DE19920276A1 - Thermoplastic molding compounds - Google Patents

Abstract

The invention relates to thermoplastic moulding materials containing A) between 10 and 99 % by weight of at least one thermoplastic polymer, B) between 1 and 50 % by weight of a mixture consisting of b1) at least one phosphorous compound and b2) at least one stabiliser compound of the general formulas (I) to (IV). In formula (I), R<1> and R<2> represent, independently of one another, a hydrogen radical, a C1 to C10 alkyl radical, a C6 to C12 aryl radical, a C7 to C13 aralkyl radical, or a C7 to C13 alkylaryl radical, a, b independently of one another, have the values 1 to 5, c, d independently of one another, have the values 0 to 10. In formula (II), R<3> represents a hydrogen radical, a C1 to C10 alkyl radical, a C6 to C12 aryl radical, a C7 to C13 aralkyl radical, a C7 to C13 alkylaryl radical, e has the value 1 to 4, f has the value 1 to 100. In formula (III), R<4> and R<13> independently of one another, represent NCO or NHCOOR', whereby R' represents an alkyl polyetherglycol or an alcohol containing between 1 and 20 C-atoms, R<5>, R<6>, R<7>, R<8>, R<9>, R<10>, R<11>, R<12> independently of one another, represent a hydrogen radical, a C1 to C10 alkyl radical, a C6 to C12 aryl radical, a C7 to C13 aralkyl radical, a C7 to C13 alkylaryl radical, g indicates 0 to 5, h indicates 1 to 100. In formula (IV) R<14>, R<15>, R<16> independently of one another, represent a hydrogen radical or a radical (a), whereby R<17> represents a hydrogen radical, a C1 to C10 alkyl radical, a C6 to C12 aryl radical, a C7 to C13 aralkyl radical, a C7 to C13 alkylaryl radical, or (CH2)1-N=C=O, whereby 1 indicates 1 to 20, i indicates 2 to 8, j indicates 1 to i-k, k indicates 0 to i-j, whereby j + k </= i, or at least two of these groups. Said thermoplastic moulding materials also contain C) between 0 and 40 % by weight of a flame-retardant which is different from b1); and D) between 0 and 70 % by weight of additives. The weight percentages of components A) to D) always correspond to 100 %.

Description

The invention relates to thermoplastic molding compositions containing

• A) 10 to 99 wt .-% of at least one thermoplastic polymer
• B) 1 to 50 wt .-% of a mixture of
  • 1. b ₁ ) at least one phosphorus compound and
  • 2. b ₂ ) at least one stabilizer compound of the general formulas I to IV
    in which
    R ¹ , R ² independently of one another are a hydrogen, C ₁ - to C ₁₀ -alkyl, C ₆ - to C ₁₂ -aryl, C ₇ - to C ₁₃ -aralkyl, C ₇ - to C ₁₃ -alkylaryl radical,
    a, b are independently 1 to 5,
    c, d are independently 0 to 10;
    in which
    R ^{3 is} a hydrogen, C ₁ - to C ₁₀ -alkyl, C ₆ - to C ₁₂ -aryl, C ₇ - to C ₁₃ -aralkyl, C ₇ - to C ₁₃ -alkyl aryl radical,
    e 1 to 4,
    f 1 to 100;
    in which
    R ⁴ , R ¹³ independently of one another NCO or NHCOOR ', where R' is an alkylpolyether glycol or an alcohol having 1 to 20 C atoms,
    R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^{12 are} independently hydrogen, C ₁ - to C ₁₀ alkyl, C ₆ - to C ₁₂ aryl, C ₇ to C ₁₃ aralkyl, C ₇ to C ₁₃ alkylaryl radical,
    g 0 to 5,
    h 1 to 100;
    in which
    R ¹⁴ , R ¹⁵ , R ¹⁶ independently of one another hydrogen radical or
    
  wherein R ^{17 is} a hydrogen, C ₁ to C ₁₀ alkyl, C ₆ to C ₁₂ aryl, C ₇ to C ₁₃ aralkyl, C ₇ to C ₁₃ alkylaryl, or
  (CH ₂ ) ₁ -N = C = O, where
  l 1 to 20,
  i 2 to 8,
  j 1 to ik,
  k 0 to ij, where
  j + k ≦ i, or at least two of them
  mean.
• C) 0 to 40% by weight of a flame retardant, different from b ₁ )
• D) 0 to 70 wt .-% of other additives, wherein the weight percent of components A) to D) always give 100%.

Furthermore, the invention relates to the use of the invention according to the molding compositions for the production of fibers, films and mold bodies and the moldings available in this case.

There is an increasing market interest for halogen-free flame protected thermoplastics, especially polyester. Essentials demands on the flame retardant are: light color, off reaching temperature stability for incorporation into Thermopla and its effectiveness in reinforced and unreinforced Polymer (so-called wicking effect on glass fibers).

In addition to the halogen-containing systems, four halogen-free FR systems are in principle used in thermoplastics:

• - Inorganic flame retardants that show efficacy must be used in high amounts.
• Nitrogen-containing FR systems, such as melamine cyanurate, which has a limited effectiveness in thermoplastics z. B. polyamide shows. In reinforced polyamide, it is only in conjunction with shortened glass fibers effectively. In polyesters is melamine cyanurate alone is not effective.
• - Phosphorus-containing FR systems, which are generally not in polyesters are particularly effective.
• - Phosphorus / nitrogen-containing FR systems, such. For example ammonium polyphosphates or melamine phosphates used for thermoplastics, which are processed at temperatures above 200 ° C, none have sufficient thermal stability.

From JP-A 03/281 652 polyalkylene terephthalates are known, which melamine cyanurate and glass fibers and a phosp horhaltiges flame retardant. Contain these molding compounds Derivatives of phosphoric acid such as phosphoric acid ester (valence stage +5), which under thermal stress to "blooming" nei gene.

These disadvantages are also evident for the combination of melamine cyanurate (MC) with resorcinol bis (diphenyl phosphate), which consists of JP-A 05/070 671 is known. Furthermore show this form when processing high phenol values and not ausrei ing mechanical properties.

From JP-A 09/157 503 are polyester molding compounds with MC, Phosphorus compounds and lubricants known which less than 10% reinforcing agent. Flame retardant and mechani The properties of such molding compositions are improved needy as well as migration and phenol formation at the verar processing.

From EP-A 699 708 and BE-A 875 530 are phosphinic salts as Flame retardant for polyester known.

In WO 97/05 705 combinations of MC with phosphorus containing compounds and lubricants for polyester disclosed.

From EP-A 628 541 and WO-A 96/17011 are carbodiimides as Hy drolysis stabilizers for thermoplastics known.

In particular, in electronic components are in phosphor containing flame retardant thermoplastics the stabilities at ho continuous use temperatures (against dry heat) still ver improvement worthy. At the same time show such flame retardants an increased tendency to corrosion on contact with metal parts, so that both efflorescence or cleavage products of the flame retardant to Short circuits lead to such components.

The present invention was therefore based on the object halogen-free flame-retardant thermoplastics available len, the improved stability at high continuous use show temperatures and the degradation of the polymer matrix in dry ner, reduce warm environment. At the same time should bloom and corrosion tendency of the flame retardants are minimized. Accordingly, the molding compositions defined above were found. Be Preferred embodiments can be found in the dependent claims.  

As component A), the molding compositions according to the invention contain 10 to 99, preferably 20 to 95 and in particular 30 to 80 wt .-% a thermoplastic polymer.

Basically, the beneficial effect in the molding compositions according to the invention in thermoplastics of any kind. An enumeration of suitable thermoplastics can be found, for example in the plastic paperback (Hrsg. Saechtling), edition 1989, where also sources of supply are called. Process for the preparation Such thermoplastics are known to those skilled in the art known. Below are some preferred types of plastic et which explains in more detail.

1. polycarbonates and polyesters

Generally, polyesters based on aromatic dicarbon acids and an aliphatic or aromatic dihydroxy connection used.

A first group of preferred polyesters are polyalkylene tereph thalates with 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, for. B. halogens 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 t-Butylgrup pen.

These polyalkylene terephthalates can be prepared by the reaction of aroma dicarboxylic acids, their esters or other ester-forming Derivatives with aliphatic dihydroxy compounds in themselves be be known manner.

Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, Terephthalic acid and isophthalic acid or mixtures thereof NEN. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cyclo aliphatic dicarboxylic acids such as adipic acid, azelaic acid, Sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids be set.

Of the aliphatic dihydroxy compounds diols with 2 to 6 carbon atoms, especially 1,2-ethanediol, 1,3-propane diol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclo  hexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or their mixtures are preferred.

Particularly preferred polyesters (A) are polyalkylene tereph thalates derived from alkanediols containing 2 to 6 carbon atoms, to call. Of these, in particular, polyethylene terephthalate lat, polypropylene terephthalate and polybutylene terephthalate or their mixtures are preferred. Further preferred are PET and / or PBT containing up to 1% by weight, preferably up to 0.75% by weight 1,6-hexanediol and / or 5-methyl-1,5-pentanediol as further mono contain units.

The viscosity number of the polyesters (A) is generally in Be ranging from 50 to 220, preferably from 80 to 160 (measured in a 0.5% by weight solution in a phenol / o-dichlorobenzene sequence mixed (weight ratio 1: 1 at 25 ° C) according to ISO 1628).

Particularly preferred are polyesters whose carboxyl end groups content up to 100 meq / kg, preferably up to 50 meq / kg and ins special is up to 40 meq / kg polyester. Such poly For example, esters can be prepared by the process of DE-A 44 01 055 getting produced. The carboxyl end group content becomes more common determined by titration method (eg potentiometry).

Particularly preferred molding compositions contain as component A) a mixture of polyethylene terephthalate (PET) and polyalkylene terephthalates having 3 to 10 C atoms in the alcohol part, in particular Polybutylene terephthalate (PBT). The proportion of polyethylene tereph Thalates is preferably in the mixture up to 50, in particular 10 to 30 wt .-%, based on 100 wt .-% A).

Such molding compositions of the invention show very good flame protective properties and better mechanical properties.

Furthermore, it is advantageous PET recyclate (also scrap PET ge called) in admixture with polyalkylene terephthalates such as PBT put.

Recyclates are generally understood as:

• 1. so-called Post Industrial Recyclate: this is about Production waste in polycondensation or Ver working z. B. sprues in the injection molding, starting in injection molding or extrusion or edge sections of extruded sheets or foils.  
• 2nd Post Consumer Recyclate: this is art fabric after use by the end user collected and processed. The quantity by far dominating articles are blow-molded PET bottles for mine water, soft drinks and juices.

Both types of recyclate can be either as regrind or in shape of granules present. In the latter case, the tubes are recycled after separation and purification in an extruder molten zen and granulated. This is usually the handling, the Rie selectivity and dosing for further processing steps made easier.

Both granulated and as regrind present recyclates can be used, whereby the maximum edge length 6 mm, should preferably be less than 5 mm.

Due to the hydrolytic cleavage of polyesters in the Ver working (by traces of moisture) it is recommended that the Re to pre-dry cyclically. The residual moisture content after drying is preferably 0.01 to 0.7, in particular 0.2 to 0.6%.

Another group to be mentioned are fully aromatic polyesters which of aromatic dicarboxylic acids and aromatic dihydroxy Derive connections.

As aromatic dicarboxylic acids are already in the Polyalkylene terephthalates described compounds. Prefers are mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of about 80% Terephthalic acid with 20% isophthalic acid to about equivalent Mixtures of these two acids used.

The aromatic dihydroxy compounds preferably have the general formula

in which Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m the value 0 until 2 has. The compounds I can also carry C ₁ -C ₆ -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

As a parent of these compounds its example, dihydroxydiphenyl,
Di (hydroxyphenyl) alkane,
Di (hydroxyphenyl) cycloalkane,
Di (hydroxyphenyl) sulfide,
Di (hydroxyphenyl) ether,
ketone di- (hydroxyphenyl),
di- (hydroxyphenyl) sulfoxide,
α, α'-di (hydroxyphenyl) -dialkylbenzol,
Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene
Resorcinol and
Hydroquinone and their nuclear alkylated or ring-halogenated derivatives called.

Of these will be
4,4'-dihydroxydiphenyl,
2,4-di- (4'-hydroxyphenyl) -2-methylbutane
α, α'-di (4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-di (3'-methyl-4'-hydroxyphenyl) propane and
2,2-di- (3'-chloro-4'-hydroxyphenyl) propane,
and in particular
2,2-di- (4'-hydroxyphenyl) propane
2,2-di (3 ', 5-dichlordihydroxyphenyl) propane,
1,1-di- (4'-hydroxyphenyl) cyclohexane,
3,4'-dihydroxybenzophenone,
4,4'-dihydroxydiphenylsulfone and
2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane
or mixtures thereof are preferred.

Of course, you can also mixtures of polyalkylene use terephthalates and wholly aromatic polyesters. These generally contain from 20 to 98% by weight of the polyalkylene tereph thalates and 2 to 80 wt .-% of wholly aromatic polyester.

Among polyesters in the context of the present invention are also intended Polycarbonates obtained by polymerization of aromatic dihydroxy compounds, especially bis (4-hydroxy phenyl) -2,2-propane (bisphenol A) or its derivatives, e.g. B. with Phosgene are available. Corresponding products are in themselves be  Known and described in the literature and mostly in the Trade available. The amount of polycarbonates is up to 90% by weight, preferably up to 50% by weight, especially 10 to 30 wt .-% based on 100 wt .-% of component (A).

Of course, polyester block copolymers such as Copolyetherester can be used. Such products are on known and in the literature, for. In US-A 3,651,014, described. Also in the trade are obtained corresponding products Lich, z. Hytrel® (DuPont).

2. Vinylaromatic polymers

The molecular weight of these known and commercially available polymers is generally in the range of 1500 to 2,000,000, preferably in the range of 70,000 to 1,000,000.

Only representative here are vinyl aromatic polymers Styrene, chlorostyrene, α-methylstyrene and p-methylstyrene called; in minor proportions (preferably not more than 20, ins not more than 8% by weight), comonomers can also be used (Meth) acrylonitrile or (meth) acrylic acid ester involved in the construction his. Particularly preferred vinylaromatic polymers are poly styrene and impact modified polystyrene. It goes without saying that mixtures of these polymers can be used. The preparation is preferably carried out according to EP-A-302 485 described method.

Preferred ASA polymers are composed of a soft or rubber phase of a graft polymer of:

• 1. A ₁ 50 to 90 wt .-% of a graft base based on
  • 1. A ₁₁ 95 to 99.9 wt .-% of a C ₂ -C ₁₀ alkyl acrylate and
  • 2. A ₁₂ 0.1 to 5 wt .-% of a difunctional monomer having two olefinic, non-conjugated double bonds, and
• 2. A ₂ 10 to 50 wt .-% of a graft from
  • 1. A ₂₁ 20 to 50 wt .-% of styrene or substituted styrenes of the general formula I or mixtures thereof, and
  • 2. A ₂₂ 10 to 80 wt .-% acrylonitrile, methacrylonitrile, acrylic acid esters or methacrylic acid esters or mixtures thereof,
  in mixture with a hard matrix based on a SAN copolymer A ₃ ) from:
• 3. A ₃₁ 50 to 90, preferably 55 to 90 and in particular 65 to 85 wt .-% of styrene and / or substituted styrenes of the general formula I and
• 4. A ₃₂ 10 to 50, preferably 10 to 45 and in particular 15 to 35 wt .-% of acrylonitrile and / or methacrylonitrile.

The component A ₁ ) is an elastomer, which has a glass transition temperature of less than -20, in particular less than -30 ° C.

For the preparation of the elastomer, the main monomers A ₁₁ ) used are esters of acrylic acid having 2 to 10 C atoms, in particular 4 to 8 C atoms. Particularly preferred monomers which may be mentioned here are tert-butyl, isobutyl and n-butyl acrylate and also 2-ethylhexyl acrylate, of which the latter two are particularly preferred.

In addition to these esters of acrylic acid are used from 0.1 to 5, in particular 1 to 4 wt .-%, based on the total weight of A ₁₁ + A _{12 of} a polyfunctional monomer having at least two olefinic, non-conjugated double bonds. Of these, difunctional compounds, ie having two non-conjugated double bonds, are preferably used. For example, divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate may be mentioned here, of which the last two are particularly preferred.

Process for the preparation of the graft A ₁ are known per se and z. As described in DE-B 12 60 135. Corresponding products are also commercially available.

Be particularly advantageous in some cases, the Her Position proven by emulsion polymerization.

The exact polymerization conditions, in particular the nature, Dosie tion and amount of the emulsifier are preferably chosen so that the latex of the acrylic ester, which is at least partially crosslinked, an average particle size (weight average d ₅₀ ) in the range of about 200 to 700, in particular from 250 to 600 nm. Preferably, the latex has a narrow particle size distribution, ie the quotient

is preferably less than 0.5, in particular less than 0.35.

The proportion of the graft to the graft polymer A ₁ A ₁ + A ₂ is 50 to 90, preferably 55 to 85 and in particular 60 to 80 wt .-%, based on the total weight of A ₁ + _A2.

On the graft A ₁ , a graft A _{2 is} grafted by copolymerization of
A ₂₁ 20 to 90, preferably 30 to 90 and in particular 30 to 80 wt .-% of styrene or substituted styrenes of the general formula

wherein R represents alkyl radicals having 1 to 8 C atoms, hydrogen atoms or halogen atoms and R ^{1 represents} alkyl radicals having 1 to 8 C atoms or halogen atoms and n is 0, 1, 2 or 3, and
A ₂₂ 10 to 80, preferably 10 to 70 and in particular 20 to 70 wt .-% of acrylonitrile, methacrylonitrile, acrylic acid esters or methacrylic acid esters or mixtures thereof is available.

Examples of substituted styrenes are α-methylstyrene, p-methylstyrene, p-chlorostyrene and p-chloro-α-methylstyrene, of which styrene and α-methylstyrene are preferred.

Preferred acrylic or methacrylic acid esters are those whose homopolymers or copolymers with the other monomers of component A ₂₂ ) have glass transition temperatures of more than 20 ° C; In principle, however, other acrylic acid esters may also be used, preferably in amounts such that the overall result for component A _{2 is} a glass transition temperature T _g above 20 ° C.

Particularly preferred are esters of acrylic or methacrylic acid with C ₁ -C ₈ -alcohols and epoxy-containing esters such as glycidyl acrylate or glycidyl methacrylate. As very particularly preferred examples are methyl methacrylate, t-butyl methacrylate, glycidyl methacrylate and n-butyl acrylate called, the latter due to its property to form polymers with very low T _g , is preferably used in not too high proportion.

The graft shell A ₂ ) may be in one or more, z. B. two or three, process steps are made, the gross composition remains unaffected.

Preferably, the graft shell is made in emulsion, such as this z. B. in DE-PS 12 60 135, DE-OS 32 27 555, DE-OS 31 49 357 and DE-OS 34 14 118 is described.

Depending on the selected conditions arises in the grafting mix polymerization a certain proportion of free copolymers of styrene or substituted styrene derivatives and (meth) acrylic nitrile or (meth) acrylic esters.

The graft copolymer A ₁ + A ₂ generally has an average particle size of 100 to 1000 nm, in particular from 200 to 700 nm, (d ₅₀ weight average). The conditions in the preparation of the elastomer D ₁ ) and in the grafting are therefore preferably chosen so that particle sizes result in this range. Measures are known and z. For example, in DE-PS 12 60 135 and DE-OS 28 26 925 and in Journal of Applied Polymer Science, Vol. 9 (1965), pp 2929-2938 described. The particle size increase of the latex of the elastomer may, for. B. be accomplished by agglomeration.

For the purposes of this invention, the graft polymer (A ₁ + A ₂ ) also includes the free, non-grafted homopolymers and copolymers which are formed in the graft copolymerization to prepare component A ₂ ).

The following are some preferred graft polymers:

• 1. 60% by weight of the grafting base A ₁
  A ₁₁ 98 wt .-% n-butyl acrylate and
  A ₁₂ 2 wt .-% Dihydrodicyclopentadienylacrylat and
  40 wt .-% graft A ₂ from
  A ₂₁ 75 wt .-% of styrene and
  A ₂₂ 25 wt .-% acrylonitrile
• 2. Pfropfgrundlage as in 1 with 5 wt .-% of a first graft shell of styrene and
  35 wt .-% of a second graft
  A ₂₁ 75 wt .-% of styrene and
  A ₂₂ 25 wt .-% acrylonitrile
• 3. Grafting base as in 1 with 13 wt .-% of a first graft stage of styrene and 27 wt .-% of a second grafting Styrene and acrylonitrile in a weight ratio of 3: 1.

The products contained as component A ₃ ) may, for. B. according to the method described in DE-AS 10 01 001 and DE-AS 10 03 436 Ver. Also commercially available such copolymers are available. Preferably, the weight average molecular weight determined by light scattering is in the range of 50,000 to 500,000, especially 100,000 to 250,000.

The weight ratio of (A ₁ + A ₂ ): A ₃ is in the range of 1: 2.5 to 2.5: 1, preferably 1: 2 to 2: 1, and more preferably 1: 1.5 to 1.5 : 1.

Suitable SAN polymers as component A) are described above (see A ₃₁ and A ₃₂ ).

The viscosity number of the SAN polymers, measured according to DIN 53 727 as 0.5 wt .-% solution in dimethylformamide at 23 ° C. is generally in the range of 40 to 100, preferably 50 to 80 ml / g.

ABS polymers as polymer (A) in the multiphase polymer mixtures according to the invention have the same structure as described above for ASA polymers. Instead of the acrylate rubber A ₁ ) of the grafting base in the ASA polymer, conjugated dienes are usually used, so that preferably the following composition results for the grafting base Aq:
A ₄₁ 70 to 100 wt .-% of a conjugated diene and
A ₄₂ 0 to 30 wt .-% of a difunctional monomer having two olefinic non-conjugated double bonds.

Grafting A ₂ and the hard matrix of the SAN copolymer A ₃ ) remain unchanged in the composition. Such products are commercially available. The production methods are known to the person skilled in the art, so that further details are unnecessary.

The weight ratio of (A ₁ + A ₂ ): A ₃ is in the range of 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

Particularly preferred compositions of the molding compositions according to the invention comprise, as component A), a mixture of:
A ₁ ) 10 to 90 wt .-% of a polybutylene terephthalate
A ₂ ) 0 to 40 wt .-% of a polyethylene terephthalate
A ₃ ) 1 to 40 wt .-% of an ASA or ABS polymers or mixtures thereof.

Such products are under the trademark Ultradur® S (eh UltraBrend® S) from BASF Aktiengesellschaft.

Further preferred compositions of component A)
A ₁ ) 10 to 90 wt .-% of a polycarbonate
A ₂ ) 0 to 40% by weight of a polyester, preferably polybutylene terephthalate,
A ₃ ) 1 to 40 wt .-% of an ASA or ABS polymers or mixtures thereof.

Such products are under the trademark Terblend® the BASF AG available.

3. polyamides

The polyamides of the molding compositions according to the invention have in all Commonly a viscosity number of 90 to 350, preferably 110 to 240 ml / g determined in a 0.5% by weight solution in 96 wt .-% sulfuric acid at 25 ° C in accordance with ISO 307th

Semicrystalline or amorphous resins having a molecular weight (Weight average) of at least 5000, as z. Tie U.S. 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 to be written are preferred.

Examples of these are polyamides, which differ from lactams with 7 to Derive 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides prepared by reaction of Dicarboxylic acids are obtained with diamines.

As dicarboxylic acids are alkanedicarboxylic acids with 6 to 12, esp in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids used. Here are only adipic acid, azelaic acid, sebacin acid, dodecanedioic acid and terephthalic and / or isophthalic acid as Called acids.  

Suitable diamines are particularly alkanediamines with 6 to 12, ins particular 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-aminocyclohexyl) -propane.

Preferred polyamides are polyhexamethylene adipamide, poly hexamethylene sebacic acid amide and polycaprolactam and copoly amide 6/66, in particular with a content of 5 to 95 wt .-% of Caprolactam units.

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

Furthermore, polyamides obtained by copolymerization of two or more of the aforementioned monomers are available, or Mixtures of several polyamides suitable, wherein the mixture relationship is arbitrary.

Furthermore, such partially aromatic copolyamides have PA 6 / 6T and PA 66 / 6T proved to be particularly advantageous, the Triamine content less than 0.5, preferably less than 0.3 wt .-% is (see EP-A 299 444).

The preparation of the preferred partially aromatic copolyamides with low triamine content can after the in EP-A 129 195 and 129 196 procedures described.

4. polyphenylene ether

Suitable polyphenylene ethers generally have a molecular weight weight (mean weight) in the range of 10 000 to 80 000, preferably from 20,000 to 60,000 and in particular from 40,000 up to 55 000 on.

The molecular weight distribution is generally gel permeation chromatography (GPC). For this purpose, PPE Samples dissolved in THF under pressure at 110 ° C. At room temperature with THF as the eluent 0.16 ml of a 0.25% solution injected on suitable separation columns. The detection is done all in common with a UV detector. The separation columns are appropriate calibrated with PPE samples of known molecular weight distribution.  

This corresponds to a reduced specific viscosity η _{red of} from 0.2 to 0.9 dl / g, preferably from 0.35 to 0.8 and in particular from 0.45 to 0.6, measured in a 0.5% by weight. solution in chloroform at 25 ° C.

The unmodified polyphenylene ethers a ₁ ) are known per se and are preferably prepared by oxidative coupling of phenols disubstituted in the o-position.

As examples of substituents, halogen atoms such as chlorine or Chromium and alkyl radicals having 1 to 4 carbon atoms, the preferential have no α-tertiary tertiary hydrogen atom, for. B. Methyl, ethyl, propyl or butyl radicals. The alkyl In turn, radicals can be replaced by halogen atoms such as chlorine or bromine or be substituted by a hydroxyl group. Further examples possible substituents are alkoxy, preferably up to 4 carbon atoms or optionally by halogen atoms and / or alkyl groups substituted phenyl radicals. Also suitable are copolymers of various phenols such. B. copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Of course It is also possible to use mixtures of different polyphenylene ethers become.

The polyphenylene ethers used as component a ₁ ) may optionally contain process-related defects, which are described in, for example, White et al., Macromolecules 23, 1318-1329 (1990).

Preferably, such polyphenylene ethers are used with vinyl aromatic polymers compatible, d. H. whole or far are soluble in these polymers (see A. Noshay, Block Copolymers, pp. 8-10, Academic Press, 1977 and O. Olabisi, Po lymer-Polymer Miscibility, 1979, p. 117 to 189).

Examples of polyphenylene ethers are poly (2,6-dilauryl-1,4-pheny len) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimeth oxi-1,4-phenylene) ether, poly (2,6-diethoxy-1,4-phenylene) ether, Poly (2-methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-ethyl-6-stea ryloxy-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, Poly (2-methyl-6-phenyl-1,4-phenylene) ether, poly (2,6-dib cyl-1,4-phenylene) ether, poly (2-ethoxy-1,4-phenylene) ether, Poly (2-chloro-1,4-phenylene) ether, poly (2,5-dibromo-1,4-pheny len) ether. Preference is given to using polyphenylene ethers, in where the substituents are alkyl radicals having 1 to 4 carbon atoms are such as poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-di ethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-pheny len) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether,  Poly (2,6-dipropyl-2,4-phenylene) ether and poly (2-ethyl-6-pro ether pyl-1,4-phenylene).

Furthermore, graft copolymers of polyphenylene ether and vinyl aromatic polymers such as styrene, α-methylstyrene, vinyltoluene and chlorostyrene suitable.

Functionalized or modified polyphenylene ethers are on known, for. From WO-A 86/02 086, WO-A 87/00 540, EP-A-222,246, EP-A-223,116 and EP-A-254,048 and are preferred used for blends with PA or polyester.

Usually, an unmodified polyphenylene ether a ₁ ) is prepared by incorporation of at least one carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea , Lactam or halobenzyl modified so that a sufficient compatibility Ver z. B. is ensured with the polyamide.

The modification is generally carried out by reacting an unmodified polyphenylene ether a ₁ ) with a modifying agent which contains at least one of the abovementioned groups and at least one C-C double or C-C triple bond in solution (WO-A 86/2 086). , in aqueous dispersion, in a gas phase method (EP-A-25 200) or in the melt, optionally in the presence of suitable vinyl aromatic polymers or impact modifiers carried out, optionally free radical initiator may be present.

Suitable modifiers (a ₃ ) are, for example, maleic acid, methylmaleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the mono- and diesters of these acids, for. B. from C ₁ - and C ₂ - to C ₈ -alkanols (a ₃₁ ), the mono- or diamides of these acids such as N-phenylmaleimide (monomers a ₃₂ ), maleic hydrazide. Furthermore, mention may be made, for example, of N-vinylpyrrolidone and (meth) acryloylcaprolactam (a ₃₃ ).

A modified polyphenylene ether is preferably used in the molding compositions according to the invention as component A), which is prepared by reacting

• 1.a ₁ ) 70 to 99.95, preferably 76.5 to 99.94 wt .-% of an unmodifi ed polyphenylene ether,
• 2. a ₂ ) 0 to 25, preferably 0 to 20 wt .-% of a vinyl aromatic polymer,
• 3. a ₃ ) 0.05 to 5, preferably 0.05 to 2.5 wt .-% of at least one compound formed from the group
  • 1. a ₃₁ ) an α, β-unsaturated dicarbonyl compound,
  • 2. a ₃₂ ) of an amide group-containing monomer having a poly merisierbaren double bond and
  • 3. a ₃₃ ) a lactam group-containing monomer having a polymerizable double bond,
• 4.a ₄ ) 0 to 5, preferably 0.01 to 0.09 wt .-% of a radical starter,

where the percentages by weight are based on the sum of a ₁

) to a ₄

) be in the course of 0.5 to 15 minutes at 240 to 375 ° C in suitable mixing and kneading aggregates such as twin-screw extruders is available.

The vinyl aromatic polymer a ₂ ) should preferably be compatible with the translated polyphenylene ether, as described above under 2.

Examples of preferred, compatible with polyphenylene ethers vinylaromatic polymers are the already mentioned monograph from Olabisi, pp. 224 to 230 and 245.

Radical starters a ₄ ) may be mentioned:
Di- (2,4-dichlorobenzoyl) peroxide, tert-butyl peroxide, di- (3,5,5-trimethylhexanol) peroxide, dilauroyl peroxide, didecanoyl peroxide, dipropionyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexoate, tert-butyl peroxydiethylacetate , tert-butyl peroxyisobutyrate, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butylperoxy-3,3,5-trimethylhexoate, tert-butyl peracetate, tert-butyl perbenzoate, 4,4-di-tert-butyl peroxyvaleric acid butyl ester, 2,2-di-tert-butyl peroxybutane, dicumyl peroxide, tert-butylcumyl peroxide, 1,3-di- (tert-butylperoxyisopropyl) benzene and di-tert-butyl peroxide. Mention may also be made of organic hydroperoxides such as di-isopropylbenzene monohydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, p-methyl hydroperoxide and pinane hydroperoxide and highly branched alkanes of the general structure

where R ¹ to R ^{6 are} alkyl groups having 1 to 8 C atoms, alkoxy groups having 1 to 8 C atoms, aryl groups such as phenyl, naphthyl or 5- or 6-membered heterocycles having a π-electron system and nitrogen, oxygen or sulfur as heteroatoms represent. The substituents R ¹ to R ⁶ may in turn contain functional groups as substituents, such as carboxyl, carboxyl derivative, hydroxyl, amino, thiol or epoxy groups. Examples are 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane and 2,2,3,3-tetraphenylbutane.

Particularly preferred polyphenylene ether A) in the Invention according to the molding compositions by modification with maleic acid, Maleic anhydride and fumaric acid. Such poly phenylene ethers preferably have an acid number of 1.8 to 3.2, especially from 2.0 to 3.0.

The acid number is a measure of the degree of modification of the poly phenylene ether and is generally by titration with bases determined under inert gas conditions.

The acid number generally corresponds to the amount of base in mg, which for the neutralization of 1 g of such an acid-modified Polyphenylenethers B) is required (according to DIN 53 402).

5. Thermoplastic polyurethanes

Other suitable thermoplastics are thermoplastic poly called urethanes (TPU), as described for example in the EP-A 115 846 and EP-A 115 847 and EP-A 117 664 described are.

Suitable TPUs can be prepared, for example, by imple mentation of

• a) organic, preferably aromatic diisocyanates,
• b) polyhydroxyl compounds having molecular weights of 500 to 8000 and  
• c) chain extenders with molecular weights of 60 to 400 in the presence of, if appropriate
• d) catalysts,
• e) Auxiliaries and / or additives.

For the starting materials (a) to (c), catalysts (d), auxiliaries and additives (e) that can be used for this purpose, we would like to carry out the following:

• a) As organic diisocyanates (a) are, for example aliphatic, cycloaliphatic and preferably aromatic Diisocyanates into consideration. In detail, be ge exemplary Aliphatic diisocyanates, such as hexamethylene diisocya nat, cycloaliphatic diisocyanates, such as isophorone diisocya nat, 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and -2,6-cy clohexane diisocyanate and the corresponding isomers mixtures of 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocya nat and the corresponding isomer mixtures and preference example, aromatic diisocyanates, such as 2,4-tolylene diisocyanate, Mixtures of 2,4- and 2,6-toluene diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate. Mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'- and / or 2,4'-diphenylmethane diisocyanates, 4,4'-diiso cyanato-diphenylethane (1,2) and 1,5-naphthylene diisocyanate. Preferably used are hexamethylene diisocyanate, iso Phoron diisocyanate, 1,5-Naphthylendiisocyanat, Diphenylme than-diisocyanate isomer mixtures with a 4,4'-Diphenylme than diisocyanate content of greater than 96 wt .-% and ins particular 4,4'-diphenylmethane diisocyanate.
• b) As higher molecular weight polyhydroxyl compounds (b) with Molekularu large weights of 500 to 8000 are preferably poly etherols and polyesterols. However, hydroxyl-containing polymers, for example polyacetals, such as polyoxymethylenes and especially water-insoluble formals, eg. B. Polybutandiolformal and Polyhexandiolformal, and poly carbonates, in particular those of diphenyl carbonate and 1,6-hexanediol, prepared by transesterification, with the above-mentioned molecular weights. The polyhydroxyl compounds must be at least predominantly linear, ie difunctional in the sense of the isocyanate reaction. The polyhydroxyl compounds mentioned can be used as individual components or in the form of mixtures.
  Suitable polyetherols can be prepared by reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule containing bound two active hydrogen atoms. As alkylene oxides are z. B. called: ethylene oxide, 1,2-propylene oxide, 1,2- and 2,3-butylene oxide. Preferably used are ethylene oxide and mixtures of propylene oxide-1,2 and ethylene oxide. The alkylene oxides can be used individually, alternately one after the other or as a mixture. Examples of suitable starter molecules are: water, amino alcohols, such as N-alkyldiethanolamines, for example N-methyldiethanolamine and diols, such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. Optionally, mixtures of starter molecules can be used. Suitable polyetherols are also the hydroxyl-containing polymerization of tetrahydrofuran (Polyoxytetra methylenglykole).
  Preferably used are polyetherols of propylene oxide-1,2 and ethylene oxide, in which more than 50%, preferably, 60 to 80% of the OH groups are primary hydroxyl groups and in which at least a portion of the ethylene oxide is arranged as end-permanent block; z. B. in particular polyoxy tetramethylene glycols.
  Such polyetherols can be obtained by z. B. to the starter molecule first, the propylene oxide-1,2 and then the polymerized ethylene oxide or first copolymerized all the propylene oxide-1,2 in admixture with a portion of the ethylene oxide and the remainder of the ethylene oxide then polymerized or gradually first a portion of the ethylene oxide, then all of the propylene oxide-1,2 and then the remainder of the ethylene oxide, grafted to the starter molecule.
  The substantially linear polyetherols have molecular weights of 500 to 8000, preferably 600 to 6000 and in particular 800 to 3500. They can be used both individually and in the form of mixtures with one another.
  Suitable polyesterols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms and polyhydric alcohols. Examples of suitable dicarboxylic acids are:
  aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, eg. B. be used in the form of an amber, glutaric and adipic acid mixture. Likewise, mixtures of aromatic and aliphatic dicarboxylic acids can be used. For the preparation of the polyesterols it may be advantageous, if appropriate, to use the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters having 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid chlorides, instead of the dicarboxylic acids. Examples of polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, pentanediol-1,5, hexanediol-1,6, decanediol-1, 10, 2, 2-dimethylpropanediol-1,3, propanediol-1,3 and dipropylene glycol. Depending on the desired properties, the polyhydric alcohols can be used alone or, if appropriate, in mixtures with one another.
  Also suitable are esters of carbonic acid with the diols mentioned, in particular those having 4 to 6 carbon atoms, such as 1,4-butanediol and / or 1,6-hexanediol, condensation products of ω-hydroxycarboxylic acids, for example ω-hydroxy caproic acid and preferably polymerization products of Lactones, for example optionally substituted ω-caprolactones.
  As polyesterols are preferably used Dialkylengly kol-polyadipate having 2 to 6 carbon atoms in the alkylene radical, such as. B. Ethandiol polyadipate, 1,4-butanediol polyadipate, ethanediol-butanediol-1,4-polyadipate, 1,6-hexanediol neopentyl glycol polyadipate, polycaprolactones and in particular 1,6-hexanediol-1,4-butanediol polyadipates.
  The polyesterols have molecular weights of 500 to 6000, preferably from 800 to 3500.
• c) As chain extenders (c) having molecular weights of 60 to 400, preferably 60 to 300, are preferably aliphatic diols having 2 to 12 carbon atoms, preferably with 2, 4 or 6 carbon atoms, such as. As ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular butanediol-1,4 into consideration. However, also suitable are diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, such as. As terephthalic acid-bis-ethylene glycol or -butandiol-1,4, hydroxyalkylene ethers of hydroquinone, such as. B. 1,4-di- (β-hydroxyethyl) hydroquinone, (cyclo) aliphatic diamines, such as. 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, isophorone-diamine, ethylenediamine, 1,2-, 1,3-propylenediamine, N-methyl-propylenediamine -1,3, N, N'-dimethyl-ethylenediamine and aromatic diamines, such as. B. 2,4- and 2,6-tolylenediamine, 3,5-diethyl-2,4- and -2,6-toluenediamine diamine and primary ortho-di-, tri- and / or tetraalkyl-substituted 4,4'- Diamino diphenylmethane.
  To adjust the hardness and melting point of the TPU, the synthesis components (b) and (c) can be varied in relatively wide molar ratios. Molar ratios of polyhydroxyl compounds (b) to chain extenders (c) of from 1: 1 to 1:12, in particular from 1: 1.8 to 1: 6.4, have proven successful, with the hardness and the melting point of the TPU increasing Content of diols increases.
  To prepare the TPU, the synthesis components (a), (b) and (c) are reacted in the presence of optionally catalysts (d), auxiliaries and / or additives (e) in amounts such that the equivalence ratio of NCO groups of Diisocyanates (a) to the sum of the hydroxyl groups or hydroxyl and amino groups of components (b) and (c) 1: 0.85 to 1.20, preferably 1: 0.95 to 1: 1.05 and in particular 1: 0 , 98 to 1.02.
• d) Suitable catalysts, which in particular the reaction between the NCO groups of the diisocyanates (a) and the Hydroxyl groups of the structural components (b) and (c) Beschleuni are known in the art and customary tertiary amines, such as. Triethylamine, dimethyl cyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and similar and in particular organic metal compounds such as titanic acid esters, iron compounds such as. B. ferric (III) - acetyl-acetonate, tin compounds, e.g. As tin diacetate, tin dioctoate, tin dilaurate or the Zinndialkylsalze aliphati shear carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or similar. The catalysts become more common in amounts of 0.001 to 0.1 parts per 100 parts of poly hydroxyl compound (b) used.

In addition to catalysts, the structural components (a) to (c) can also Additives and / or additives (e) are incorporated. Called For example, lubricants, inhibitors, stabilizers ge Hydrolysis, Light, Heat or Discoloration, Dyes, Pig mente, inorganic and / or organic fillers and Weichma  and additives for the production of foamed TPU Moldings.

Further information on the above auxiliary and additional Materials are the specialist literature, for example, the monograph of J.H. Saunders and K.C. Frisch "High Polymers", Vol. XVI, Polyure thane, Part 1 and 2, published by Interscience Publishers 1962 and 1964 or DE-OS 29 01 774 can be seen.

As component B), the molding compositions according to the invention contain 1 to 50, preferably 5 to 30 and in particular 5 to 20 wt .-% of a mixture of

• 1. b ₁ ) at least one phosphorus compound and
• 2. b ₂ ) at least one stabilizer compound of the general formulas I to IV
  in which
  R ¹ , R ² independently of one another are a hydrogen, C ₁ - to C ₁₀ -alkyl, C ₆ - to C ₁₂ -aryl, C ₇ - to C ₁₃ -aralkyl, C ₇ - to C ₁₃ -alkylaryl radical,
  a, b are independently 1 to 5,
  c, d are independently 0 to 10;
  
  in which
  R ^{3 is} a hydrogen, C ₁ - to C ₁₀ -alkyl, C ₆ - to C ₁₂ -aryl, C ₇ - to C ₁₃ -aralkyl, C ₇ - to C ₁₃ -alkyl aryl radical,
  e 1 to 4,
  f 1 to 100;
  in which
  R ⁴ , R ¹³ independently of one another NCO or NHCOOR ', where R' is an alkylpolyether glycol or an alcohol having 1 to 20 C atoms,
  R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^{12 are} independently hydrogen, C ₁ - to C ₁₀ alkyl, C ₆ - to C ₁₂ aryl, C ₇ to C ₁₃ aralkyl, C ₇ to C ₁₃ alkylaryl radical,
  g 0 to 5,
  h 1 to 100;
  in which
  R ¹⁴ , R ¹⁵ , R ¹⁶ independently of one another hydrogen radical or
  in which
  R ^{17 is} a hydrogen, C ₁ - to C ₂₀ -alkyl, C ₆ - to C ₁₂ -aryl, C ₇ - to C ₁₃ -aralkyl radical, C ₇ - to C ₁₃ -alkylaryl radical,
  i 2 to 8,
  j 1 to ik
  k 0 to i, where j + k ≦ i
  or at least two of them, or
  (CH ₂ ) ₁ -N = C = O, where l is 1 to 20, dissolved
  

mean.

According to the invention, R ¹ and R ^{2 are} each, independently of one another, preferably C ₁ - to C ₁₀ -, more preferably C ₁ - to C ₄ - and, moreover, preferably C ₃ -alkyl radical. Of these, a 2-propyl radical is particularly preferred.

The variables a and b are each independently of one another preferably 1, 2, 3 or 4 and more preferably 2. In the case where a and b are each 2, the corresponding ones are. Radicals R ¹ and R ^{2 in} each case on the carbons in adjacent position to the carbon to which the NCN group on the benzene ring closes.

In addition to the C ₆ - to C ₁₂ -aryl radicals, particular preference is given to C ₆ - to C ₁₀ -aryl and C ₆ - to C ₈ -aryl being preferred. Of the abovementioned aryl radicals, particular preference is given to phenyl and naphthyl radicals. Preferred aralkyl radicals having preferably 7 to 14 carbon atoms are toluene, xylyl, tert-butyl-phenyl and di-tert-butyl-phenyl. As the alkylaryl group having preferably 7 to 14 carbon atoms, benzyl is preferable.

In the present invention, the variables c and d are independently Other preferably 0, 1, 2, 3, 4 or 5 and more preferably 0, 1 or 2. It is furthermore preferred if c and d are each because 0 are.

For the preferred meaning of radical R ³ according to the invention, the remarks on radicals R ¹ and R ² apply.

Preferably, the variable e is 1, 2 or 3 and more preferably 3. In the event that the variable e is 3, it is preferred that the radicals R ^{3 are} each bonded to the carbon atoms of the benzene ring adjacent to them to which a nitrogen is bound.

The integer variable f preferably has the values in the range from 1 to 50, and more preferably in the range of 1 to 20.

R 'is preferably derived from a C ₁ to C ₁₀ and more preferably C ₂ to C ₅ alcohol. Among these alcohols, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol and isopentanol are again preferred, with ethanol being particularly preferred.

When R 'is an alkylpolyether glycol, C ₁ to C ₁₀ alkylpolyether glycols are preferred and C ₁ to C ₅ alkylpolyether glycols are particularly preferred. Of these, in turn, methyl, ethyl, propyl, Isopropylpolyetherglycole are preferred and Methylpolyetherglycol be particularly preferred.

For the preferred meanings of R ^5, R ^6, R ^7, R ^8, R ^9, R ^10, R ¹¹ and R ^12, the statements made to R ¹ and R ² with the Un apply terschied that instead of 2-Propylrestes here a methyl radical is particularly preferred.

The variable g preferably has the values 0, 1, 2, 3 and be more preferably 0. The variable h preferably has the values 1, 2, 3, 4, 5, 6, 7, 9 or 10 and more preferably the values 2, 3, 4, 5, 6.

In the radicals R ¹⁴ , R ¹⁵ and R ¹⁶ , it is preferred that these are not a hydrogen atom.

For R ¹⁷ , the same applies to R ⁵ to R ¹² . The varia ble i is preferably 3, 4 or 5 and more preferably 5, so that forms a cyclohexyl ring with the carbon over which the cyclic radical is attached to the nitrogen of the heterocycle. Furthermore, it is preferable that the variable i is 1.

In the event that a cyclohexyl ring is formed, the variable k is preferably 4. In this case, it is again preferred that in each case 2 of 4 radicals R ¹⁷ are bonded to one carbon of the cyclohexyl ring and to the other, also 2 radicals R ¹⁷ carrying carbon, are spaced by an intermediate carbon material.

A preferred embodiment of the molding compositions according to the invention contains 0.01 to 50 wt .-%, preferably I to 20 wt .-%, in particular 0.05 to 2 wt .-%, based on 100% component B), of at least one stabilizer compound b ₂ ) and 99, 99 to 50 wt .-%, preferably 99 to 80 and in particular 99.95 to 98 wt .-%, of at least one phosphorus compound b ₁ ).

According to preferred phosphorus compounds have 6 to 120, preferably 6 to 80 and more preferably 8 to 40 carbon atoms.

All the phosphorus compounds known to those skilled in the art come into consideration. Of these, in particular the organic phosphorus compounds are preferred, which are used industrially or in which a low storage stability or a high corrosion tendency or both. Among these organic phosphorus compounds, those having the general formula (V) are particularly preferred.

in which
R ¹⁸ , R ¹⁹ , R ²⁰ independently of one another are an alkyl, alkylaryl, arylalkyl or cycloalkyl radical having 7 to 40 carbon atoms,
X is a sulfur or oxygen atom,
m, n, o independently of one another denote 0 or 1.

In one embodiment of the phosphorus compound with the general In my formula V it is preferred that two of the variables m, n and o is 0 and a 1 means.

Examples of phosphine oxides as phosphorus compounds are tri phenylphosphine oxide, tritolylphosphine oxide, trisnonylphenyl phosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, tris (n-octyl) phosphine oxide, Tris (cyanoethyl) phosphine oxide, benzylbis (cyclohexyl) phosphine oxide, benzylbisphenylphosphine oxide, phenylbis - (n-hexyl) phosphine oxide. Preference is furthermore given to oxidized reaction products Phosphine with aldehydes, in particular from t-butylphosphine with Glyoxal. Particular preference is given to using triphenylphosphine oxide, tricyclohexylphosphine oxide and tris (n-octyl) phosphine oxide.  

Also suitable as a phosphorus compound is triphenylphosphine fid and its derivatives of phosphine oxides as described above and triphenyl phosphate.

Phosphorus compounds of the valence state ± 0 is elemental Phosphorus. Eligible are red and black phosphorus. Prefers is red phosphorus.

Phosphorus compounds of the "oxidation state" +1 are z. B. Hypo phosphite. Examples are organic hypophosphites, such as Cellulose hypophosphite esters, esters of hypophosphorous acids with Diols, such as. B. of 1,10-dodecyldiol. Also substituted Phosphinic acids and their anhydrides, such as. B. diphenylphosphine acid, can be used. Furthermore, there are p-Tolylphosphinic acid, di-cresylphosphiric anhydride. It come but also compounds such as hydroquinone, ethylene glycol, propy glycol bis (diphenylphosphinic) ester u. a. in question. Further are suitable aryl (alkyl) phosphinic acid amides, such as. B. diphenyl phosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphine acid derivatives, such as. B. p-Tolylsulfonamidodiphenylphosphine acid. Hydroquinone and ethylene glycol are preferably used col-bis (diphenylphosphinic) ester and the bis-diphenyl Phosphinate of hydroquinone.

Preferred phosphorus compounds are, in particular, phosphinic acid salts of the formulas (VI) and / or diphosphinic acid salts of the formula (VII) or their polymers or mixtures thereof

where the substituents have the following meanings:
R ¹ , R ^{2 is} hydrogen, C ₁ -C ₆ alkyl, preferably C ₁ -C ₄ alkyl, linear or branched, z. Methyl, ethyl, n -propyl, isopropyl, n -butyl, tert -butyl, n -pentyl; where preferably at least one radical R ¹ or R ² , in particular R ¹ and R ² , is hydrogen,
R ^{3 is} C ₁ -C ₁₀ -alkylene, linear or branched, e.g. Methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-penty len, n-octylene, n-dodecylene;
Arylene, e.g. Phenylene, naphthylene;
Alkylarylene, e.g. Methyl-phenylene, ethyl-phenylene, tert-butyl-phenylene, methyl-naphthylene, ethyl-naphthylene, tert-butyl-naphthylene;
Aralkylene, z. Phenyl-methylene, phenyl-ethylene, phenyl-propylene, phenyl-butylene;
M is an alkaline earth, alkali metal, A ₁ , Zn, Fe, boron, Ti, Zr;
m is an integer of 1 to 3;
n is an integer from 1 to 3;
x 1 or 2.

Particularly preferred are compounds in which R ¹ and R ² is hydrogen, wherein M is preferably A ₁ or Zn and Calciumphosp hinat is very particularly preferred.

Such products are commercially available for. B. as calcium hypophosphite available.

Suitable salts of formula (V1) or (VII) in which only one radical R ¹ or R ^{2 is} hydrogen are sodium benzene phosphinate (Na [HC ₆ H ₅ PO ₂ ]) and calcium benzene phosphinate and Zn ((CH ₃ ) ₂ PO ₂ ) ₂ , Zn ((C ₂ H ₅ ) CH ₃ PO ₂ ) ₂ and Al [(C ₂ H ₅ ) (CH ₃ ) PO ₂ ] ₃ .

Processes for the preparation are known from EP-A 699 708 and BE-A 875 530 known.

Phosphorus compounds of the oxidation state +3 are derived from the phosphorous acid. Suitable are cyclic phosphonates derived from pentaerythritol, neopentyl glycol or catechol as in general formula VIII

where R "is a C ₁ - to C ₄ -alkyl radical, preferably methyl radical, P = 0 or 1 (Amgard® P45 from Albright & Wilson).

Further, phosphorus of valence state +3 is in tri aryl (alkyl) phosphites, such as. B. triphenyl phosphite, tris (4-decyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris nonylphenyl phosphite (eg Irgaphos® TNPP from Ciba Geigy AG) or phenyldidecyl phosphite u. a. contain. But it comes also diphosphites, such as. For example, propylene glycol 1,2-bis (diphosphite) or cyclic phosphites other than pentaglythritol, neopentyl derive glycol or catechol in question.

Particularly preferred as phosphorus compounds of Oxidation state +3 methylneopentyl glycol phosphonate and phosphite and dimethyl pentaerythritol diphosphonate and phosphite.

The most important phosphorus compounds of the +4 oxidation state are. Hypodiphosphates, such as. For example, tetraphenyl hypodiphosphate or bisneo pentyl-hypodiphosphate into consideration.

Suitable phosphorus compounds of the oxidation state +5 are, in particular, alkyl- and aryl-substituted phosphates. Examples are phenylbisdodecylphosphate, phenylethylhydrogenphosphate, phenylbis (3,5,5-trimethylhexyl) phosphate, ethyldiphenylphosphate, 2-ethylhexyldi (tolyl) phosphate, diphenylhydrogenphosphate, bis (2-ethylhexyl) -p-tolylphosphate, tritolylphosphate, bis ( 2-ethylhexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate, p-tolyl bis (2,5,5-trimethylhexyl) phosphate or 2-ethylhexyldiphenyl phosphate. Particularly suitable are phosphorus compounds in which each radical is an aryloxy radical. Especially suitable is tri phenyl phosphate and resorcinol bis (diphenyl phosphate) (RDP) and its ring-substituted derivatives of the general formula IX

in which
R ²¹ to R ^{24 is} an aromatic radical having 6 to 20 C atoms, preferably a phenyl radical which may be substituted by alkyl groups having 1 to 4 C atoms, preferably methyl,
R ^{25 is} a divalent phenol radical, preferred

with Y is -CH ₂ -, C =O, S, SO ₂ , -C (CH ₃ ) ₂ -, preferably -C (CH ₃ ) ₂ -
and q is an average value between 0.1 and 100, preferably 0.5 to 50, in particular 0.8 to 10 and especially 1 to 5.

Particularly preferred is the phosphorus compound of general formula X.

With
R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ independently of one another are hydrogen, C ₁ - to C ₆ -alkyl,
Z as the previously defined remainder Y
r, s, t, u are independently 1, 2, 3, 4 or 5, wherein 1 and the para position of the corresponding radical to the phosphorus is preferred.

The commercially available RDP products under the trademarks Fyroflex® RDP (Akzo Nobel) and CR 733-S (Daihachi) are conditional by the manufacturing process mixtures of approx. 85% RDP with approx. 2.5% triphenyl phosphate and about 12.5% oligomeric proportions, in where the degree of oligomerization is usually less than 10.  

Furthermore, cyclic phosphates can also be used as phosphorus be used. Particularly suitable here Diphenylpentaerythritol diphosphate and phenylneopentyl phosphate.

Except the above-mentioned low molecular weight phosphorus compounds are still oligomeric and polymeric phosphorus compounds in question.

Such polymeric, preferably halogen-free organic Phosphorus compounds with phosphorus in the polymer chain arise for example, in the production of pentacyclic, unsaturated Phosphorindihalogeniden, as described for example in DE-A 20 36 173 is described. The molecular weight measured by vapor pressure osmometry in dimethylformamide, the poly phospholine oxides should range from 500 to 7000, preferably range from 700 to 2000. The phosphor has this the oxidation state -1.

Furthermore, inorganic coordination polymers of Aryl (alkyl) phosphinic acids such as. For example, poly-b-sodium (I) -methyl phenylphosphinate can be used as phosphorus compounds. Your Preparation is given in DE-A 31 40 520. The phosphor has the oxidation number +1.

Furthermore, such, preferably halogen-free, polymers Phosphorus compounds by the reaction of a phosphonic acid chloride, such as. As phenyl, methyl, propyl, styryl and vinyl phosphonic dichloride with bifunctional phenols, such as. B. Hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, bisphenol, Tetramethylbisphenol-A arise.

Further, preferably halogen-free, polymeric phosphorus compounds contained in the molding compositions according to the invention may be by reaction of phosphorus oxychloride or phosphoric acid ester dichlorides with a mixture of mono-, bi- and trifunctional phenols and other hydroxyl groups carrying compounds produced (see Houben-Weyl-Müller, Thieme-Verlag Stuttgart, Organic Phosphorus Compounds Part II (1963)). Furthermore, polymeric phosphonates by transesterification Reactions of phosphonic acid esters with bifunctional phenols (see DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diamines or hydrazides (see U.S. Patent 4,403,075) getting produced. In question is also the inorganic Poly (ammonium phosphate).  

There may also be oligomeric pentaerythritol phosphites, phosphates and phosphonates according to EP-B 8486, z. B. Mobile Antiblazeâ 19 (eingetra trademark of the company Mobil Oil) as phosphorus compounds be used.

Furthermore, a component B) according to the invention is preferred which over a period of 1 to 100, preferably 2 to 50 and FITS It prefers 10 to 30 days from the time of contact bringing the phosphorus compound with the stabilizer compound a maximum of 20, preferably a maximum of 15 and most preferably a maximum 5% of the acid number at the time of contacting differs.

The phosphorus compound and the stabilizer compound and Gege if necessary, other auxiliary and auxiliary equipment usually to be given Substances can according to all those skilled in the well-known Procedures are brought into contact with each other. However, it has changed mixing in tanks with agitated mixers or mixing the for example, by a downpipe moving composition over proven a static mixer.

The composition of component B according to the invention preferably for increasing the storage stability or for reducing the metal corrosion tendency of phosphorus compounds used.

Usually, the storage stability on the deviation of Acid value over the storage period of the corresponding composition certainly.

As storage stability is preferred that the acid number over a Period of 5 days, preferably 2 weeks and more preferably one month by a maximum of 10, preferably a maximum of 5 and especially preferably at most 1% of the acid number at the beginning of vorgenann period.

The strength of the metal corrosion tendency results from the Ver same as before corrosion of a corresponding compound with or without stabilizer compound under otherwise identical conditions over a same period.

Particularly preferred stabilizer compounds include minde at least one of the following is represented by its structural formulas connections:  

Stabaxol® 1 (Rhein Chemie GmbH)

Stabaxol® p (Rhein Chemie GmbH)

Elastostab® (Elastogran GmbH)

with R = NHCOOR ', R' = methyl polyether glycol, R '= ethanol
R = NCO or reaction product
Carbodiimide-free isocyanurates:

Vestanat® 1890/100 (Hüls AG)

Basonat® H / 100 (BASF AG)

As component C), the thermoplastic molding compositions according to the invention 0 to 40, preferably 1 to 30, preferably 1 to 20, and in particular 5 to 15 wt .-% of a flame retardant, ver different from b ₁ ). Preferred flame retardants are for combination with b ₂ ), in particular nitrogen compounds.

The melamine cyanurate which is preferably suitable according to the invention (component C) is a reaction product of preferably equimolar amounts of melamine (formula XI) and cyanuric acid or isocyanuric acid (formulas XIa and XIb)

You get it z. B. by reaction of aqueous solutions of the starting compounds at 90 to 100 ° C. The commercially available product is a white powder with a mean particle size d ₅₀ of 1.5-7 μm.

Other suitable compounds (often as salts or adducts Melamine borate, oxalate, phosphate prim., -phos phat sec. and pyrophosphate sec., neopentyl glycol boric acid melamine and polymeric melamine phosphate (CAS No. 56 386-64-2).

Suitable guanidine salts are

CAS-No. G-carbonate 593-85-1 G-cyanurate prim. 70285-19-7 G-phosphate prim. 5423-22-3 G-phosphate sec. 5423-23-4 G-sulfate prim. 646-34-4 G-sulfate sec. 594-14-9 Pentaerythritborsäureguanidin N / A. Neopentylglycolborsäureguanidin N / A. Urea phosphate green 4861-19-2 urea cyanurate 57517-11-0 ammeline 645-92-1 ammelide 645-93-2 melem 1502-47-2 Melon 32518-77-7

For the purposes of the present invention, compounds are intended to be so probably z. B. benzoguanamine itself and its adducts or salts as also the nitrogen-substituted derivatives and its adducts or salts are understood.

Also suitable are ammonium polyphosphate (NH ₄ PO ₃ ) _n with n about 200 to 1000, preferably 600 to 800, and tris (hydroxyethyl) isocyanate (THEIC) of the formula XII

or its reaction products with aromatic carboxylic acids Ar (COOH) _m , which may optionally be present in admixture with each other, wherein Ar is a mono-, di- or trinuclear aromatic six-membered system and m is 2, 3 or 4.

Suitable carboxylic acids are, for example, phthalic acid, isoph thalian acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, mellophanic acid, Prehnic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalene dicar carboxylic acids and anthracene carboxylic acids.  

The preparation is carried out by reacting the tris (hydroxy ethyl) isocyanurates with the acids, their alkyl esters or theirs Halides according to the methods of EP-A 584 567.

Such reaction products are a mixture of monomeric and oligomeric esters, which may also be crosslinked. The degree of oligomerization is usually from 2 to about 100, preferably from 2 to 20. Preference is given to mixtures of THEIC and / or its reaction products with phosphorus-containing nitrogen compounds, in particular (NH ₄ PO ₃ ) _n or melamine pyrophosphate or polymeric melamine phosphate. The mixing ratio z. B. from (NH ₄ PO ₃ ) _n to THEIC is preferably 90 to 50 to 10 to 50, especially 80 to 50 to 50 to 20 wt .-%, based on the mixture of such components B).

Also suitable are benzoguanamine compounds of formula XIII

in the R, R 'straight-chain or branched alkyl radicals having 1 to 10 C atoms, preferably hydrogen, and in particular their Adducts with phosphoric acid, boric acid and / or pyrophosphoric acid.

Also preferred are allantoin compounds of the formula XIV

where R, R 'have the meaning given in formula XIII and their salts with phosphoric acid, boric acid and / or pyrophosphoric acid and glycolurils of the formula XV or its salts with the abovementioned acids

in which R has the meaning given in formula XIII.

Suitable products are commercially or according to DE-A 196 14 424 he hältlich.

The usable according to the invention cyanoguanidine (formula XVI) he holds z. B. by reaction of calcium cyanamide (calcium cyanamide) with carbon dioxide, wherein the resulting cyanamide dimerized at pH 9 to 10 to cyanoguanidine.

The commercially available product is a white powder with a Melting point from 209 ° C to 211 ° C.

As component D), the molding compositions 0 to 70, in particular up to 50 wt .-% of other additives enthal th.

As component D), the molding compositions 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2 wt .-% min at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22 C Atoms with aliphatic saturated alcohols or amines with 2 to 40, preferably 2 to 6 carbon atoms.

The carboxylic acids can be 1- or 2-valent. As examples pelargonic acid, palmitic acid, lauric acid, margaric acid, Do decanedioic acid, behenic acid and most preferably stearic acid, Capric acid and montanic acid (mixture of fatty acids with 30 bis 40 C-atoms).  

The aliphatic alcohols can be 1 to 4 valent. Examples for alcohols, n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, wherein Glycerol and pentaerythritol are preferred.

The aliphatic amines can be monohydric to trihydric. Examples these are stearylamine, ethylenediamine, propylenediamine, hexame thylenediamine, di (6-aminohexyl) amine, wherein ethylenediamine and hexa methylenediamine are particularly preferred. Preferred esters or Amides are correspondingly glycerol distearate, glycerol tristearate, Ethylene diamine distearate, glycerol monopalmitate, glycerol trilaurate, Glycerol monobehenate and pentaerythritol tetrastearate.

It is also possible to use mixtures of different esters or amides or Ester can be used in combination with amides, the Mi ratio is arbitrary.

Usual additives D) are, for example, in amounts up to 40, preferably up to 30% by weight of elastomeric polymers (often also as Schlagzähmodifier, elastomers or rubbers be characterized), which are different from component A).

In general, these are copolymers which are preferably composed of at least two of the following monomers:
Ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters having 1 to 18 carbon atoms in the alcohol component.

Such polymers are z. B. in Houben-Weyl, methods of orga nische Chemie, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by C. B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977) described.

The following are some preferred types of such elastomers presented.

Preferred types of such elastomers are the so-called ethylene Propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers.

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

As diene monomers for EPDM rubbers are konju greedy dienes such as isoprene and butadiene, non-conjugated dienes with 5 to 25 C atoms, such as penta-1,4-diene, hexa-1,4-diene, He  xa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-2,4-diene, cycli dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and Dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-nor bornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-iso propenyl-5-norbornene and tricyclodienes such as 3-methyl-tri cyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Preference is given to hexa-1,5-diene, 5-ethylidenenorbornene and dicyclo pentadiene. The diene content of the EPDM rubbers is vorzugswei 0.5 to 50, in particular 1 to 8 wt .-%, based on the Ge total weight of the rubber.

EPM or EPDM rubbers may preferably also be reactive Carboxylic acids or derivatives thereof may be grafted. Here are z. B. Acrylic acid, methacrylic acid and their derivatives, e.g. B. Glyci dyl (meth) acrylate, and called maleic anhydride.

Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. In addition, the rubbers can still di carboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, eg. As esters and anhydrides, and / or epoxy groups contained tend tend monomers. These dicarboxylic acid derivatives or epoxy-containing monomers are preferably incorporated by addition of dicarboxylic acid or epoxy groups containing monomers of all general formulas I or II or III or IV to the monomer mixture in the rubber

wherein R ¹ to R ^{9 represent} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer of 0 to 20, g is an integer of 0 to 10 and p is an integer of 0 to 5.

The radicals R ¹ to R ⁹ preferably denote hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

Preferred compounds of formulas I, II and IV are maleic acid maleic anhydride and epoxy group containing esters of Acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycine dylmethacrylate and the esters with tertiary alcohols, such as t-Bu tylacrylat. Although the latter have no free carboxyl groups but in their behavior they approach the free acids and are therefore termed monomers with latent carboxyl groups net.

Advantageously, the copolymers consist of 50 to 98 wt .-% Ethy len, 0.1 to 20 wt .-% of epoxy-containing monomers and / or Methacrylic acid and / or acid anhydride groups containing Monomers and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of
50 to 98, in particular 55 to 95 wt .-% ethylene,
0.1 to 40, in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and
1 to 45, in particular 10 to 40 wt .-% n-butyl acrylate and / or 2-ethylhexyl acrylate.

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

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

The ethylene copolymers described above can according to are prepared by known methods, preferably by random copolymerization under high pressure and elevated tem temperature. Corresponding methods are generally known.

Preferred elastomers are also emulsion polymers whose Her position z. As in Blackley in the monograph "Emulsion Polymeri The usable emulsifiers and kata Lystoren are known per se.

Basically, homogeneously constructed elastomers or sol be used with a shell structure. The cup-like Construction is determined by the order of addition of the individual monomers certainly; Also, the morphology of the polymers is from this addition order affected.

Only representative are here as monomers for the production the rubber part of the elastomers acrylates such. For example, n-butylacry lat and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof. These monomers can Kings nen with other monomers such. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl meth acrylate, methyl acrylate, ethyl acrylate and propyl acrylate copolymeri be siert.

The soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers may be the core, the outer shell or a middle shell (for elastomers with more than two) structure); in multi-shell elastomers can also consist of several shells of a rubber phase.

Are in addition to the rubber phase still one or more Hartkompo nents (with glass transition temperatures of more than 20 ° C) on the structure involved in the elastomer, they are generally by  Polymerization of styrene, acrylonitrile, methacrylonitrile, α-Me methylstyrene, p-methylstyrene, acrylic esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as Main monomers produced. In addition, here can lower Shares of other comonomers are used.

In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are for. For example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups by the concomitant use of monomers of the general formula

can be introduced
where the substituents may have the following meanings:
R ^{10 is} hydrogen or a C ₁ - to C ₄ -alkyl group,
R ^{11 is} hydrogen, a C ₁ - to C ₈ -alkyl group or an aryl group, in particular phenyl,
R ^{12 is} hydrogen, a C ₁ - to C ₁₀ -alkyl, a C ₆ - to C ₁₂ -aryl group or -OR ¹³
R ^{13 is} a C ₁ - to C ₈ -alkyl or C ₆ - to C ₁₂ -aryl group which may optionally be substituted by O- or N-containing groups,
X is a chemical bond, a C ₁ - to C ₁₀ -alkylene or C ₆ -C ₁₂ -arylene group or

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

Also, the graft monomers described in EP-A 208 187 are suitable for the introduction of reactive groups on the surface.

Other examples are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (N-t- Butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-diethylamino) ethyl called acrylate.

Furthermore, the particles of the rubber phase can also be crosslinked his. Crosslinking monomers are, for example, Bu ta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclo pentadienyl acrylate and those described in EP-A 50 265 Links.

Furthermore, so-called graft-crosslinking monomers (graft linking monomers), d. H. Monomers with two or more polymerizable double bonds in the polymerisati react on different speeds. Vorzugswei Such compounds are used in which at least one reactive group at about the same speed as the rest Monomers polymerized while the other reactive group (or reactive groups) e.g. B. polymerized much slower (Polymerize). The different rates of polymerization a certain amount of unsaturated dop pelbindungen in rubber with it. Will then be on a grafted another phase so react such rubber the double bonds present in the rubber at least partially with the grafting monomers to form chemical bonds gen, d. H. the grafted phase is at least partially over linked chemical bonds with the graft.

Examples of such graft-linking monomers are allyl groups containing monomers, in particular allyl esters of ethylenically un saturated carboxylic acids such as allyl acrylate, allyl methacrylate, Diallyl maleate, diallyl fumarate, diallyl itaconate or the like ing monoallyl compounds of these dicarboxylic acids. There are also there are a variety of other suitable graft-linking monomials rer; for more details, for example, on the U.S. Patent 4,148,846.

In general, the proportion of these crosslinking monomers on the toughening modifying polymer up to 5% by weight preferably not more than 3 wt .-%, based on the impact mod discriminating polymers.  

In the following, some preferred emulsion polymers are listed. First, graft polymers having a core and at least one outer shell, which have the following structure:

Instead of graft polymers having a multi-shell structure can also be homogeneous, d. H. single-shell elastomers from Bu ta-1,3-diene, isoprene and n-butyl acrylate or their copolymers be used. These products can also be used by others of crosslinking monomers or monomers having reactive groups getting produced.

Examples of preferred emulsion polymers are n-butyl acrylate lat / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers with an inner core of n-butyl acrylate or on buta dienbasis and an outer shell of the above Copolymers and copolymers of ethylene with comonomers, the reak deliver effective groups.

The elastomers described may also be other customary Method, for. B. by suspension polymerization, who made the.  

Silicone rubbers, as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are described if preferred.

Of course, mixtures of the above can be added led rubber types are used.

As fibrous or particulate fillers are coals fabric fibers, glass fibers, glass beads, amorphous silica, asbestos, Calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, Chalk, powdered quartz, mica, barium sulfate and feldspar ge called in amounts up to 50 wt. 4, In particular 1 to 40%, in particular 20 to 35 wt .-% are used.

Preferred fibrous fillers are carbon fibers, Aramid fibers and potassium titanate fibers called glass fibers are particularly preferred as E-glass. These can be called rovings or cut glass in the commercial forms.

The fibrous fillers can for better compatibility with the thermoplastic with a silane compound superficially pretreated.

Suitable silane compounds are those of the general formula

(X (CH ₂ ) _n ) _k -Si (OC _m H _{2m + 1} ) _4-k

in which the substituents have the following meanings:

X NH ₂ -,

n is an integer from 2 to 10, preferably 3 to 4
m is an integer from 1 to 5, preferably 1 to 2
k is an integer from 1 to 3, preferably 1.

Preferred silane compounds are aminopropyltrimethoxysilane, Aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyl triethoxysilane and the corresponding silanes, which as Substituent X contain a glycidyl group.

The silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1 wt .-% (based on D) used for surface coating.  

Also suitable are acicular mineral fillers.

Under acicular mineral fillers is in the sense of Invention a mineral filler with pronounced acicular character understood. As an example, be needle-shaped ger called wollastonite. Preferably, the mineral is one L / D (length diameter) ratio of 8: 1 to 35: 1 before given from 8: 1 to 11: 1. The mineral filler can optionally with the abovementioned silane compounds pretreated; however, the pretreatment is not necessarily required.

As further fillers are kaolin, calcined kaolin, Wollastonite, called talc and chalk.

As component D) the inventive thermoplastic Molding conventional processing aids such as stabilizers, Oxidation retardants, anti-heat decomposition and decomposition agents by ultraviolet light, lubricants and mold release agents, dyeing such as dyes and pigments, nucleating agents, Weichma cher etc.

As examples of oxidation inhibitors and heat stabilizers are sterically hindered phenols and / or phosphites, hydrochi none, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in Concentrations up to 1 wt .-%, based on the weight of called thermoplastic molding compositions.

As UV stabilizers, generally in amounts up to 2 wt .-%, based on the molding composition, are ver various substituted resorcinols, salicylates, benzotriazoles and Called benzophenones.

Inorganic pigments, such as titanium dioxide, ultramarine blue, Iron oxide and carbon black, and organic pigments such as phthalo cyanines, quinacridones, perylenes, and dyes such as nigrosine and Anthrachinone be added as colorant.

As nucleating agents, sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc are used.

Other lubricants and mold release agents which are commonly used in Amounts up to 1 wt .-% are used, are preferably long chain fatty acids (eg stearic acid or behenic acid), the Salts (eg Ca or Zn stearate) or montan waxes (mixtures from straight-chain, saturated carboxylic acids with chain lengths of  28 to 32 carbon atoms) and low molecular weight polyethylene or Po lypropylenwachse.

Examples of plasticizers are dioctyl phthalate, Dibenzyl phthalate, butyl benzyl phthalate, carbon hydrogenated oils, called N- (n-butyl) benzenesulfonamide.

The molding compositions according to the invention may still contain 0 to 2% by weight containing fluorine-containing ethylene polymers. This is it to polymers of ethylene having a fluorine content of 55 to 76 wt .-%, preferably 70 to 76 wt .-%.

Examples include polytetrafluoroethylene (PTFE), tetrafluoro ethylene-hexafluoropropylene copolymers or tetrafluoroethylene copo lymerisates with smaller proportions (usually up to 50% by weight) copolymerizable ethylenically unsaturated monomer. These be z. By Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494 and by Wall in "Fluoropoly mers "(Wiley Interscience, 1972).

These fluorine-containing ethylene polymers are distributed homogeneously in the molding compositions and preferably have a particle size dso (Number average) in the range of 0.05 to 10 microns, in particular from 0.1 to 5 μm. These small particle sizes can be especially preferred by using aqueous dispersions of fluorine-containing ethylene polymers and their incorporation in achieve a polyester melt.

The thermoplastic molding compositions according to the invention can according to known processes are prepared in which the off gang components in conventional mixing devices such as screws extruders, Brabender mills or Banbury mills and mixes then extruded. After extrusion, the extrudate can abge cooled and crushed. It can also be individual components are premixed and then the remaining starting materials individually and / or also mixed. The mixing tempe Temperatures are usually 230 to 290 ° C.

In a preferred procedure, components B) to D) with a polyester prepolymers or polyamide prepolymers ge mixed, compounded and granulated. The obtained Gra Then, in a solid phase, the pure material is subjected to inert gas under inert gas ierlich or discontinuously at a temperature below the Melting point of component A) to the desired viscosity condensed.  

The novel thermoplastic molding compositions are characterized due to good mechanical properties and good flame protection out. The processing is largely without changes tion of the polymer matrix and the mold coating and Metallkorro The tendency to lean is greatly reduced. In particular, derar tige molded body improved stability over dry Heat or heat. They are suitable for the production of F 03771 00070 552 001000280000000200012000285910366000040 0002019920276 00004 03652asern, Fo and moldings, in particular for applications in the electrical and electronics area. These applications are especially Lam parts such as lampholders and holders, plugs and Plug strips, bobbins, housing for capacitors or switching contactors and circuit breakers, relay housings and reflectors.

Examples

Component A / 1: Polybutylene terephthalate with a viscosity number (CV) of 130 ml / g (Ultradur®B 4520 der BASF AG), VZ measured in 0.5% solution Phenol / o-dichlorobenzene (1: 1 mixture) at 25 ° C according to ISO 1628

Component A / 2: Polyethylene terephthalate with a VZ of 97 ml / g

Component b ₁ ) resorcinol bis (diphenyl phosphate) (CR 733-S from Daihachi)

Component b ₂₁ ) Stabaxol® 1 (Rhein Chemie GmbH)

Component b ₂₂ ) Stabaxol® p (Rhein Chemie GmbH)

Component b ₂₃ ) Elastostab® (Elastogran GmbH)

with R = NHCOOR ', R' = methyl polyether glycol,

Component b ₂₄ ) Elastostab® (Elastogran GmbH)

Component b ₂₅ ) Basonat® H / 100 (BASF AG)

Component b ₂₆ ) Vestanat® 1890/100 (Hüls AG)

Component b ₂₇ ) Elastostab® (Elastogran GmbH)

with R = NHCOOR ', R' = ethanol

Component C): melamine cyanurate

Component D / 2: 1: 1 Mixture of Irgafos® 168 and pentaerythritol tetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox® 1010) (Ciba Spezialitatenchemie AG)

The components A) to D) were on a twin-screw extruder mixed at 250 to 260 ° C and extruded in a water bath. To Granulation and drying were done on an injection molding machine Test specimen sprayed and tested.

The test of stability at elevated service temperatures was carried out as follows: There were molded parts (platelets 60 × 60 × 2 mm, approx. 11 g). In each case a molding was on Weighed the analytical balance and placed in an aluminum tray in the Convection oven heated to the specified temperature.

After the respective storage period (0/10/20 days at 130 ° C.), the impact strength a _{k in} accordance with ISO 75 1 eU was determined on the samples cooled under vacuum.

Granules were also under the above conditions (0/10/20 days at 130 ° C) stored and the VZ determined ge according to ISO 1628.

Assessment of discoloration after 30 days at 130 ° C visually by comparison with the starting material
- - = distinct brown color
- = slight browning
+ = slight discoloration (barely tolerable)
++ = almost the same color as the starting material.

Cu corrosion: Storage of a copper plate in direct contact with granules and visual assessment of deposit formation.
strong: clearly black
light: isolated dark spots on the copper plate detectable.

The composition of the molding compositions and the results of the measurements are shown in the table.

Claims (9)

1. Thermoplastic molding compositions containing

• A) 10 to 99 wt .-% of at least one thermoplastic poly mers
• B) 1 to 50 wt .-% of a mixture of
  • 1. b ₁ ) at least one phosphorus compound and
  • 2. b ₂ ) at least one stabilizer compound of the general my formulas I to IV
    in which
    R ¹ , R ² independently of one another are a hydrogen, C ₁ to C ₁₀ -alkyl, C ₆ to C ₁₂ -aryl, C ₇ to C ₁₃ -aralkyl, C ₇ to C ₁₃ -alkylaryl radical,
    a, b are independently 1 to 5,
    c, d are independently 0 to 10;
    in which
    R ^{3 is} a hydrogen, C ₁ - to C ₁₀ -alkyl, C ₆ - to C ₁₂ -aryl, C ₇ - to C ₁₃ -aralkyl, C ₇ - to C ₁₃ -alkylaryl radical,
    e 1 to 4,
    f 1 to 100;
    in which
    R ⁴ , R ¹³ independently of one another NCO or NHCOOR ', where R' is an alkylpolyether glycol or an alcohol having 1 to 20 C atoms,
    R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² independently of one another are hydrogen, C ₂ - to C ₁₀ -alkyl, C ₆ - to C ₁₂ -aryl, C ₇ - to C ₁₃ -aralkyl, C ₇ - to C ₁₃ -alkylaryl,
    g 0 to 5,
    h 1 to 100;
    in which
    R ¹⁴ , R ¹⁵ , R ¹⁶ independently of one another hydrogen radical or
    
  in which
  R ^{17 is} a hydrogen, C ₂ - to C ₁₀ -alkyl, C ₆ - to C ₂₂ -aryl, C ₇ - to C ₁₃ -aralkyl, C ₇ - to C ₁₃ -alkylaryl, or
  (CH ₂ ) ₁ -N = C = O, where I is 1 to 20,
  i 2 to 8,
  j 1 to ik,
  k 0 to ij, where j + k ≦ i, or at least two thereof

mean,

• A) 0 to 40 wt .-% of a flame retardant, different from b ₁ )
• B) 0 to 70 wt .-% of other additives, wherein the weight percent of components A) to D) always give 100%.

2. Thermoplastic molding compositions according to claim 1, containing based on 100% B)

• 1.b ₁ ) 50 to 99.99% by weight
• 2.b ₂ ) 0.01 to 50% by weight

3. Thermoplastic molding compositions according to claims 1 or 2, in the component A) is selected from the group of Polyesters, polyamides, polyphenylene ethers, vinylaromatic polymers lymerer, thermoplastic polyurethanes or their Mixtures. 4. Thermoplastic molding compositions according to claims 1 to 3, ent retaining as component A) at least one polyalkylene Phthalate with 3 to 10 carbon atoms in the alcohol part, which, based on 100% by weight of A), up to 50% by weight of polyethylene may contain phthalate. 5. Thermoplastic molding compositions according to claims 1 to 4, where in the phosphorus compound b ₁ ) the general formula V has
in which
R ¹⁸ , R ¹⁹ , R ²⁰ independently of one another are an alkyl, alkylaryl, arylalkyl or cycloalkyl radical having 7 to 40 carbon atoms,
X is a sulfur or oxygen atom,
m, n, o are independently 0 or 1
mean. 6. Thermoplastic molding compositions according to claims 1 to 5, where in the phosphorus compound is selected from the group Tri phenylphosphine oxide, triphenylphosphine sulfide, triphenyl phosphate, resorcinol bis (diphenyl phosphate) or triphenyl phosphine or mixtures thereof. 7. Thermoplastic molding compositions according to claims 1 to 6, ent holding a nitrogen compound as another flame retardant medium C). 8. Use of thermoplastic molding compositions according Ansprü chen 1 to 7 for the production of fibers, films and mold bodies. 9. Shaped body, obtainable from the thermoplastic molding compositions according to claims 1 to 7.