear laser beam is moved across the parts to be joined. A mask between the laser and the component is used to specifically shade the radiation and only hit the components where they are to be welded. The finest structures in the mask allow high resolutions and weld seam widths of just 10 µm.

Details of the aforementioned embodiments of the Durchstrah lung laser welding can be found in V. Mattus and J. Engel, "Laser beam welding of thermoplastics using the transmission method", Corporate typeface of BASF Aktiengesellschaft Ludwigshafen, Techni Information for experts 07/00, publication date Nov. 2000.

The molded parts I and II to be connected are usually available rend the effect of the laser radiation on the to be connected Get in touch with each other. For example, they touch by lying on top of or against each other. You can use the Apply additional contact pressure to molded parts, if necessary so. By applying pressure to the joint seam contour during the welding process can be a joining path (often referred to as a melting path). Read through it If there are distortions or tolerances of the molded parts I and II or one Compensate for falling spots in the area of the weld seam.

However, it is also possible between the moldings I and II ei Leave a small gap (joint gap).

iii) The colorants

The molded part I and the molded part II contain colorants. Under A colorant means all coloring substances DIN 55 944, which in inorganic and organic colorants so how natural and synthetic can be divided (see Römpps Chemie-Lexikon, 1981, 8th edition, p. 1237).

Colorants covering the entire visible range of the electromagnet absorbing the spectrum are black. Colorants that are im visible range of the electromagnetic spectrum not absor beers are white. Colorants that are in the visible area of the selectively absorb the electromagnetic spectrum, so only Partial areas of the visible light that absorb are colored (not white, not black).

According to DIN 55943 (Sept. 1984) and DIN 55945 (Aug. 1983), a Pigment in the application medium (here in polymer A or B) practically insoluble, inorganic or organic, colored or achromatic colorant. Dyes are in solvents and / or Binding agents (here in polymer A or B) soluble, anorga niche or organic, colored or achromatic colorants.

The nomenclature is used below to designate the colorants the Color Index (C.I.) is used. All colorant names such as "Solvent Orange 60" or "Pigment Red 101" are C.I. designations nations. For the sake of brevity, the part of the name "C.I." after sometimes omitted below.

According to the invention, the molded part I contains at least one colorant, which is in the visible range of the electromagnetic spectrum selectively absorbed. The molded part I thus contains at least one colorful dye.

The colorants contained in the molded part I are preferred selects from the colorants listed in Table 1. The specified Colorant concentrations represent preferred farms of the invention and relate to the total mass of the mold partly I. Column 1 of Table 1 corresponds to the list in An Proverb 2.

Table 1

Colorant for molded part I (laser-transparent)

Some of the colorants mentioned can have different structures are present that differ slightly from each other. For example, pigments with different metal ions can be used varnished, creating different shapes of the pigment hen. These forms are made according to C.I. possibly by adding a A colon and a number, e.g. B. Pigment Red 48 for the pigment lacquered with sodium, Pigment Red 48: 1 with calcium lacquered, pigment red 48: 2 lacquered with barium, pigment red 48: 3 lacquered with strontium, pigment red 48: 4 lacquered with magnesium. The C.I. colorant names mentioned here are to be used in this way stand that they encompass all of these shapes or structures. she are listed in the Color Index. Pigment Red 48: 3 is special preferred.

In the case of black molded parts, the molded part 1 contains at least two of the colorants listed in Table 1.

The molded part I preferably contains in total (sum of all Farbmit tel) 0.01 to 5, particularly preferably 0.015 to 2 and very particularly more preferably 0.02 to 0.4% by weight of colorants.

The colorants contained in the molded part II are preferred chooses from soot, bone charcoal, C.I. Pigment Black 11 and the for the molding I mentioned colorants (see Table 1). In the Table 2 indicated colorant concentrations before Drawn embodiments of the invention and relate to the total mass of the molded part II. Column 1 of Table 2 ent speaks the list in claim 3.

Table 2

Colorant for molded part II (laser absorbing)

In the case of the laser-absorbing molded part II, the upper limit is applicable The only thing to consider is the preferred colorant concentration, that the laser radiation has a certain minimum penetration depth into the Molding II must have so that the required for welding Liche melt can form. Very high colorant concentrations in the molded part II would lead to the laser radiation only at the interface molded part I / molded part II is absorbed, whereby No or too little melt and thus none or a deficiency adherent weld seam is created.

Particularly suitable carbon blacks are those which have a pore volume men, determined by means of DBP absorption (DBP = dibutyl phthalate) ge according to DIN 53 601, from 10 to 300, preferably 40 to 150 and esp special 90 to 120 ml / 100 g.

The DBP adsorption rate is generally according to DIN 53 601 or ASTM-D 2414 determines and represents a measure of the structure of each soot. The term structure is understood to be the interlinking from primary soot particles to aggregates. To determine this characteristic size becomes 10 g of pigment black, which is measured in a kneader with Power transmission (plastograph) is presented as long as Dibu tylphthalate is added dropwise until the maximum torque (network point of soot) is exceeded.

Carbon blacks with a BET specific surface area (according to DIN 60 132 or ASTM D 3037) of at least 10 to 1000, preferably 30 to 500, in particular 100 to 300 m ² / g are preferred.

Furthermore, soot with iodine adsorption (according to DIN 53 582 or ASTM-D 1510) from 23 to 500 preferred.

Carbon blacks with a pH value determined in accordance with DIN are also preferred EN ISO 787/9 or ASTM D 1512, from 1 to 14, in particular 3 to 11.

The mean primary particle size is usually 5 to 500, preferably 10 to 100 and especially 14 to 60 nm.

Such types of soot are z. B. under the trademark Printex® (from Degussa AG) or Raven® (from Columbian) available.

Bone charcoal is a mineral black pigment containing ele mentary carbon, and is also called bone black, elves leg black or C.I. Pigment Black 9. Preferred Kno Cherubs contain 70 to 90, in particular 75 to 85 wt .-% Calcium phosphate and 10 to 30, in particular 15 to 25 wt .-% Koh fuel. Preferred charcoals have a density of 2.3 to 2.8, in particular 2.4 to 2.6 g / ml, and a particle size of 1 up to 50, in particular 2 to 25 µm.

The molded part II preferably contains a total of (sum of all Farbmit tel) at least 0.01% by weight of colorants.

The colorants contained in the molded part I are according to the invention and their concentrations selected so that the molded part I on the point to be connected is transparent to the laser radiation is.

The wording of the claim means "for laser radiation permeable "that the laser radiation from the molded part I is not or is only absorbed to a minor extent, the molded part I. accordingly, the laser radiation passes through completely or predominantly leaves. In particular, the molded part I does not absorb more than 40% the laser radiation.

The colorants contained in the molded part II are according to the invention and their concentrations selected so that the molded part II the point to be connected absorbs the laser radiation.

The wording of the claim means "the laser radiation absorbed biert "that the laser radiation from the molded part II completely or is predominantly absorbed, the molded part II therefore the laser radiation does not pass through or only to a minor extent. In particular, the molded part II leaves no more than 40% of the laser radiation through.

To carry out the invention, for example, those in obi according to Tables 1 and 2 contained colorants and quantities (Concentration ranges) suitable. Based on this information and be A person skilled in the art can easily find further suitable ones Determine colorants and their concentrations. He can with for example from a polymer and a certain amount of one Test specimens colored with dye (e.g. sheets 2 mm thick) and their transmission T, reflection R and absorption A for measuring laser light of a certain wavelength. The following applies: T + R + A = 100%. Colorants with a high transmission are for the laser-transparent molded part I suitable, colorant with a high absorption are suitable for the laser-absorbing molded part II. In addition to the selection of the colorant, the person skilled in the art can Transmission or absorption, of course, also by combination nation of several colorants, and by varying the colorants concentration (s), adjust.

If the desired color impression of the moldings I and II is black is, the molding I contains at least two of those for molding I. called colorants. The black color impression of the molded part I. is essentially created by superimposing the colors of the two or more colorant to black than overall color impression.

According to the invention, the colorants are made from the colorants mentioned tel and their proportions selected so that the moldings I and II substantially the same to the human eye Have color impression.

The wording of the claim means "for the human eye essentially the same color impression "that the molded parts for the inexperienced observers are roughly the same color. It is so an observer with average color perception ge means what the end user of plastic products is like. The wording therefore does not mean that a coloristically ge schulter specialist or a specialist for polymer coloring none Can recognize differences between the molded parts, and he signifies does not mean that the methods of colorimetry (measuring be judgment of colors, e.g. B. According to the CIE system, CIE = Commission Internationale d'Eclairage) did not find any differences sen.

In the following it will be explained on the basis of specific applications 1 to 5, how the person skilled in the art can select the suitable colorants in such a way that that the moldings I and II one for the human eye in the we have essentially the same color impression. The specified color with Tel concentrations represent preferred embodiments of the Er and relate to the total mass of the molded part I. or II.

• - Application 1: both molded parts I and II made of partially crystalline or crystalline polymers such as polyamide, poly butylene terephthalate, polyoxymethylene, or polypropylene; Desired color impression of both molded parts: black

Molded part I (laser-transparent): The selection can be made using the fol Tables 3 and 4 and the explanations below be taken.

Table 3

suitable colorants for laser-transparent, partially crystalline or crystalline, black polymers (e.g. PA, PBT, POM, PP)

Preferred concentration ranges of the colorants mentioned here can be found in Table 1.

To achieve black, at least two colorants must be selected, although they cannot all belong to the same group. Accordingly, at least one colorant must be selected from at least two of the groups. Colorants from the following groups can be combined:

• a) 2 + 3
• b) 1 + 6
• c) 5 + 6
• d) 4 + 5
• e) 4 + 5 + 1
• f) 4 + 5 + 2

Furthermore, any soluble colorant (i.e. any dye, according to C.I. as "Solvent..." designated) of groups 2, 3, 4 and 6 and any Group 5 soluble brown colorant for Er Aiming a black can be used, provided that it is in the ge called maximum concentration (upper limit). aside from that can be a black also by combining at least each generate a colorant from all groups 1 to 6; so at least at least one colorant from each of the six groups.

Such a black is preferably characterized by a Value L * <20, measured according to DIN 5033 and evaluated according to DIN 6173.

Preferred colorant combinations to achieve a black are, for. B .:

• - C.I. Solvent Green 3 + C.I. Solvent Red 179, and
• - C.I, Solvent Green 20 + C.I. Solvent Red 111,
• - As well as mixtures of these colorants in which at least one red and at least one green colorant is included.

The concentrations for Solvent Green are preferably 3 and Solvent Red 179 in each case 0.01 to 0.2, in particular each 0.03 up to 0.12% by weight, and for Solvent Green 20 and Solvent Red 111 each because 0.05 to 0.5, in particular 0.1 to 0.4% by weight in each case, be moved to the molded part I.

Molded part II (laser absorbing)

Table 4

suitable colorants for laser-absorbing, partially crystalline or crystalline, black polymers (e.g. PA, PBT, POM, PP)

At least one of the above must be used to achieve black Colorants can be selected. Printex®60 carbon black is preferred.

• - Application 2: both molded parts I and II made of partially crystalline or crystalline polymers such as polyamide, polybuty lenterephthalate, polyoxymethylene or polypropylene; ge Desired color impression of both molded parts: red

Molded part I (laser-transparent): z. B. each of the color medium from group 2 of table 3, preferably in concentrations from 0.01 to 1, in particular 0.01 to 0.5% by weight.

Molded part II (laser-absorbing): Bay, for example, is suitable ferroxe 665, a mixture of C.I. Pigment Red 101 and C.I. Pig ment Black 11. Bayferrox® 665 is preferred in concentrate from 0.5 to 3% by weight is used. Each of the colors is also included tel from group 2 of table 3 suitable, but preferred higher concentrations for the laser-absorbing molded part II used as in Table 1 for the laser transparent form part I.

• - Application 3: both molded parts I and II made of partially crystalline or crystalline polymers such as polyamide, polybuty lenterephthalate, polyoxymethylene or polypropylene; ge Desired color impression of both molded parts: blue

Molded part I (laser-transparent): z. B. each of the color medium from group 4 of table 3, preferably in concentrations from 0.015 to 2, in particular 0.015 to 1% by weight.

Molded part II (laser-absorbing): C.I. Pigment Blue 15, preferably in concentrations of 1 to 3% by weight. Likewise, each of the colorants from Group 4 of Table 3 is suitable gnet, but preferred for the laser-absorbing molded part II higher concentrations are used than those in Table 1 for the laser-transparent molded part I indicated.

• - Application 4: both molded parts I and II made of partially crystalline or crystalline polymers such as polyamide, polybuty lenterephthalate, polyoxymethylene or polypropylene; ge Desired color impression of both molded parts: green

Molded part I (laser-transparent): z. B. each of the color medium from group 3 of table 3, preferably in concentrations from 0.0005 to 1, in particular 0.0005 to 0.5% by weight.

Molded part II (laser-absorbing): C.I. Pigment Green 7, preferably in concentrations of 1 to 3 each Wt%. Likewise, each of the colorants is from group 3 of the table 3 suitable, but preferred for the laser-absorbing Part II higher concentrations can be used than in Ta Belle 1 specified for the laser-transparent molded part I.

• - Application 5: both molded parts I and II made of amorphous poly mers such as polystyrene, styrene-acrylonitrile copolymer or other styrene copolymers, polysulfones, polyethersulfo nen, polymethyl methacrylate, and their blends; desired the color impression: black

Molded part I (laser-transparent): z. B. C.I. Solvent Yellow 93 together with C.I. Solvent Violet 13. The preferred ones Concentrations for Solvent Yellow 93 are from 0.1 to 0.2, ins especially about 0.15% by weight and for Solvent Violet 13 from 0.25 to 0.4, in particular about 0.325% by weight.

Molded part II (laser-absorbing): For example, carbon black is suitable, preferably in concentrations of at least 0.01% by weight. Special The Printex® 60 carbon black is more preferably used.

The above applications 1 to 5 show by way of example how the Those skilled in the art from the colorants mentioned, depending on the type of polymer A and B and, depending on the desired color impression, the appropriate color medium and can select the appropriate concentrations. It ver it is clear that the applications 1 to 5 mentioned above other colorant selections are also possible and useful. One Such a selection can be made by the person skilled in the art on the basis of the information given and make application examples yourself.

If the colorants are pigments, they have these generally have an average particle diameter of 0.01 to 100 micrometers, preferably from 0.01 to 10 micrometers. Of the mean particle diameter can be, for. B. by means of electron micros copy (light scattering) or measurement of the sedimentation speed can be determined.

The colorants can be mixed with the polymer A or B in a customary manner Way to be mixed. For example, you can use polymer and color medium with melting of the polymer in an extruder, ban Mix the bury mixer, kneader, roller frame or calender. the However, components can also be used "cold" and that powdery or granular mixture is only used in the Processing melted and homogenized.

The components, if appropriate with those mentioned, are preferred th additives, in an extruder or other mixing process direction at temperatures of 100 to 320 ° C with melting of the thermoplastic polymers mixed, and discharged. The Ver Use of an extruder is particularly preferred, especially ei nes co-rotating, tightly intermeshing twin-screw extrusion that.

In particular, one can also initially use the colorant or agents Mix a comparatively small amount of the polymer where created by a colorant concentrate (so-called masterbatch). In As a rule, a masterbatch contains 0.005 to 30% by weight of colorant. The colorant-free polymer is then defined with a Amount of the masterbatch mixed, creating the finished, incorporated colored polymer A or B is formed. The benefits of coloring with Masterbatches are particularly in the better dosability, the more precise color setting and the more homogeneous distribution of the Colorant in the colored polymer. A masterbatch can do one thing or contain more of the colorants mentioned. From this it follows that one or more masterbats are used to color the polymer ches may be required.

The advantages of the method according to the invention over conventional joining methods such as heating element, vibration, rotary welding, gluing or riveting are in particular:

• - No mechanical stress on sensitive components that are in the composite molded part III are encapsulated (e.g. Elek electronic components, mechanical or optical components), like them occurs during vibration or spin welding
• - no problems with polymer sticking to heating elements melt like in heated tool welding
• - Low, localized heat load on the polymers, because also suitable for temperature-sensitive molded parts
• - no large-scale melt expulsion, no bubbles forming on the Weld
• - No contact between the welding device and the ver binding molded parts, therefore almost wear-free
• - high flexibility and ability to be integrated into existing ones Manufacturing processes
• - no use of solvents as with gluing
• - The weld seam is very smooth and even and is therefore sufficient high optical requirements
• - Even high-temperature thermoplastics can be welded
• - also repair welds on already welded joints set moldings are possible.

With the method according to the invention can be made of two or more individual molded parts I and II composite molded parts III manufacture of all kinds.

Such composite molded parts III are in particular housings, Containers, packaging, utensils, components, loading fastening elements, etc. The method is particularly suitable for Manufacture of assembled molded parts, the other components contain. Such other components can, for. B. mechanical (including precision mechanics), electrical, electronic, optical, acoustic or other components made of metals, glasses, ceramics be ken, polymers, rubber or other materials.

Examples of such composite molded parts III are:

• - Housing for vehicle electrics and electronics, e.g. B. Airbag control tion, anti-lock braking system, stability control ESP, electro niche locking systems, sensors for oil level and oil pressure, tem temperature and pressure sensors
• - Radio keys, driving authorization systems
• - conventional vehicle locking systems
• - silencer
• - Motor vehicle circuit housings
• - Housings / frames for lamps (also lamps in cars)
• - Intake pipes, air ducts, air intake hoses
• - Cooling water tanks in vehicles
• - Bumpers, especially welding of the body sides communicate with the bumper, welding of the support part the outer skin, welding of fastening elements)
• - Containers that have to meet high tightness requirements, z. B. Tanks and reservoirs for solids, liquids and Gases (including vehicle fuel tanks)
• - Filter housings that meet high tightness requirements must, for solid, liquid and gaseous media, aerosols etc., air filter, oil filter
• - pump housing
• - Connection of lines for liquids or gases, the ho hen tightness requirements must meet, z. B. Hose connections, corrugated pipes
• - Sealing welds
• - fasteners, e.g. B. dowels
• - gas cartridges and cartridges
• - primers, e.g. B. for airbag propellants
• - House window with frame and window pane
• - machine housing, e.g. B. Drills, saws, milling machines
• - Housing for electronic components, e.g. B. Computer chips
• - Safety and reporting devices, e.g. B. encapsulated IR Sensors, keyless door opening systems (card readers, Keyless Go Cards)
• - photocells
• - Device housings or containers that are dustproof or waterproof should, e.g. B. waterproof photo, video and other Cameras, microscopes
• - Device housings that are filled with a protective gas and therefore should be gas-tight, e.g. B. optical devices such as microscopes, Cameras and camera lenses, binoculars
• - Dosing devices in the technical and medical field
• - glasses
• - packaging, e.g. B. Films + injection molded parts
• - Foil gloves
• - Devices in medical technology
• - lighters.

In addition, the method according to the invention can be used, for example

• - for connecting materials that are difficult to connect, e.g. B. Hart- Soft connections, connection of high temperature thermoplastics
• - for fixing panels, covers, lids, functions share, etc. z. B. in motor vehicles, such as seat backs, back Backrests, hat racks, carpets, floor linings, armatures Built-in panels, door panels, ventilation systems, rear linings, interior linings of the trunk
• - to generate defined column, e.g. B. for the microsystem technology
• - for connecting only partially connected components, e.g. B. as Replacement for rivets
• - for the installation of predetermined breaking points, e.g. B. a spatially resolved to achieve mechanical resilience
• - for textile applications, e.g. B. for fixation or connection of fabrics such as oil filters, felts, fleeces, carpets
• - for repair welds on already welded forms share.

The laser-absorbing molded part II can be before or after the connection marked with the molded part I by high-energy radiation or labeled by a for marking or labeling processing of thermoplastic polymers suitable high-energy Radiation impinges directly on the molded part II. Using When it comes to laser radiation, one speaks of laser marking.

With this, a high-quality marking on a plastic molding or labeling arises, the absorption of the high-energy Radiation, such as laser radiation, causes a color change reaction ken. There are two methods of laser marking, the Masks (projection) and beam deflection labeling (scanning of the laser beam). When writing masks, pulsed lasers are used used. A laser beam with a sufficiently large aperture be a mask lights up showing all the information to be transmitted tion contains. The mask is labeled with a lens on the tending surface, the information can be shared with one umpteen laser pulses can be applied to the workpiece. With big ones The mask can be scanned with several pulses. the The maximum size of the labeling field is determined by the necessary Energy density limited. The projection method thus allows quick lettering; since a mask must be created is however, it is not that flexible. With the beam deflection labeling the laser beam goes through two moveable mirrors and a plan field lens directed onto the workpiece to be marked.

As a laser-sensitizing measure, laser marking are common: addition of colorants, additive of toxic arsenic or Cd compounds, suitable addition 15393 00070 552 001000280000000200012000285911528200040 0002010054859 00004 15274neter Monomers in the copolymerization, coating of the substrate with special lacquer and color films, inks, etc. The one is common storage of soot (DE-A 29 36 926) or bone charcoal (EP-A 522 370) or of antimony trioxide in thermoplastic Ela stomere.

Special plastic additives with high absorption capacity, especially for the wavelength of the Nd: YAG laser, enable markings with high contrast, good contour definition and good abrasion resistance (C. Herkt-Maetzky, Kunststoffe 81 (1991) 4). Other processes work with radiation-sensitive, bleachable additives (and possibly additional, less radiation-sensitive, non-discolourable compounds). The radiation-sensitive dyes are then destroyed by irradiation and the background or complementary color of the polymer matrix then remains at the irradiated areas and a visual, colorful contrast marking is created. Such color changes lead to good contrasts (EP-A 327 508). Plastics that contain commercially available colored pigments can be partially labeled with the frequency-doubled Nd: YAG laser, as a large number of pigments and dyes are absorbed at 532 nm. The pigments are bleached out with the consequence of a color change. By adding modified mica pigments, molding compounds can be produced that can be _{labeled with the CO 2} laser (C. Herkt-Maetzky, Kunststoffe 81 (1991) 4). Processes are also possible in which pigments are applied to a carrier material and are thermally melted into the surface with the aid of the laser (EP-A 419 377). According to EP 400 305, copper hydroxyphosphates and other colorless additives such as molybdenum sulfide can be used to improve the writability, especially of polyesters. Those skilled in the art will find further measures to improve the laser writability in EP-A 249 082 and WO 95/01580, as well as EP-A 954 447.

The high-energy radiation used upon writing of the molded part II generally has a wavelength in the range from 150 to 1500, preferably in the range of 150 to 1100 nm example as CO are here ₂ laser (10600 nm) and Nd:. YAG lasers (1064 or 532 nm) or UV laser mentioned, the latter being in particular excimer lasers with the following wavelengths:

F ₂ excimer laser 157 nm ArF excimer laser 193 nm KrCl excimer laser 222 nm KrF excimer laser 248 nm XeCl excimer laser 308 nm XeF excimer laser 351 nm

as well as frequency-multiplied Nd: YAG lasers with wavelengths of 355 nm (frequency tripled) or 266 nm (frequency quadrupled).

Nd: YAG lasers (1064 or 532 nm), KrF- Laser (248 nm) and XeCl laser (308 nm).

The energy densities of the lasers used for marking or inscription are generally in the range from 0.3 mJ / cm ² to 50 J / cm ^2, preferably 0.5 mJ / cm ² to 20 J / cm ² and particularly preferably 1 mJ / cm ² to 10 J / cm ² .

When using pulsed lasers, the pulse frequency is im generally in the range from 0.1 to 10,000, preferably from 0.5 up to 5000 and in particular from 1 to 1000 Hz and the pulse lengths (Duration of the individual pulses) in the range from 0.1 to 1000 preferably from 0.5 to 500 and particularly preferably from 1 to 100 ns. Depending on the energy density of the laser used, the pulse length and the type of shaped body irradiated are sufficient Achieving good lettering generally 1 to 20,000 before preferably 1 to 5000 and in particular 1 to 3000 pulses.

Corresponding lasers that are incorporated in the method according to the invention are commercially available.

Excimer lasers are particularly suitable for projection (Mas method). But it is also possible to move the beam with mirroring (scanning). With a homogeneous beam cross cut the irradiation of a mask of about 2 cm × 2 cm is possible lich. By using suitable optics, the beam can cross cut but also further expanded. With excimer lasers can be well labeled with just one pulse (with ent speaking adapted energy density), so that compared to Nd: YAG lasers can also be used to produce very fast inscriptions. In the series production of injection molded parts such. B. must the Be writing time less than the injection molding time (<approx. 30 s) ge divided by the number of mold cavities. It follows that in In these cases, the injection-molded molds run at high speeds must be labeled. Such high speeds are sometimes not possible with the Nd: YAG laser, only achievable with 1-pulse mask bombardment.

Even higher demands on the marking speed provide continuous processes such as B. profile extrusion with Material speeds of several m / s. Enough for this not even the high writing speeds of Nd: YAG lasers the end.

As radiation sources for labeling can also continue to kon continuous UV lamps such as mercury, xe or deuterium lamps are used are set. Such products are also commercially available lich.

The process of the invention requires fewer colorants than the prior art methods. It saves with it Colorant costs and continues to avoid those mentioned at the beginning ten problems that arise when incorporating large amounts of colorant into Polymers can occur. In particular, it enables the laser welding of individual molded parts to form composite molded parts len, which are visually homogeneous (un danger of the same color). Not only black, but also colored (multicolored) composite molded parts len. The weld seam has a very good seal against fluids liquids and gases. It is also smooth and even, and ge meets high optical and aesthetic requirements.

Examples

Polymers A and B used:

The polymer names used in Table 6 are as follows Meaning:

PA66 GF30: Polyamide 66 (polyhexamethylene adipamide) with egg ner viscosity number VN of 150 ml / g, measured as 0.5 wt .-% Solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307, was with glass fibers from OCF, type 123D10P, diameter 10 micro meter, mixed. The glass fiber content was 30% by weight. The VZ of the glass fiber-containing polyamide was 145 ml / g as measured as to described before.

PBT GF30: polybutylene terephthalate with a viscosity number VZ of 130 ml / g, measured as a 0.5% strength by weight solution in a 1: 1 mixture Schung phenol / o-chlorobenzene at 25 ° C according to ISO 1183, was with Glass fibers from PPG, type 3565, diameter 10 micrometers, mixed. The glass fiber content was 30% by weight. The VZ of the glass fiber-containing PBT was 105 ml / g, measured as before be wrote.

PA66: Polyamide 66 (polyhexamethylene adipamide) without glass fibers, with a viscosity number of 150 ml / g, measured as 0.5 % strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307

PA6 GF30: polyamide 6 (polycaprolactam) with a viscosity number VZ of 150 ml / g, measured as a 0.5% by weight solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307, was with glass fiber from the company OCF, type 123D10P, diameter 10 micrometers mixed. The glass fiber content was 30% by weight. The VZ of the glas fiber-containing polyamide was 145 ml / g, measured as before be wrote.

PP: Polypropylene homopolymer without glass fibers, with a melt Flow rate MFR of 1.8 g / 10 min, determined according to ISO 1133 at 230 ° C and 2.16 kg load.

Colorants used

The colorants mentioned in Table 6 were defined by their C.I. designation. In all cases, trade usual qualities used.

Printex® 60 from Degussa was used as the carbon black. Table 5 summarizes the properties of the soot together.

Table 5

Properties of the carbon black used

Mixing the polymers with the colorants and producing the test specimen to be welded

The polymers were in a conventional twin screw manner extruder mixed with the colorants. Type and concentrations the polymers and colorants are shown in Table 6. Man he held colored polymer granules.

From the polymer granules were in a known manner on a Injection molding machine strip-shaped test specimens with the dimensions 80 × 28 × 2 mm.

Used laser welding system

The welds were made using the transmission laser welding method. A system for laser marking was used, which was operated in continuous wave (cw) mode. The parameters held constant were as follows:
Laser system: Nd: YAG marking laser type FOBALAS 94 S from Foba, Lüdenscheid, DE
Wavelength: 1064 nm
Lens focal length: 160 mm
Focus distance: 55 mm
Aperture width: 5.0 mm
Lamp current: 26 A
average Beam power: 35 W.

Welding the specimens

The laser-transparent and laser-absorbing ones, each 2 mm thick strip-shaped test specimens were min dried in vacuo at 80 ° C. for at least 12 hours.

Then a laser-transparent test specimen and a laser-absorbing specimens on their 80 mm long sides Laying them on top of one another under light pressure and overlapping, where with the laser-absorbing test specimen at the bottom. The width of the The overlap was 10 mm.

The welding was carried out with an edge distance of approx. 5 mm each both edges, i.e. roughly in the middle of the overlap zone, as Weld line parallel to the edges. The laser beam applied next on the laser-transparent and then on the laserabsorbie renden test specimen and was continuously over the test specimen emotional.

The speed of movement v _{max of} the laser beam is given in Table 6.

Testing of the welded test specimens

The test specimens welded to one another were subjected to a tensile test Subject to based on ISO 527. The test speed was 10 mm / min. The distance between the clamping jaws was 100 mm. As a result The shear strength was obtained in MPa, see Table 6.

In addition to the shear strength, the weldability was also assessed according to the "principle of maximum welding speed". This procedure was chosen because, with a good connection, test specimens that are welded overlapped usually fail not in the actual weld but in the polymer material adjoining the weld (i.e. next to the weld), e.g. B. tear or break. An assessment of the weld seam solely on the basis of the shear strength would therefore be insufficient. In the "principle of maximum welding speed", the speed was determined at which there was a transition from pure failure of the weld seam to pure failure of the test specimen. This "transition _{speed" v max} was therefore the maximum speed with which the test specimen could just barely be welded, so that the joined molded part next to the weld seam and not the weld seam itself failed: if v ≦ v _max , the test specimen broke alongside of the weld seam, _{if v <v max} , the weld seam itself broke. The specification of v _max and the shear strength at v _max thus enabled a clear differentiation between different test specimen materials and colors.

v _max was determined by gradually reducing the welding speed until the first material fractures occurred. The previously calculated shear strength at the joint breakage was specified as the weld seam strength.

Table 6 summarizes the composition of the test specimens and the loading assessment of the weld together. Those mentioned in Table 6 Colorant concentrations in% are% by weight and relate to the respective molded part I and II. In columns 2 and 3 of the The table shows the information corresponding to the table header orderly.

Table 6

Composition of the test specimens and assessment of the weld seam (So. = Solvent, Printex = soot Printex®, V = for comparison, nb = not determined)

Explanation

The table shows that with the method according to the invention Can produce composite moldings, the difference are homogeneous in color compared to the processes of the prior art. In contrast to DE-A 195 10 493, according to which laser absorption rende molding must contain 1 to 2 wt .-% colorant, comes that Process according to the invention with only 0.1% by weight of colorant (carbon black) in the laser-absorbing molded part, so with a tenth of this Lot.

The process enables molded parts to be joined together Chen polymers (Examples 1 to 6 and 8 to 9) or from various those polymers (PA 6 with PA 66, Example 7).

The test specimens of Comparative Example 1V can be ver weld, but the finished composite molding has ver different colors, so the color is inhomogeneous.

The specimens of Comparative Examples are 2V to 5V and 7V uniformly black (a molded part composed of it would therefore be homogeneous in color black / black), but leave them do not weld.

Comparative example 2V shows for glass fiber reinforced PA 66 that Carbon black is unsuitable as a colorant for the laser-transparent molded part I. net is. Comparative example 3V repeats comparative example 2V, However, the concentration of the "interfering" soot in the laser transparent molded part I was reduced from 0.1 to 0.01%. Even this measure does not lead to success. The same applies to PBT, comparative examples 7V and 8V. The finished molded part from Ver The same example 8V is also due to the reduced Soot concentration in molded part I inhomogeneous in color (gray / black).

A replacement of the carbon black in molded part I by the black dye Nigrosine in various concentrations (comparative examples 4V and 5V) receives the uniform color impression black / black, but does not lead to the desired weldability.

Comparative Examples 6V and 9V give composite form parts that are inhomogeneous in color. In addition, mean the low maximum welding speed of only 3.5 mm / s in Example 6V that productivity is low: per unit of time only a short weld can be produced.

Claims (11)

1. A method for connecting a molded part I made of a colorant-containing thermoplastic polymer A with a molded part II made of a colorant-containing thermoplastic polymer B by laser radiation, in which

• 1. the laser radiation passes through the molded part I at the point to be connected and hits the molded part II,
• 2. the molded part I contains at least one colorant which selectively absorbs in the visible range of the electromagnetic spectrum,
• 3. the colorants contained in the molded part I and their concentrations are selected in such a way that the molded part I is permeable to the laser radiation at the point to be connected,
• 4. the colorants contained in the molded part II and their concentrations are selected in such a way that the molded part II absorbs the laser radiation at the point to be connected,
• 5. the colorants contained in both moldings I and II and their proportions are selected so that the moldings I and II have a color impression we sentlichen the same for the human eye.

2. The method according to claim 1, characterized in that the im Colorants contained in molded part I are selected from C.I. Pigment orange 64, C.I. Solvent Orange 60, C.I. Solvent Orange 106, C.I. Solvent Orange 111, C.I. Pigment red 48, C.I. Pigment red 101, C.I. Pigment red 144, C.I. Pigment red 166, C.I. Pigment red 178, C.I. Pigment red 254, C.I. Solvent Red 52, C.I. Solvent Red 111, C.I. Solvent Red 135, C.I. Sol vent Red 179, C.I. Pigment green 7, C.I. Pigment green 17, C.I. Pigment Green 50, C.I. Solvent Green 3, C.I. Solvent Green 20, C.I. Pigment blue 15, C.I. Pigment blue 29, C.I. Pigment blue 36, C.I. Pigment yellow 93, C.I. Pigment yellow 110, C.I. Pigment yellow 150, C.I. Pigment yellow 180, C.I. Pigment yellow 184, C.I. Solvent Yellow 21, C.I. Solvent Yellow 93, C.I. Pigment brown 24, C.I. Pigment violet 19, C.I. Solvent Violet 13, C. T. and Solvent Violet 46. 3. The method according to claims 1 to 2, characterized net that the colorants contained in the molding II selected are made of soot, charcoal, C.I. Pigment Black 11, and the for the molding I mentioned colorants. 4. The method according to claims 1 to 3, characterized net that in the case of black moldings the molding I at least at least two of the colorants mentioned in claim 2 contains. 5. The method according to claims 1 to 4, characterized in that the molded part I the colorant

• a) CI Solvent Green 3 and CI Solvent Red 179, or
• b) CI Solvent Green 20 and CI Solvent Red 111, or
• c) Mixtures of these colorants which contain at least one red and at least one green colorant.

6. The method according to claims 1 to 5, characterized net that the molding II as a colorant carbon black or bone charcoal or a mixture of these. 7. The method according to claims 1 to 6, characterized net that the thermoplastic polymers A and B are selected are from the group of polyoxymethylenes, polycarbonates, Polyesters, polyolefins, polyacrylates, polymethacrylates, poly amides, vinyl aromatic polymers, polyarylene ethers, polyures thane, polyisocyanurates, polyureas, polylactides, thermoplastic elastomers, halogen-containing polymers, polymers containing imide groups, cellulose esters, silicone-poly mers, or mixtures thereof, the polymers A and B can be the same or different. 8. The method according to claims 1 to 7, characterized net that the laser radiation has a wavelength of 150 to 11000 nm. 9. The method according to claims 1 to 8, characterized net that the molded part II before or after connecting to the Molded part I marked by high-energy radiation or be is written by adding a mark or lettering high energy suitable for thermoplastic polymers Radiation impinges directly on the molded part II. 10. Use of the method according to claims 1 to 9 for Manufacture of composite moldings III, the up Builds are made up of two or more individual molded parts I and II. 11. Composite molded parts III, which are made up of two or more individual moldings I and II, obtainable after Process according to claims 1 to 9.