KR20130100912A - Component comprising an insert part and plastics jacketing and process for the production thereof - Google Patents

Abstract

The present invention relates to a component comprising an insert and a plastic jacket consisting of two or more plastic components, wherein the insert is surrounded by a first plastic component A1 or a first plastic component A2 and comprises a first plastic component. Element A1 or first plastic component A2 is surrounded by a second plastic component B, wherein the second plastic component B is B1: 10 to 99.99% by weight of at least one thermoplastic polyester, and B2: 0.01 to 50% by weight %, B21: at least one highly branched or hyperbranched polycarbonate having an OH value of 1 to 600 mg KOH / g polycarbonate (according to DIN 53249, part 2) or B22: A _x B _y type wherein , x is at least 1.1, and y is at least 2.1) of at least one highly branched or hyperbranched polyester, or mixtures thereof.

Description

COMPONENT COMPRISING AN INSERT PART AND PLASTICS JACKETING AND PROCESS FOR THE PRODUCTION THEREOF}

The present invention relates to a component comprising an insert, and a plastic jacket consisting of two or more plastic components, wherein the insert is surrounded by plastic component A and comprises a second plastic configuration surrounding the first plastic component A There is element B. The present invention also relates to a method of making said component.

Components comprising inserts and plastic jackets are used, for example, in the automotive industry or in the aerospace industry where, for example, metallic inserts are used for the integration of electronic components. In order to prevent moisture or liquids from entering and to prevent damage to electronic components by moisture or liquids, a leak-proof or coherent coupling is required here. Even when temperature changes are applied to the components, leakage protection must be maintained. One cause of defective leak-proof properties in mating bonds in composite structures consisting of metallic inserts and plastic jackets can be induced, for example, by the metal component being poorly wetted by the plastic component and causing poor adhesion. Can be. Differences in thermal expansion between metallic and plastic components also cause stresses that can cause cracking.

Plug-shaped components in which plastic jackets surround the metallic insert are known, for example, from EP-B 0 249 975. In order to achieve a leaktight bond between the plastic and the metal, a flexible plastic material is introduced between the outer plastic material and the metallic insert. Flexible plastic materials are, for example, unreinforced thermoplastic elastomers.

EP-A 1 496 587 discloses a composite component in which a flat cable emerges out through a sealed structure made of plastic material. The openings are filled with liquid rubber and then hardened in order to seal the gaps in the portions of the cable coming out of the plastic material.

DE-C 100 53 115 also describes passages for cables consisting of plastic jackets. Sealing is here achieved through a sealant having adhesive properties to both the material of the bushing and the jacket material of the line. Mentioned examples of suitable sealants are fats, waxes, resins, bitumen and the like.

Another plug connector in which a solid jacket of plastic material accepts metallic pins is also known from EP-A 0 245 975. In order to achieve a leakproof bond, a flexible plastic material is used between the metal pin and the outer jacket.

WO-A 2008/099009 also discloses a component in which a plastic layer covers the insert. In this component the metallic insert is first coated with a low viscosity plastic composition and in the second step a hard plastic component is injected around the coating. Suitable plastics mentioned with low viscosity are polyamides, aliphatic polyesters, or polyesters based on aliphatic and aromatic dicarboxylic acids and on aliphatic dihydroxy compounds.

DE-B 10 2005 033 912 also discloses another casing passageway in which electrical contact is conducted through the casing, where the casing passage is sealed in a manner that prevents the entry of undesired materials. To achieve sealing, a galvanizing process is used to increase the depth of roughness of the conductor element in the sealing area.

A disadvantage of plastic jackets of inserts throughout the prior art is that they do not provide adequate leakproof properties, especially when used under temperature varying conditions.

It is therefore an object of the present invention to provide a component comprising an insert and plastic jackets, where the plastic jackets provide adequate leakproof properties even during storage under temperature varying conditions.

This object is achieved through a component comprising an insert and a plastic jacket consisting of two or more plastic components, wherein the insert is surrounded by a first plastic component A1 or a first plastic component A2, wherein the first Plastic component A1

A11: 5 to 80% by weight of at least one polyester based on aliphatic and aromatic dicarboxylic acids and on aliphatic dihydroxy compounds, based on the total weight of components A11 and A12;

A12: 20 to 95% by weight, based on the total weight of components A11 and A12, derived from polylactide (PLA), polycaprolactone, polyhydroxyalkanoate, and aliphatic dicarboxylic acids and aliphatic diols At least one homo- or copolyester selected from the group consisting of polyesters; And

A13: 0.05 to 15% by weight, based on the total weight of components A11 and A12, a) styrene-based, acrylate-based and / or methacrylate-based copolymers containing epoxy groups, b) bisphenol A epoxides Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups

Lt; / RTI >

The first plastic component A2

A21: 10 to 100% by weight of one or more thermoplastic styrene (co) polymers, based on the total weight of components A21 and A22,

A22: 0 to 90% by weight of at least one thermoplastic (co) polyester, based on the total weight of components A21 and A22, and

A23: 0.05 to 15% by weight, based on the total weight of components A21 and A22, a) styrene-based, acrylate-based and / or methacrylate-based copolymers containing epoxy groups, b) bisphenol A epoxides Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups

Lt; / RTI >

The first plastic component A1 or the first plastic component A2 is surrounded by a second plastic component B,

The second plastic component B is

B1: 10 to 99.99% by weight of one or more thermoplastic polyesters, and

B2: 0.01-50% by weight,

B21: one or more highly branched or hyperbranched polycarbonates having an OH value of 1 to 600 mg KOH / g polycarbonate (according to DIN 53249, part 2), or

B22: one or more highly branched or hyperbranched polyesters of the form A _x B _y , wherein x is at least 1.1 and y is at least 2.1, or

Its mixture

Lt; / RTI >

The first plastic component A1 or the first plastic component A2 and / or the second plastic component B is

C: 0 to 60% by weight of one or more additional adjuvants

It is also possible to include.

The second plastic component B of the present invention is also composed of at least one polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds, further comprising polylactide, polycaprolactone, polyhydroxyalkanoate, And a first plastic component A1 consisting of a polyester derived from at least one homo- or copolyester selected from the group consisting of aliphatic dicarboxylic acids and aliphatic diols, or at least one thermoplastic styrene (co) polymer. And, if necessary, in combination with the first plastic component A2 consisting of one or more thermoplastic (co) polyesters, especially when compared to plastic jackets known in the prior art, even when the component is used under temperature changing conditions. Significantly improved anti-leakage properties are achieved. Further improvement is achieved by injecting the first plastic component A1 or A2 around the inner circumference and by injecting the second plastic component B around the outer circumference.

The advantage of using component B is that through the addition of highly branched or hyperbranched polycarbonates and / or highly branched or hyperbranched polyesters, the component has been improved for the first plastic component A1 or A2. It is adhesive and therefore provides better leakage protection properties for bonding. In addition, the advantage is better flowability and thus better processing properties. A further advantage is that the use of highly branched or hyperbranched polycarbonates and / or polyesters does not result in a decrease in mechanical properties when the amount of additive is increased. In addition, the structure of highly branched or hyperbranched polycarbonates and / or highly branched or hyperbranched polyesters can be easily adapted to the requirements of the application of thermoplastics. In addition, because of their defined configuration, highly branched or hyperbranched polycarbonates and / or highly branched or hyperbranched polyesters associate advantageous properties such as high functionality, high reactivity, low viscosity and good solubility. .

1st pla stick  Component A1

According to the invention, the first plastic component A1 is

A11: 5 to 80% by weight of at least one semiaromatic polyester based on aliphatic and aromatic dicarboxylic acid and aliphatic dihydroxy compound based on the total weight of components A11 and A12;

A12: 20 to 95% by weight, based on the total weight of components A11 and A12, derived from polylactide (PLA), polycaprolactone, polyhydroxyalkanoate, and aliphatic dicarboxylic acids and aliphatic diols At least one homo- or copolyester selected from the group consisting of polyesters; And

A13: 0.05 to 15% by weight, based on the total weight of components A11 and A12, a) styrene-based, acrylate-based and / or methacrylate-based copolymers containing epoxy groups, b) bisphenol A epoxides Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups

.

In particularly preferred semiaromatic polyester A11,

Among particularly preferred semiaromatic polyesters, A1 is an essential component.

1) 1 to 30 to 99 mol% of at least one aliphatic or at least one cycloaliphatic dicarboxylic acid, or ester-forming derivative thereof, or mixtures thereof,

1b) 1 to 70 mol% of one or more aromatic dicarboxylic acids, or ester-forming derivatives thereof, or mixtures thereof, and

1c) 0-5 mol% of sulfonate group-containing compounds

A mountain component, and

2) one or more C ₂ -C ₁₂ Alkanediols, one or more C ₅ -C ₁₀ Diol component selected from cycloalkanediol or mixtures thereof

And, where appropriate, also

3) 3a) at least one dihydroxy compound of formula (I) comprising an ether functionality

<Formula I>

(Wherein n is 2, 3 or 4 and m is an integer from 2 to 250),

3b) at least one hydroxycarboxylic acid of formula (IIa) or (IIb)

<Formula IIa>

<Formula IIb>

Wherein p is an integer from 1 to 1500, r is an integer from 1 to 4, G is phenylene,-(CH ₂ ) _q- (where q is an integer from 1 to 5), -C (R ) H- and -C (R) HCH ₂ , wherein R is a radical selected from the group consisting of methyl, ethyl)

3c) at least one amino-C ₂ -C ₁₂ Alkanols or one or more amino-C ₅ -C ₁₀ Cycloalkanols, or mixtures thereof,

3d) one or more diamino-C ₁ -C ₈ alkanes,

3e) at least one 2,2'-bisoxazoline of formula III

<Formula III>

Wherein R ¹ is a single bond, a (CH ₂ ) _z -alkylene group, wherein z = 2, 3 or 4, or a phenylene group,

3f) polyamides obtainable through polycondensation of natural amino acids, dicarboxylic acids having 4 to 6 carbon atoms and diamines having 4 to 10 carbon atoms, compounds of formulas IVa and IVb

&Lt; Formula IVa >

&Lt; Formula IVb >

(Wherein s is an integer from 1 to 1500, t is an integer from 1 to 4, T is phenylene,-(CH ₂ ) _u- (where u is an integer from 1 to 12), -C (R ² ) H- and -C (R ² ) HCH ₂ , wherein R ² is a radical selected from the group consisting of methyl, ethyl

And polyoxazolines having a repeating unit V

(V)

Wherein R ³ is hydrogen, C ₁ -C ₆ -alkyl, C ₅ -C ₈ -cycloalkyl, phenyl having up to 3 substituents which are unsubstituted or C ₁ -C ₄ -alkyl, or tetrahydrofuryl )

At least one aminocarboxylic acid selected from the group consisting of

Or a mixture of 3a) to 3f)

A component selected from, and

4) 4a) at least one compound having at least three groups capable of ester formation,

4b) at least one isocyanate,

4c) at least one divinyl ether,

Or a mixture of 4a) to 4c)

Component selected from

There is a polyester comprising at least one component selected from.

In one preferred embodiment, the acid component 1) of the semiaromatic polyester A11 comprises 30 to 70 mol%, in particular 40 to 60 mol% 1a) and 30 to 70 mol%, especially 40 to 60 mol% 1b).

Aliphatic acids and corresponding derivatives 1a) which can be used are generally those having from 2 to 10 carbon atoms, preferably from 4 to 6 carbon atoms. It may be linear or branched. Cycloaliphatic dicarboxylic acids which can be used for the purposes of the present invention are generally those having from 7 to 10 carbon atoms, in particular 8 carbon atoms. However, it is also possible in principle to use dicarboxylic acids having more carbon atoms, for example up to 30 carbon atoms.

Examples that may be mentioned are: malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, azeleic acid, sebacic acid, fumaric acid, 2, 2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid , Maleic acid and 2,5-norbornanedicarboxylic acid.

Mention may be made in particular of the ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids which may likewise be used: di-C ₁ -C ₆ -alkyl esters such as dimethyl, diethyl, di- n-propyl, diisopropyl, di-n-butyl, diisobutyl, di-tert-butyl, di-n-pentyl, diisopentyl, or di-n-hexyl ester. It is also possible to use anhydrides of dicarboxylic acids.

The dicarboxylic acids or their ester-forming derivatives can be used here individually or in the form of mixtures of two or more thereof.

Preference is given to using succinic acid, adipic acid, azelaic acid, sebacic acid, brazic acid, or their corresponding ester-forming derivatives, or mixtures thereof. Particular preference is given to using succinic acid, adipic acid or sebacic acid, or their corresponding ester-forming derivatives, or mixtures thereof. Particular preference is given to using adipic acid or its ester-forming derivatives, for example alkyl esters thereof, or mixtures thereof. If a polymer mixture having "hard" or "brittle" component A12, for example polyhydroxybutyrate or in particular polylactide, is used, the aliphatic dicarboxylic acids used are preferably sebacic acid or sebacic acid and adipic acid. It contains a mixture of. If a polymer mixture having "soft" or "toughness" component A12 is produced, for example polyhydroxybutyrate-co-valorate, the aliphatic dicarboxylic acids used are preferably succinic acid or a mixture of succinic acid and adipic acid. It includes.

Another advantage of succinic acid, azelaic acid, sebacic acid and brazil is that they are available in the form of renewable raw materials.

Aromatic dicarboxylic acids 1b) which may be mentioned are generally those having from 8 to 12 carbon atoms, preferably 8 carbon atoms. For example, mention may be made of terephthalic acid, isophthalic acid, 2,6-naphthoic acid and 1,5-naphthoic acid, and also ester-forming derivatives thereof. Di-C ₁ -C ₆ -alkyl esters, for example dimethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl, di-tert-butyl, di-n- Pentyl, diisopentyl or di-n-hexyl esters may be mentioned in particular. Anhydrides of dicarboxylic acids 1b) are equally suitable ester-forming derivatives.

However, it is also possible in principle to use aromatic dicarboxylic acids 1b) with more carbon atoms, for example up to 20 carbon atoms.

Such aromatic dicarboxylic acid or ester-forming derivatives of 1b) can be used individually or in the form of mixtures made of two or more thereof. Particular preference is given to using terephthalic acid or its ester-forming derivatives, for example dimethyl terephthalate.

Compounds used containing sulfonate groups include mainly alkali metal or alkaline earth metal salts of dicarboxylic acids containing sulfonate groups, or ester-forming derivatives thereof, preferably alkali metal salts of 5-sulfoisophthalic acid, or their Mixtures, particularly preferably sodium salts.

According to one of the preferred embodiments, the acid component 1) comprises 40 to 60 mol% 1a), 40 to 60 mol% 1b) and 0 to 2 mol% 1c). According to another preferred embodiment, the acid component 1) comprises 40 to 59.9 mol% 1a), 40 to 59.9 mol% 1b) and 0.1 to 1 mol% 1c), in particular 40 to 59.8 mol% 1a), 40 to 59.8 mol% 1b) and 0.2 to 0.5 mol% 1c).

Diol 2) is generally selected from branched or linear alkanediols having from 2 to 12 carbon atoms, preferably from 4 to 6 carbon atoms, or from cycloalkanediols having from 5 to 10 carbon atoms.

Examples of suitable alkanediols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-dimethyl-2- Ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3- Propanediol, 2,2,4-trimethyl-1,6-hexanediol, in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol and 2,2-dimethyl-1,3-propanediol (neopentyl Glycol); Cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or 2,2,4,4-tetramethyl- 1,3-cyclobutanediol. Particular preference is given to 1,4-butanediol in combination with adipic acid, in particular as component a1), and 1,3-propanediol in combination with sebacic acid, in particular as component a1). Another advantage of 1,3-propanediol and 1,4-butanediol is that it is available in the form of renewable raw materials. It is also possible to use mixtures of various alkanediols.

Depending on whether excess acid end groups or functional groups of OH end groups are required, excess Component A or Component B can be used. According to one preferred embodiment, the molar ratio of components A and B used may range from 0.4: 1 to 1.5: 1, preferably from 0.6: 1 to 1.1: 1.

The polyester on which the polyester mixture of the present invention is based may comprise additional components together with components 1) and 2).

The dihydroxy compounds 3a) used are preferably diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran (polyTHF), particularly preferably diethylene glycol, triethylene glycol and polyethylene glycol Included here, it is also possible to use mixtures thereof, or compounds having various variables n (see Formula I), examples of which are known, for example, using ethylene oxide first, followed by propylene oxide Particular preference is given to polyethylene glycols based polymers comprising propylene units (n = 3), obtainable via polymerization using the process as described above, and having various variables n in which the units formed of ethylene oxide dominate. The molar mass (M _n ) of polyethylene glycol is generally selected within the range of 250 to 8000 g / mol, preferably 600 to 3000 g / mol.

According to one preferred embodiment, for the preparation of semiaromatic polyesters, for example, from 15 to 98 mol%, preferably from 60 to 99.5 mol% of diols 2) and from 0.2 to based on the molar amount of 2) and 3a) It is possible to use 85 mol%, preferably 0.5 to 30 mol% of dihydroxy compound 3a).

In one preferred embodiment, the hydroxycarboxylic acids 3b) used include glycolic acid, D-, L- or D, L-lactic acid, 6-hydroxyhexanoic acid, cyclic derivatives thereof such as glycolide (1,4 -Dioxane-2,5-dione), D- or L-diactide (3,6-dimethyl-1,4-dioxane-2,5-dione), p-hydroxybenzoic acid, and also oligomers thereof Polymers such as 3-polyhydroxybutyric acid, polyhydroxyvaleric acid, polylactide (available in the form of, for example, NatureWorks® Cargill), or else 3-polyhydroxy A mixture of butyric acid and polyhydroxyvaleric acid (the latter obtainable as Biopol® from Zenca), using low molecular weight cyclic derivatives thereof for the preparation of semiaromatic polyesters Particularly preferred.

Examples of usable amounts of hydroxycarboxylic acid are 0.01 to 50% by weight, preferably 0.1 to 40% by weight, based on the amounts of 1) and 2).

Amino-C ₂ -C _{12 with} 4-aminomethylcyclohexanemethanol Alkanols or amino-C ₅ -C ₁₀ cycloalkanols (component 3c) are preferably amino-C ₂ -C ₆ alkanols, such as 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5 -Aminopentanol, 6-aminohexanol, or else amino-C ₅ -C ₆ cycloalkanols such as aminocyclopentanol and aminocyclohexanol, or mixtures thereof.

The diamino-C ₁ -C ₈ alkanes (component 3d) used are preferably diamino-C ₄ -C ₆ alkanes such as 1,4-diaminobutane, 1,5-diaminopentane and 1,6 Diaminohexane (hexamethylenediamine, “HMD”).

In one preferred embodiment, the material used to prepare the semiaromatic polyester comprises from 0.5 to 99.5 mol%, preferably from 0.5 to 50 mol% of 3c), and 2) molar amount based on the molar amount of 2). On the basis of 0 to 50 mol%, preferably 0 to 35 mol% of 3d).

2,2'-bisoxazoline 3e) of formula III is generally described in Angew. Chem. Int. Edit., Vol. 11 (1972), pp. 287-288]. Particularly preferred bisoxazolines are those wherein R ¹ is a single bond and (CH ₂ ) _z -alkylene groups, where z = 2, 3 or 4, for example methylene, ethane-1,2-diyl, propane- 1,3-diyl, propane-1,2-diyl or phenylene group. Particularly preferred bisoxazolins which may be mentioned are 2,2'-bis (2-oxazoline), bis (2-oxazolinyl) methane, 1,2-bis (2-oxazolinyl) ethane, 1,3 -Bis (2-oxazolinyl) propane or 1,4-bis (2-oxazolinyl) butane, in particular 1,4-bis (2-oxazolinyl) benzene, 1,2-bis (2-oxazoli Yl) benzene or 1,3-bis (2-oxazolinyl) benzene.

In the preparation of the semiaromatic polyester A11, for example based on the total molar amount of components 2), 3c), 3d) and 3e), for example 70 to 98 mol% 2), up to 30 mol% 3c) and 0.5 To 30 mol% 3d) and 0.5 to 30 mol% 3e) can be used. In another preferred embodiment it is possible to use 0.1 to 5% by weight, preferably 0.2 to 4% by weight of 3e) based on the total weight of 1) and 2).

Component 3f) used may include natural aminocarboxylic acids. Among these are valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, alanine, arginine, aspartamic acid, cysteine, glutamic acid, glycine, histidine, proline, serine, tyrosine, asparagine and glutamine.

Preferred aminocarboxylic acids of the formulas IVa and IVb are those wherein s is an integer from 1 to 1000, t is an integer from 1 to 4, preferably 1 or 2, and T is phenylene and-(CH ₂ ) _u- (where u is selected from the group 1, 5 or 12).

Furthermore 3f) may also be a polyoxazoline of formula (V). However, 3f) can also be a mixture of various aminocarboxylic acids and / or polyoxazolines.

In one preferred embodiment, the usable amount of 3f) is from 0.01 to 50% by weight, preferably from 0.1 to 40% by weight, based on the total amount of components 1) and 2).

An additional component that can optionally be used to prepare the semi-aromatic polyester is compound 4a) comprising at least three groups capable of ester formation.

Compound 4a) preferably comprises 3 to 10 functional groups capable of forming ester linkages. Particularly preferred compounds 4a) have 3 to 6 such types of functional groups, in particular 3 to 6 hydroxy groups and / or carboxy groups in the molecule. His examples that may be mentioned are as follows.

Tartaric acid, citric acid, malic acid;

Trimethylolpropane, trimethylolethane;

Pentaerythritol;

Polyethertriol;

Glycerol;

Trimesic acid;

Trimellitic acid, trimellitic anhydride;

Pyromellitic acid, pyromellitic dianhydride, and

Hydroxyisophthalic acid.

The amount of compound 4a) used is generally from 0.01 to 15 mol%, preferably from 0.05 to 10 mol%, particularly preferably from 0.1 to 4 mol%, based on component 1).

Component 4b) used includes one isocyanate or a mixture of various isocyanate (s). It is possible to use aromatic or aliphatic diisocyanates. However, it is also possible to use relatively high functional isocyanates.

For the purposes of the present invention, aromatic diisocyanates 4b)

Tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate , Naphthylene 1,5-diisocyanate or xylylene diisocyanate.

Of these, diphenylmethane 2,2'-, 2,4'- and 4,4'-diisocyanate are particularly preferred as component 4b). The latter diisocyanate is generally used in the form of a mixture.

Tri (4-isocyanatophenyl) methane can also be used as trinuclear isocyanate 4b). For example, multinuclear aromatic diisocyanates are prepared during the preparation of mononuclear or binuclear diisocyanates.

Component 4b) may also comprise up to 5% by weight of uretdione groups, for example based on the total weight of component 4b), for example to cap isocyanate groups.

For the purposes of the present invention, aliphatic diisocyanates 4b) are in particular linear or branched alkylene diisocyanates or cycloalkylene diisocyanates with 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example hexa. Methylene 1,6-diisocyanate, isophorone diisocyanate or methylene-bis (4-isocyanatocyclohexane). Particularly preferred aliphatic diisocyanates 4b) are hexamethylene 1,6-diisocyanate and isophorone diisocyanate.

Preferred isocyanurates include alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example isophorone diisocyanate or methylene-bis (4-iso). Aliphatic isocyanurate derived from cyanatocyclohexane). The alkylene diisocyanate may here be linear or branched. Particular preference is given to cyclic trimers, pentamers or higher oligomers of n-hexamethylene diisocyanate-based isocyanurates, for example n-hexamethylene diisocyanate.

The amount of component 4b) generally used is 0.01 to 5 mol%, preferably 0.05 to 4 mol%, particularly preferably 0.1 to 4 mol%, based on the total molar amount of 1) and 2).

The divinyl ether 4c) used may generally include any conventional and commercially available divinyl ether. Preference is given to using 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether or 1,4-cyclohexanedimethanol divinyl ether, or mixtures thereof.

The amount of divinyl ether preferably used is 0.01 to 5% by weight, in particular 0.2 to 4% by weight, based on the total weight of 1) and 2).

Examples of preferred semiaromatic polyesters are based on the following components.

1), 2), 4a)

1), 2), 4b)

1), 2), 4a), 4b)

1), 2), 4c)

1), 2), 3a)

1), 2), 3a), 4c)

1), 2), 3c), 3d)

1), 2), 3c), 3d), 3e)

1), 2), 4a), 3c), 3e)

1), 2), 3c), 4c)

1), 2), 3c), 4a)

1), 2), 3a), 3c), 4c)

1), 2), 3b)

Among these, semi-aromatic polyesters based on 1), 2), 4a), or 1), 2), 4b), or 1), 2), 4a), and 4b) are particularly preferred. In another preferred embodiment, the semi-aromatic polyester is based on 1), 2), 3c), 3d), 3e), or 1), 2), 4a), 3c), 3e).

Semi-aromatic polyester A11, consisting of terephthalic acid (10-40 mol%), 1,4-butanediol (50 mol%) and adipic or sebacic acid (10-40 mol%) (100% by weight of monomer total) Copolyesters are preferred. Particular preference is given to random copolyesters consisting of terephthalic acid (15-35 mol%), 1,4-butanediol (50 mol%) and adipic acid (15-35 mol%) (100% by weight of total monomer).

Homo- or copolyester A12 is a group consisting of polylactide (PLA), polycaprolactone, polyhydroxyalkanoates such as PHB or PHB / V, and polyesters derived from aliphatic dicarboxylic acids and aliphatic diols Is preferably selected from.

In one preferred embodiment, the melting point of the at least one polyester included in plastic component A1 is lower than the melting point of polyester B1 of the second plastic component B.

An advantage of the lower melting point is that the initial melting of the first plastic component A1 can provide a leak-tight bond, especially when the second component B is injected onto the material.

The first plastic component A1 may also comprise one or more additives. The additives here are mainly impact modifiers, flame retardants, nucleating agents, carbon blacks, pigments, colorants, release agents, heat-aging stabilizers, antioxidants, processing stabilizers, lubricants and antiblocking agents, waxes, plasticizers, surfactants, antistatic agents and invincibles. It is selected from the group consisting of. The proportion of the additives based on the mass of the plastic component A1 is preferably in the range from 0 to 15% by weight.

The material may also include fibrous or particulate fillers. Suitable fibrous or particulate fillers may be inorganic or organic. Examples of suitable materials include glass fibers, carbon fibers, aramid fibers, kaolin, calcined kaolin, talc, chalk, silicates, mica, wollastonite, montmorillonite, cellulose fibers such as cotton, flax, hemp, hemp, nettle ), Such as fibers, amorphous silica and powdered quartz. Of the fibrous or particulate fillers, particulate fillers are particularly preferred. Very particular preference is given to mineral and glass beads, in particular glass beads. The proportion of fibrous or particulate filler based on the mass of plastic component A1 is preferably in the range from 0 to 50% by weight. If the first plastic component A1 comprises glass beads, the proportion of glass beads is preferably in the range from 0.1 to 40% by weight, based on the total weight of the first plastic component A1.

In order to improve compatibility with the first plastic component A1, the surface of the filler can be treated, for example with an organic compound or a silane compound.

Examples of suitable impact modifiers for the first plastic component A1 include ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile, and 1 to 18 carbon atoms, respectively, in the alcohol component. It is a copolymer which consists of two or more monomer units chosen from the acrylate and methacrylate which have. Suitable impact modifiers are known, for example, from WO-A 2007/009930.

The first plastic component A1 may comprise a flame retardant in an amount of from 0 to 50% by weight, based on the total mass of the first plastic component A. Examples of suitable flame retardants are flame retardants including halogen-containing flame retardants, halogen-free flame retardants, melamine-cyanurate-based flame retardants, phosphorus-containing flame retardants and expanded graphite.

According to the invention, plastic component A1 comprises at least one compatibilizer A13. The proportion of the at least one compatibilizer is in each case preferably in the range from 0.05 to 5% by weight, in particular in the range from 0.1 to 3% by weight, based on the total mass of the plastic component A1.

The compatibilizer used can improve the binding of component A12 into the matrix of semiaromatic polyester A11 or can act as an adhesion promoter between the first plastic component A1 and the second plastic component B. Examples of suitable compatibilizers are styrene (co) polymers grafted with glycidyl methacrylate, such as Macromol. Symp. 2006, 233, pp. 17-25. Other suitable materials are styrene (co) polymers grafted with isocyanate groups, poly [methylene (phenylene isocyanate)], bisoxazolin, styrene copolymers grafted with oxazoline groups, or styrene copolymers grafted with maleic anhydride. to be. Particularly suitable materials are styrene copolymers equipped with epoxy functionality and a proportion of methacrylic acid. Preference is given to random, epoxy-functionalized styrene-acrylic acid copolymers having a molar mass M _w of 3000 to 8500 g / mol and functionalized with more than two epoxy groups per molecular chain. Particular preference is given to random, epoxy-functionalized styrene-acrylic acid copolymers having a molar mass M _w of 5000 to 7000 g / mol and functionalized with more than 4 epoxy groups per molecular chain.

1st pla stick  Component A2

According to the invention, the first plastic component A2 is

A21: 10 to 100% by weight of at least one thermoplastic styrene (co) polymer, based on the total weight of components A21 and A22,

A22: 0 to 90% by weight of at least one thermoplastic (co) polyester, based on the total weight of components A21 and A22,

A23: 0.05 to 15% by weight, based on the total weight of components A21 and A22, a) styrene-based, acrylate-based and / or methacrylate-based copolymers containing epoxy groups, b) bisphenol A epoxides Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups

.

In one preferred embodiment, the first plastic component A2 comprises 50 to 100% by weight of one or more thermoplastic styrene (co) polymers, more preferably 70 to 100% by weight. Correspondingly, the proportion of the at least one thermoplastic (co) polyester is preferably 0 to 50% by weight, more particularly 0 to 30% by weight. In a particularly preferred embodiment, there are 70 to 90% by weight thermoplastic styrene (co) polymer and 10 to 30% by weight thermoplastic (co) polyester.

Thermoplastic styrene (co) polymer A21 is preferably microparticles made of styrene-butadiene copolymer, styrene-acrylonitrile copolymer (SAN), α-methylstyrene-styrene-acrylonitrile copolymer, diene polymer or alkyl acrylate The particulate rubber phase consisting of a styrene-acrylonitrile copolymer having a rubber phase, and a diene polymer or an alkyl acrylate is selected from the group consisting of α-methylstyrene-styrene-acrylonitrile copolymer (other than styrene in the copolymer The proportion of each monomer is 15 to 40% by weight).

Component A21 is generally 15 to 60% by weight, preferably 25 to 55% by weight, in particular 30 to 50% by weight, of graft rubber, and 40 to 85% by weight, preferably 45 to 75% by weight, in particular 50 to 70 weight percent thermoplastic styrene (co) polymers, each weight percent based on the total weight of the particulate graft rubber and thermoplastic (co) polymer, totaling 100 weight percent.

The thermoplastic styrene (co) polymer A21 may also comprise α-methylstyrene or n-phenylmaleimide in a proportion of 0 to 70% by weight.

Wherein the proportion of monomer units other than styrene, or of α-methylstyrene or n-phenylmaleimide, is always based on the weight of the thermoplastic styrene (co) polymer A21.

In one preferred embodiment, styrene component A21 is particularly preferably composed of butadiene based particulate graft rubber as the rubber phase, and vinylaromatic monomer and vinyl cyanide (SAN) as a thermoplastic hard phase, in particular styrene and acrylonitrile Copolymers consisting of styrene, α-methylstyrene and acrylonitrile.

Preference is given to using acrylonitrile-butadiene-styrene polymers (ABS) as SANs impact-modified with particulate graft rubber.

ABS polymers are generally impact-modified SAN polymers in which diene polymers, in particular 1,3-polybutadiene, are present in a copolymer matrix, in particular styrene and / or α-methylstyrene and acrylonitrile. ABS polymers and their preparation are known to those skilled in the art and are described, for example, in DIN EN ISO 2580-1, WO 02/00745 and WO 2008/020012, February 2003, and in Modern Styrenic Polymers, Edt. J. Scheirs, Wiley & Sons 2003, pp. 305-338.

Thermoplastic polyester A22 is preferably polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and a copolyester consisting of at least one diacid and at least one diol and, optionally, at least one lactone, and also It is selected from the group consisting of a mixture of two or more of the above polyesters.

Examples of suitable diacids constituting the copolyesters are terephthalic acid, adipic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, and their It is selected from the group consisting of a mixture.

Examples of suitable diols constituting the copolyesters include 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, 1,4-hexanediol, 1, 4-cyclohexanediol, 1,4-cyclo-hexanedimethanol, neopentyl glycol, polytetrahydrofuran, and mixtures thereof.

If at least one lactone is also used in the structure of the copolyester, it is preferably selected from the group consisting of ε-caprolactone, hexano-4-lactone, γ-butyrolactone and γ-valerolactone.

Thermoplastic polyester A22, random nose consisting of terephthalic acid (10-40 mol%), 1,4-butanediol (50 mol%) and adipic or sebacic acid (10-40 mol%) (100% by weight of the total monomer) Polyester is preferred. Particular preference is given to random copolyesters consisting of terephthalic acid (15-35 mol%), 1,4-butanediol (50 mol%) and adipic acid (15-35 mol%) (100% by weight of total monomer).

In one preferred embodiment, the melting point of at least one of the polyesters included in plastic component A2 is lower than the melting point of polyester B1 of the second plastic component B.

An advantage of the lower melting point is that the initial melting of the first plastic component A2 can provide a leak-tight bond, especially when the second component B is injected onto the material.

The first plastic component A2 may also comprise one or more additives. The additives here are mainly selected from the group consisting of fibrous or particulate fillers, impact modifiers, flame retardants, nucleating agents, carbon blacks, pigments, colorants, mold release agents, heat-aging stabilizers, antioxidants, processing stabilizers and compatibilizers.

Examples of suitable fibrous fillers are glass fibers, carbon fibers or aramid fibers. Examples of mainly used particulate fillers are kaolin, calcined kaolin, talc, chalk, amorphous silica and powdered quartz. Of the fibrous or particulate fillers, particulate fillers are particularly preferred. Very particular preference is given to mineral and glass beads, in particular glass beads. If the first plastic component A2 comprises glass beads, the proportion of glass beads is preferably in the range from 0.1 to 40% by weight, based on the total mass of the first plastic component A2.

In order to improve compatibility with the first plastic component A2, the surface of the filler can be treated, for example with an organic compound or a silane compound.

Examples of suitable impact modifiers for the first plastic component A2 include ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile, and 1 to 18 carbon atoms, respectively, in the alcohol component. It is a copolymer which consists of two or more monomer units chosen from the acrylate and methacrylate which have. Suitable impact modifiers are known, for example, from WO-A 2007/009930.

The first plastic component A2 may comprise a flame retardant in an amount of from 0 to 50% by weight, based on the total mass of the first plastic component A2. Examples of suitable flame retardants are flame retardants including halogen-containing flame retardants, halogen-free flame retardants, melamine-cyanurate-based flame retardants, phosphorus-containing flame retardants and expanded graphite.

In one particularly preferred embodiment, plastic component A2 comprises at least one compatibilizer. The proportion of the at least one compatibilizer is preferably in the range from 0.05 to 5% by weight, in particular in the range from 1 to 3% by weight, based on the total mass of the plastic component A2.

The compatibilizer used may improve the binding of component A22 into the matrix of styrene (co) polymer A21 or may act as an adhesion promoter between the first plastic component A2 and the second plastic component B. Examples of suitable compatibilizers are styrene (co) polymers grafted with glycidyl methacrylate, such as Macromol. Symp. 2006, 233, pp. 17-25. Other suitable materials are styrene (co) polymers grafted with isocyanate groups, poly [methylene (phenylene isocyanate)], bisoxazolin, styrene copolymers grafted with oxazoline groups, or styrene copolymers grafted with maleic anhydride. to be. Particularly suitable materials are styrene copolymers equipped with epoxy functionality and a proportion of methacrylic acid. Preference is given to random, epoxy-functionalized styrene-acrylic acid copolymers having a molar mass M _w of 3000 to 8500 g / mol and functionalized with more than two epoxy groups per molecular chain. Particular preference is given to random, epoxy-functionalized styrene-acrylic acid copolymers having a molar mass M _w of 5000 to 7000 g / mol and functionalized with more than 4 epoxy groups per molecular chain.

Second plastic component B

As component B1, the molding composition of the present invention comprises from 10 to 99.99%, preferably from 30 to 97.99%, more particularly from 30 to 95% by weight, of at least one thermoplastic polyester different from B22.

Generally, polyester B1 based on aromatic dicarboxylic acids and based on aliphatic or aromatic dihydroxy compounds is used.

The first group of preferred polyesters is more particularly polyalkylene terephthalates, having 2 to 10 carbon atoms in the alcohol moiety.

Polyalkylene terephthalates of this type are known per se and are described in the literature. Its main chain includes aromatic rings derived from aromatic dicarboxylic acids. Aromatic rings may also be substituted with halogens such as chlorine or bromine, or C ₁ -C ₄ -alkyl groups such as methyl, ethyl, isopropyl, n-propyl or n-butyl, isobutyl or tert-butyl groups.

Such polyalkylene terephthalates can be prepared through the reaction of aromatic dicarboxylic acids, or their esters or other ester-forming derivatives, with aliphatic dihydroxy compounds in a known manner.

Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, or mixtures thereof. However, up to 30 mol%, preferably up to 10 mol%, of aromatic dicarboxylic acids are aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and / or cyclohexanedicarboxylic acid. Can be replaced.

Among the aliphatic dihydroxy compounds, diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexane Preference is given to diols, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, or mixtures thereof.

Particularly preferred polyesters B1 include polyalkylene terephthalates derived from alkanediols having 2 to 6 carbon atoms. Among them, more particularly polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred. Preference is also given to PET and / or PBT comprising up to 1% by weight, preferably up to 0.75% by weight of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as additional monomeric units.

The viscosity number of polyester B1 is generally in the range from 50 to 220, preferably in the range from 80 to 160 (0.5 weight in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1) at 25 ° C. according to ISO 1628). Measured in% concentration solution).

Particular preference is given to polyesters having a carboxyl end group content of 100 meq or less, preferably 50 meq or less, in particular 40 meq or less, per kg polyester. Polyesters of this type can be produced, for example, by the method of DE-A 44 01 055. The carboxyl end group content is mainly determined by titration (eg potentiometric titration).

Particularly preferred molding compositions comprise, as component B1, for example, a mixture of PBT and a non-PBT polyester such as polyethylene terephthalate (PET). The fraction of polyethylene terephthalate in the mixture is preferably 50% by weight or less, more particularly 10 to 35% by weight, based on 100% by weight of B1.

Furthermore, it is advantageous to use PET recycled materials (also called scrap PET), where appropriate in a mixture with polyalkylene terephthalates, such as PBT.

Recyclable raw materials are generally understood to include the following.

1) Post-process recycled raw material: This is a production waste during the polycondensation step or during processing, for example sprues from injection-molding processes, start-up products from injection-molding or extrusion processes, or extruded sheets Or an edge cut from the film.

2) Post-consumer recycled raw materials: These mainly include plastic bites collected and processed after use by the end consumer. In quantitative terms, the most important articles are blow-molded PET bottles for mineral water, soft drinks and juices.

Both types of recycled raw materials can take the form of regrind or pellets. In the latter case, the crude recycled material is first separated and washed, then melted and pelletized in an extruder. This method mainly facilitates handling, free-flowing properties and weighing convenience for subsequent processing steps.

Recycled raw materials in either pellet form or in the form of regrind may be used, where the maximum edge length should be 10 mm or less, preferably 8 mm or less.

During processing (due to traces of moisture), due to hydrolysis cleavage of the polyester, it is desirable to dry the recycled material in advance. After drying, the residual moisture content is preferably at most 0.2%, in particular at most 0.05%.

Another group that may be mentioned are groups of fully aromatic polyesters derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preferably the mixture used consists of 5 to 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, in particular about 50 to about 80% terephthalic acid and about 20 to about 50% isophthalic acid.

The aromatic dihydroxy compound preferably has the following formula (VI).

&Lt; Formula (VI)

Wherein Z is an alkylene or cycloalkylene group having up to 8 carbon atoms, an arylene group having up to 12 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom, or a chemical bond and m is 0-2. The phenylene groups of the compounds may also be substituted with C ₁ -C ₆ -alkyl or alkoxy groups and fluorine, chlorine or bromine.

Examples of parent compounds of these compounds are as follows.

Dihydroxybiphenyl,

Di (hydroxyphenyl) alkane,

Di (hydroxyphenyl) cycloalkane,

Di (hydroxyphenyl) sulfide,

Di (hydroxyphenyl) ether,

Di (hydroxyphenyl) ketone,

Di (hydroxyphenyl) sulfoxide,

?,? '- di (hydroxyphenyl) dialkylbenzene,

Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene,

Resorcinol, and

Hydroquinones, and also ring-alkylated and ring-halogenated derivatives thereof.

double,

4,4'-dihydroxybiphenyl,

2,4-di (4'-hydroxyphenyl) -2-methylbutane,

?,? '- di (4-hydroxyphenyl) -p-diisopropylbenzene,

2,2-di (3'-methyl-4'-hydroxyphenyl) propane, and

2,2-di (3'-chloro-4'-hydroxyphenyl) propane is preferred,

Especially,

2,2-di (4'-hydroxyphenyl) propane,

2,2-di (3 ', 5-dichlorodihydroxyphenyl) propane,

1,1-di (4'-hydroxyphenyl) cyclohexane,

3,4'-dihydroxybenzophenone,

4,4'-dihydroxydiphenyl sulfone and

2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane

And mixtures thereof.

It is of course also possible to use mixtures of polyalkylene terephthalates and wholly aromatic polyesters. It generally comprises from 20 to 98% by weight of polyalkylene terephthalate and from 2 to 80% by weight of fully aromatic polyester.

It is of course also possible to use polyester block copolymers, such as copolyetheresters. Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,014. Corresponding products are also commercially available, for example, by Hitrel® (DuPont).

According to the invention, polyesters include halogen-free polycarbonates. Examples of suitable halogen-free polycarbonates are those based on diphenols of the general formula (VII).

(VII)

Wherein Q is a single bond, a C ₁ -C ₈ -alkylene group, a C ₂ -C ₃ -alkylidene group, a C ₃ -C ₆ -cycloalkylidene group, a C ₆ -C ₁₂ -arylene group, or Others are -O-, -S- or -SO _2- , and m is an integer of 0-2.

Phenylene radicals of diphenols can also C ₁ -C ₆ - may have a substituent such as alkoxy-alkyl, or C ₁ -C _6.

Examples of preferred diphenols of formula (VII) are hydroquinone, resorcinol, 4,4'-di-hydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxy Hydroxyphenyl) -2-methyl-butane and 1,1-bis (4-hydroxyphenyl) cyclohexane. 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, and also 1,1-bis (4-hydroxyphenyl) -3,3,5- Trimethylcyclohexane is particularly preferred.

Homopolycarbonates or copolycarbonates are suitable as component B1, copolycarbonates of bisphenol A, and also bisphenol A homopolymers.

Suitable polycarbonates may be branched in a known manner and specifically and preferably from 0.05 to 2.0 mol% of at least trifunctional compounds, for example three or more phenolic based on the total diphenols used. It can be branched by introducing a compound having an OH group.

The relative viscosity η _rel of the polycarbonates found to be particularly suitable is 1.10 to 1.50, in particular 1.25 to 1.40. This corresponds to an average molecular weight M _w (weight-average) of 10,000 to 200,000 g / mol, preferably 20,000 to 80,000 g / mol.

Diphenols of formula (VII) are known per se or can be prepared by known methods.

Polycarbonates can be prepared, for example, by reacting diphenols with phosgene in an interfacial process or with phosgene in a homogeneous-phase process (known as pyridine process), in which case the desired molecular weight is known in appropriate amounts. Chain terminators are achieved in a known manner (in the context of polydiorganosiloxane-containing polycarbonates, see eg DE-A 33 34 782).

Examples of suitable chain terminators are phenol, p-tert-butylphenol, or else long chain alkylphenols such as in DE-A 28 42 005, such as 4- (1,3-tetramethylbutyl) phenol, or monoalkylphenols Or dialkylphenols having a total of 8 to 20 carbon atoms in alkyl substituents such as in DE-A-35 06 472, such as p-nonylphenol, 3,5-di-tert-butylphenol, p-tert-octyl Phenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol and 4- (3,5-dimethyl-heptyl) phenol.

For the purposes of the present invention, halogen-free polycarbonates are polycarbonates consisting of halogen-free diphenols, halogen-free chain terminators, and when halogen-free branching agents are used, for example interfaces The content of secondary amounts of ppm levels of hydrolyzable chlorine resulting from the production of polycarbonates using phosgene in the process is not considered to ensure the term halogen-containing for the purposes of the present invention. Polycarbonates of this type having a hydrolytic chlorine content of ppm level are halogen-free polycarbonates for the purposes of the present invention.

Another suitable component B1 which may be mentioned may be amorphous polyester carbonate, wherein the phosgene is replaced with aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid during the production process. At this point, further details can be found in EP-A 711 810.

EP-A 365 916 describes other suitable copolycarbonates having cycloalkyl radicals as monomer units.

It is also possible to replace bisphenol A with bisphenol TMC. Polycarbonates of this type are available from Bayer under the trademark APEC HT®.

The molding compositions of the invention, as component B2, comprise from 0.01 to 50% by weight, preferably from 0.5 to 20% by weight, in particular from 0.7 to 10% by weight, of OH number 1 to 600 mg KOH / g polycarbohydrate as component B21. One or more highly branched or hyperbranched polycarbonates, preferably 10 to 550 mg KOH / g polycarbonate, especially 50 to 550 mg KOH / g polycarbonate (according to DIN 53240, Part 2). Or one or more hyperbranched polyesters as component B22, or mixtures thereof as described below.

For the purposes of the present invention, hyperbranched polycarbonate B21 is a non-crosslinked macromolecule having hydroxy groups and carbonate groups, which have both structural and molecular non-uniformities. Its structure is first based on the central molecule in the same way as the dendrimer, but the chain length of the branches is nonuniform. Secondly, it can also have a linear structure with functional pendant groups, or else it can be a combination of two extremes with linear and branched molecular moieties. In addition, the definitions of dendrimer and hyperbranched polymers are described in P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499].

By “hyperbranched” in the context of the present invention is meant the degree of branching (DB), ie the sum of the average number of dendritic linkages and terminal groups per molecule, which is 10 to 99.9%, preferably 20 to 99%, in particular Preferably it is 20 to 95%.

"Dendrimer type" in the context of the present invention means that the degree of branching is 99.9 to 100%. The definition of “degree of branching” is described in H. Frey et al., Acta Polym. 1997, 48, 30. For the purposes of the present invention, the terms "highly branched" and "dendrimer" are used synonymously.

The number-average molecular weight M _n of component B21 is preferably 100 to 15,000 g / mol, preferably 200 to 12 000 g / mol, in particular 500 to 10,000 g / mol (GPC, PMMA reference).

The glass transition temperature Tg is in particular -80 ° C to + 140 ° C, preferably -60 to 120 ° C (DSC, according to DIN 53765).

In particular, the viscosity (mPas) at 23 ° C. (according to DIN 53019) is from 50 to 200,000, in particular from 100 to 150,000, very particularly preferably from 200 to 100,000.

Component B21 is preferably obtainable via a process comprising at least the following steps.

a) at least one organic carbonate (BA) of the formula RO (CO) OR and at least one aliphatic alcohol (BB) having at least three OH groups is reacted with the removal of the alcohol ROH to at least one condensate (BK ), Wherein each R is, independently of each other, a straight or branched chain aliphatic, araliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms,

b) intermolecular reaction of the condensate (K) to provide a highly functional highly branched, or highly functional hyperbranched polycarbonate

Wherein the quantitative ratio of OH groups to carbonates in the reaction mixture indicates that the condensate (BK) has an average of one carbonate group and more than one OH group or one OH group and more than one carbonate group Selected to have).

Each radical R of the organic carbonate (BA) used as starting material and having the formula RO (CO) OR is independently a straight or branched chain aliphatic, araliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms. Two radicals R may also be bonded to each other to form a ring. The radicals are preferably aliphatic hydrocarbon radicals having 1 to 5 carbon atoms, particularly preferably straight or branched chain alkyl radicals.

For example, dialkyl or diaryl carbonates can be prepared from the reaction of aliphatic, araliphatic or aromatic alcohols, preferably monoalcohols with phosgene. It can also be prepared via oxidative carbonylation of alcohols or phenols using CO in the presence of precious metals, oxygen or NO _x . Regarding the preparation of the diaryl or dialkyl carbonates, see also Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 Electronic Release, Verlag Wiley-VCH.

Examples of suitable carbonates include aliphatic or aromatic carbonates such as ethylene carbonate, propylene 1,2- or 1,3-carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate , Dinaphthyl carbonate, ethyl phenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate , Dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecyl carbonate or dododecyl carbonate.

Aliphatic carbonates, especially those in which the radical has 1 to 5 carbon atoms, for example dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate Preference is given to using.

The organic carbonate is reacted with at least one aliphatic alcohol (BB) having three or more OH groups, or a mixture of two or more alcohols.

Examples of compounds having three or more OH groups include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, Based on tris (hydroxypropyl) amine, pentaerythritol, bis (trimethylolpropane), or sugars such as glucose, trivalent or higher polyhydric alcohols and ethylene oxide, propylene oxide, or butylene oxide Trivalent or higher polyvalent polyetherols or polyesterols. Particular preference is given here to glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, and also polyetherols thereof based on ethylene oxide or propylene oxide.

Such polyhydric alcohols may also be used in admixture with dihydric alcohols (BB ′), provided that the average total OH functionality of all alcohols used is greater than two. Examples of suitable compounds having two OH groups include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-, 1,3- and 1,4-butanediol, 1,2-, 1,3- and 1,5-pentanediol, hexanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, bifunctional polyetherol Or polyesterols.

The reaction of carbonates with alcohols or alcohol mixtures to provide the highly functional highly branched polycarbonates of the present invention is generally carried out by removing monofunctional alcohols or phenols from the carbonate molecules.

The highly functional highly branched polycarbonates formed through the process of the invention are terminated with hydroxy groups and / or carbonate groups after the reaction, ie no further modification takes place. It is used in various solvents such as water, alcohols such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, It has good solubility in dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, or propylene carbonate.

For the purposes of the present invention, highly functional polycarbonates have at least three, preferably at least six, more preferably at least ten, terminating or pendant functional groups in addition to the carbonate groups forming the polymer backbone. Product. The functional group is a carbonate group and / or an OH group. In principle, there is no upper limit to the number of terminating or pendant functional groups, but products with too many functional groups may have undesired properties such as high viscosity or poor solubility. The highly functional polycarbonates of the present invention mostly have up to 500 terminal or pendant functional groups, preferably up to 100 terminal or pendant functional groups.

When preparing highly functional polycarbonate B21, the ratio of compounds comprising OH groups to carbonate is the simplest resulting condensate (hereinafter referred to as condensate (BK)) with an average of one carbonate group. And more than one OH group, or one OH group and more than one carbonate group. The simplest structure here of a condensate (BK) consisting of carbonate (BA) and di- or polyalcohol (BB) is here an arrangement XY _n or Y _n X where X is a carbonate group and Y is a hydrate Hydroxy group, n generally being 1-6, preferably 1-4, particularly preferably 1-3. Reactive groups that are here formed as a single group are generally referred to below as "focal groups".

For example, if the reaction ratio is 1: 1 during the preparation of the simplest condensate (BK) from carbonate and dihydric alcohol, the average result is a molecule of type XY exemplified by formula (1).

During the preparation of condensates (BK) from carbonates and trihydric alcohols at a reaction ratio of 1: 1, the average result is a molecule of type XY ₂ exemplified by formula (2). The carbonate group is the concentrator here.

Likewise during the preparation of condensates (BK) from carbonates and tetrahydric alcohols at a reaction ratio of 1: 1, the average result is a molecule of type XY ₃ exemplified by formula (3). The carbonate group is the concentrator here.

R in formulas 1 to 3 have the definition given in the above organic carbonate (BA), and R ¹ is an aliphatic radical.

Condensates (BK) can also be prepared from carbonates and trihydric alcohols, as illustrated, for example, in Formula 4, with a molar reaction ratio of 2: 1. Here, the average result is a molecule of type X ₂ Y, where the OH group is the concentrator here. In formula (4), R and R ¹ are as defined in formula (1) to (3).

If a bifunctional compound, for example dicarbonate or diol, is also added to the component, it extends the chain, for example as illustrated in formula (5). The average result is also a molecule of XY ₂ type, where the carbonate groups are concentrators.

In formula (5), R ² is an organic, preferably aliphatic radical, and R and R ¹ are as defined above.

According to the invention, the simple condensates (BK) described for example in formulas 1 to 5 preferably react intermolecularly to form highly functional polycondensates, hereinafter referred to as polycondensates (BP). The reaction for providing the condensate (K) and the reaction for providing the polycondensate (BP) are mainly carried out in bulk or in solution at a temperature of 0 to 250 ° C., preferably 60 to 160 ° C. Any solvent which is inert to the starting material here can generally be used here. Preference is given to using organic solvents such as decane, dodecane, benzene, toluene, chlorobenzene, xylene, dimethylformamide, dimethylacetamide or solvent naphtha.

In one preferred embodiment, the condensation reaction is carried out in bulk. To accelerate the reaction, the free phenol or monohydric alcohol ROH during the reaction can be removed by distillation from the reaction equilibrium at reduced pressure if necessary.

If intended to be removed by distillation, it is generally recommended to use a carbonate which liberates the alcohol ROH with a boiling point below 140 ° C. during the reaction.

Catalysts or catalyst mixtures may also be added to accelerate the reaction. Suitable catalysts are compounds which catalyze esterification or transesterification reactions, for example alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, tertiary, preferably of sodium, potassium or cesium Amines, guanidines, ammonium compounds, phosphonium compounds, organoaluminum, organotin, organozinc, organotitanium, organozirconium or organbismuth compounds, or else double metal cyanides as described, for example, in DE 10138216 or DE 10147712 (DMC) is a compound known as a catalyst.

Potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, diazabicyclooctane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles such as imidazole, 1 -Methylimidazole or 1,2-dimethylimidazole, titanium tetrabutoxide, titanium tetraisopropoxide, dibutyltin oxide, dibutyltin dilaurate, tin dioctoate, zirconium acetylacetonate, Or mixtures thereof.

Generally the amount of catalyst added is 50 to 10,000 ppm by weight, preferably 100 to 5000 ppm by weight, based on the amount of alcohol mixture or alcohol used.

It is also possible to control the intermolecular polycondensation reaction through the addition of a suitable catalyst or else by the selection of a suitable temperature. The average molecular weight of the polymer (BP) can also be adjusted via the composition of the starting component and through the residence time.

Condensates (BK) and polycondensates (BP) produced at elevated temperatures are typically stable at room temperature for a relatively long period of time.

The nature of the condensate (BK) results in polycondensates (BP) having different structures from the condensation reaction, which have no crosslinks and have branches. Also, in an ideal case, the polycondensate (BP) has one carbonate group and more than two OH groups as a concentrator or else one OH group and more than two carbonate groups as a concentrator. The number of reactive groups here is a result of the nature and degree of polycondensation of the condensates (BK) used.

For example, the condensate (BK) according to formula (2) can be reacted via triple intermolecular condensation to provide two polycondensates (BP) represented by formulas (6) and (7).

R and R ¹ in Chemical Formulas 6 and 7 are as defined in Chemical Formulas 1 to 5 above.

There are various ways to terminate the intermolecular polycondensation reaction. For example, the temperature can be lowered to a range where the reaction is stopped and the product (BK) or polycondensate (BP) is storage-stable.

In another embodiment, as soon as the intermolecular reaction of the condensate (BK) produces a polycondensate (BP) having the desired degree of polycondensation, a product having a group reactive to the concentrator of (BP) is added to the product (BP) To terminate the reaction. If the concentrator is a carbonate group, for example mono-, di- or polyamines can be added. If the concentrator is a hydroxy group, for example mono-, di- or polyisocyanates, or compounds comprising epoxy groups or acid derivatives which react with OH groups can be added to the product (BP).

The highly functional polycarbonates of the present invention are prepared in the pressure range of 0.1 mbar to 20 bar, preferably 1 mbar to 5 bar, mostly in batch or semi-continuous or continuously operated reactors or reactor cascades.

The product of the invention can continue to be processed without further purification after its preparation, thanks to the adjustment of the reaction conditions mentioned above, and optionally thanks to the selection of a suitable solvent.

In another preferred embodiment, the polycarbonates of the present invention may comprise other functional groups than the functional groups present in this step thanks to the above reaction. Functionalization can be carried out during the process or else subsequently, ie after completion of the actual polycondensation, in order to increase the molecular weight.

If a component having functional groups or functional elements other than hydroxy or carbonate groups is added before or during the process to increase the molecular weight, the result is that randomly distributed functional groups other than carbonate or hydroxy groups It is a polycarbonate polymer which has.

This type of effect is effected during polycondensation, for example, other functional or functional elements other than hydroxy groups or carbonate groups such as mercapto groups, primary, secondary or tertiary amino groups, ether groups, carboxyl It can be achieved through the addition of compounds having derivatives of acids, derivatives of sulfonic acids, derivatives of phosphonic acids, silane groups, siloxane groups, aryl radicals or long chain alkyl radicals. Examples of compounds that can be used for reforming with carbamate groups include ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, Higher alkoxylated products of 2- (2'-aminoethoxy) ethanol or ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine, diethanolamine, dipropanolamine, diisopropanolamine, tris ( Hydroxymethyl) aminomethane, tris (hydroxyethyl) aminomethane, ethylenediamine, propylenediamine, hexamethylenediamine or isophoronediamine.

An example of a compound that can be used for modification with mercapto groups is mercaptoethanol. For example, tertiary amino groups can be prepared by introducing N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethyl-ethanolamine. For example, ether groups can be produced through co-condensation of divalent or higher polyvalent polyetherols. Long chain alkyl radicals can be introduced via reaction with long chain alkanediols, and reaction with alkyl or aryl diisocyanates produces polycarbonates having alkyl, aryl and urethane groups.

Subsequent functionalization is the addition of a process to react the resulting highly functional highly branched, or highly functional hyperbranched polycarbonate with a suitable functionalizing agent capable of reacting with the OH and / or carbonate groups of the polycarbonate. Can be achieved using an optional step (step c)).

For example, highly functional highly branched, or highly functional hyperbranched polycarbonates containing hydroxy groups can be modified through the addition of molecules comprising acid groups or isocyanate groups. For example, polycarbonates comprising acid groups can be obtained via reaction with compounds comprising anhydride groups.

Highly functional polycarbonates containing hydroxy groups are also highly functional polycarbonate polyether polyols via reaction with alkylene oxides, such as ethylene oxide, propylene oxide, or butylene oxide Can be converted to

A big advantage of the process is its cost-efficiency. Both reactions to give condensates (BK) or polycondensates (BP) and also reactions of (BK) or (BP) to give polycarbonates with other functional groups or elements can be carried out in one reactor, This is advantageous from a technical and cost-effective point of view.

The molding composition of the present invention may comprise as component B22 one or more hyperbranched polyesters of the type A _x B _y ,

Where

x is at least 1.1, preferably at least 1.3, in particular at least 2,

y is at least 2.1, preferably at least 2.5, in particular at least 3.

Naturally, mixtures can be used as units A and / or B.

A _x B _y -type polyesters are condensates consisting of an x-functional molecule A and a y-functional molecule B. For example, mention may be made of polyesters consisting of adipic acid as molecule A (x = 2) and glycerol as molecule B (y = 3).

For the purposes of the present invention, hyperbranched polyester B22 is a non-crosslinked macromolecule having hydroxy groups and carboxy groups, which have both structural and molecular non-uniformities. Its structure is first based on the central molecule in the same way as the dendrimer, but the chain length of the branches is nonuniform. Secondly, it can also have a linear structure with functional pendant groups, or else it can be a combination of two extremes with linear and branched molecular moieties. In addition, the definitions of dendrimer and hyperbranched polymers are described in P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499].

By “hyperbranched” in the context of the present invention is meant the degree of branching (DB), ie the sum of the average number of dendritic linkages and terminal groups per molecule, which is 10 to 99.9%, preferably 20 to 99%, in particular Preferably it is 20 to 95%.

"Dendrimer type" in the context of the present invention means that the degree of branching is 99.9 to 100%. The definition of “degree of branching” is described in H. Frey et al., Acta Polym. 1997, 48, 30. In the context of the present invention, the term "highly branched" is used synonymously with "dendrimer".

M _n of component B22 is preferably from 300 to 30,000 g / mol, in particular from 400 to 25,000 g / mol, very particularly from 500 to 20,000 g / mol (measured using GPC, PMMA reference, dimethylacetamide eluent). to be.

The OH value of B22 is preferably from 0 to 600 mg KOH / g polyester, preferably from 1 to 500 mg KOH / g polyester, in particular from 20 to 500 mg KOH / g polyester, in accordance with DIN 53240, and the COOH value is preferably from 0 to 600 mg KOH / g polyester, preferably 1 to 500 mg KOH / g polyester, especially 2 to 500 mg KOH / g polyester.

T _g is preferably -50 ° C to 140 ° C, in particular -50 to 100 ° C (measured using DSC, according to DIN 53765).

Particular preference is given to components B22 in which at least one of OH or COOH is greater than zero, preferably greater than 0.1 and in particular greater than 0.5.

Component B22 of the present invention is particularly obtainable through the process described below, specifically

(a) at least one dicarboxylic acid or at least one derivative thereof having at least trihydric alcohol, or

(b) at least one tricarboxylic acid or higher polycarboxylic acid or at least one derivative thereof having at least one diol

Is obtainable by reaction in the presence of a solvent and optionally in the presence of an inorganic, organometallic, or low molecular weight organic catalyst, or enzyme. Reaction in a solvent is a preferred manufacturing method.

For the purposes of the present invention, highly functional hyperbranched polyester B22 has molecular and structural non-uniformity. Its molecular non-uniformity allows it to be distinguished from dendrimers and thus can be manufactured at significantly lower costs.

Among the dicarboxylic acids which can be reacted according to the variant (a), for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suveric acid, azelaic acid, sebacic acid, undecane- α, ω-dicarboxylic acid, dodecane-α, ω-dicarboxylic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3- Dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid and cis- and trans-cyclopentane-1,3 Dicarboxylic acid,

Wherein the above-mentioned dicarboxylic acids may be substituted with one or more radicals selected from:

C ₁ -C ₁₀ -alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl,

C ₃ -C ₁₂ -cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; Preferably cyclopentyl, cyclohexyl and cycloheptyl;

Alkylene groups such as methylene or ethylidene, or

C ₆ -C ₁₄ -aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenan Tril, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.

Examples that may be mentioned as representative of substituted dicarboxylic acids are as follows: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2- Phenylsuccinic acid, itaconic acid, 3,3-dimethylglutaric acid.

Among the dicarboxylic acids which can be reacted according to variant (a) are also ethylenically unsaturated acids such as maleic acid and fumaric acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid.

It is also possible to use mixtures of two or more of the aforementioned representative compounds.

Dicarboxylic acids can be used as such or in derivative form.

The derivative is preferably as follows.

-Monomeric or other related anhydrides in polymeric form,

Mono- or dialkyl esters, preferably mono- or dimethyl esters, or corresponding mono- or diethyl esters, or else higher alcohols such as n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol mono- and dialkyl esters derived from n-pentanol, n-hexanol,

-And also mono- and divinyl esters, and

Mixed esters, preferably methyl ethyl ester.

In a preferred manufacturing process, it is also possible to use mixtures of dicarboxylic acids and one or more derivatives thereof. It is likewise possible to use mixtures of two or more derivatives of one or more dicarboxylic acids.

Particular preference is given to using succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, or mono- or dimethyl esters thereof. Very particular preference is given to using adipic acid.

Examples of trivalent or higher alcohols that can be reacted are: glycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5 -Triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, n-hexane-1,3,6-triol, trimethylolbutane, trimethylolpropane Or ditrimethylolpropane, trimethylolethane, pentaerythritol or dipentaerythritol; Sugar alcohols such as mesoerythritol, trytol, sorbitol, mannitol, or mixtures of the above trihydric alcohols. Preference is given to using glycerol, trimethylolpropane, trimethylolethane and pentaerythritol.

Examples of tricarboxylic acid or polycarboxylic acid which can be reacted according to variant (b) are benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzene- 1,2,4,5-tetracarboxylic acid and melic acid.

Tricarboxylic acids or polycarboxylic acids can be used as such or in the form of derivatives for the reaction of the present invention.

The derivative is preferably as follows.

-Monomeric or other related anhydrides in polymeric form,

Mono-, di or trialkyl esters, preferably mono-, di- or trimethyl esters, or corresponding mono-, di- or triethyl esters, or else higher alcohols such as n-propanol, isopropanol, n- Mono-, di- and triesters derived from butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, or else mono-, di- or trivinyl esters, and

Mixed methyl ethyl ester.

For the purposes of the present invention, it is also possible to use mixtures of tri- or polycarboxylic acids and one or more derivatives thereof. For the purposes of the present invention, it is likewise possible to use mixtures of two or more derivatives of one or more tri- or polycarboxylic acids in order to obtain component B22.

Examples of diols used in variant (b) of the present invention include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, Butane-1,4-diol, butane-2,3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane- 2,3-diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane-1, 6-diol, hexane-2,5-diol, heptane-1,2-diol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,5-hexadiene-3,4-diol, cyclopentanediol, cyclohexanediol, inositol And derivatives, (2) -methylpentane-2,4-diol, 2,4-dimethyl-pentane-2,4-diol, 2-ethylhexane-1,3-diol, 2,5-dimethylhexane-2, 5-diol, 2,2,4-trimethyl-pentane-1,3-diol, pinacol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, poly Glycol _{HO (CH 2 CH 2 O)} n -H or polypropylene glycols _{HO (CH [CH 3] CH} 2 O) n -H ( wherein a, n is an integer, n being ≤ 4), or two of the compounds There is a mixture of the above representative compounds. Wherein one or otherwise two hydroxy groups in the above-mentioned diols can also be replaced with SH groups. Ethylene glycol, propane-1,2-diol, and diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol are preferred.

The molar ratio of molecule A to molecule B in A _x B _y polyester in variants (a) and (b) is from 4: 1 to 1: 4, in particular from 2: 1 to 1: 2.

The trivalent or higher alcohols reacted according to variant (a) of the process may all have hydroxy groups having the same reactivity. Tri- or higher alcohols are also preferred here, wherein their OH groups initially have the same reactivity but reaction with one or more acid groups can lead to a reduction in the reactivity of the remaining OH groups as a result of steric or electronic effects. For example, this applies when trimethylolpropane or pentaerythritol is used.

However, the trihydric or higher alcohol reacting according to variant (a) may also have hydroxy groups having two or more chemical reactivity.

The different reactivity of the functional groups here can be derived from chemical causes (eg primary / secondary / tertiary OH groups) or steric causes.

For example, triols can include triols having primary and secondary hydroxy groups, with a preferred example being glycerol.

When the reaction of the invention is carried out according to variant (a), it is preferred to operate in the absence of diols and monohydric alcohols.

When the reaction of the invention is carried out according to variant (b), it is preferred to operate in the absence of mono- or dicarboxylic acids.

The process of the invention is carried out in the presence of a solvent. For example, hydrocarbons such as paraffin or aromatics are suitable. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene in the form of isomeric mixtures, ethylbenzene, chlorobenzene, and ortho- and meta-dichlorobenzene. Other solvents which are very particularly suitable in the absence of an acidic catalyst are: ethers such as dioxane or tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

According to the invention, the addition amount of the solvent is at least 0.1% by weight, preferably at least 1% by weight, particularly preferably at least 10% by weight, based on the weight of the starting material to be used and reacted. It is also possible to use an excess of solvent, for example from 1.01 to 10 times the amount, based on the weight of the starting material to be used and reacted. The amount of solvent that is more than 100 times the weight of the starting material to be used and reacted is not advantageous because at a significantly lower concentration of the reactants the reaction rate is significantly reduced resulting in an uneconomically long reaction time.

In order to carry out the preferred process according to the invention, the operation can be carried out in the presence of a dehydrating agent as an additive added at the start of the reaction. Suitable examples are molecular sieves, especially 4 ′ molecular sieves, MgSO ₄ and Na ₂ SO ₄ . It is also possible to add additional dehydrating agent or to replace the dehydrating agent with fresh dehydrating agent during the reaction. It is also possible to remove water or alcohol by distillation during the reaction and by using a water trap, for example.

The process can be carried out in the absence of an acidic catalyst. It is preferred to operate in the presence of an acidic inorganic, organometallic or organic catalyst, or a mixture of two or more acidic inorganic, organometallic or organic catalysts.

For the purposes of the present invention, examples of acidic inorganic catalysts are sulfuric acid, phosphoric acid, phosphonic acid, hypophosphoric acid, aluminum sulfate hydrate, alum, acidic silica gel (pH = 6, in particular = 5), and acidic aluminum oxide. Examples of other compounds that can be used as acidic inorganic catalysts include those of the formula Al (OR) ₃ . Aluminum compound and the formula Ti (OR) ₄ titanate, wherein each radical R may be the same or different and is independently selected from:

C ₁ -C ₁₀ -alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl,

C ₃ -C ₁₂ -cycloalkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; Preferably cyclopentyl, cyclohexyl and cycloheptyl.

Each radical R in Al (OR) ₃ or Ti (OR) ₄ is preferably identical and is selected from isopropyl or 2-ethylhexyl.

Examples of preferred acidic organometallic catalysts are selected from dialkyltin oxides R ₂ SnO, wherein R is as defined above. Particularly preferred representative compounds for acidic organometallic catalysts are di-n-butyltin oxide (commercially available as "oxo-tin"), or di-n-butyltin dilaurate.

Preferred acidic organic catalysts are, for example, acidic organic compounds having phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Sulphonic acids such as para-toluenesulfonic acid are particularly preferred. Polystyrene resins containing acidic ion exchange groups, for example sulfonic acid groups, and crosslinked with about 2 mol% divinylbenzene can also be used as acidic organic catalysts.

It is also possible to use combinations of two or more of the aforementioned catalysts. It is also possible to use immobilized forms of such organic or organometallic catalysts or else inorganic catalysts that take the form of individual molecules.

If an acidic inorganic, organometallic or organic catalyst is to be used, the amount used according to the invention is from 0.1 to 10% by weight, preferably from 0.2 to 2% by weight of the catalyst.

The process of the invention is carried out under an inert gas, for example carbon dioxide, nitrogen or a noble gas, among which mention may be made in particular of argon.

The process of the invention is carried out at a temperature of 60 to 200 ° C. It is preferable to operate at 130-180 degreeC, especially the temperature of 150 degrees C or less or less. A maximum temperature of 145 ° C. or lower is particularly preferred, and a temperature of 135 ° C. or lower is very particularly preferred.

In the process of the invention the pressure conditions are not critical in themselves. It is possible to operate at significantly lower pressures, for example from 10 to 500 mbar. The process of the invention may also be carried out at pressures above 500 mbar. The reaction at atmospheric pressure is preferred for simplicity, but it is also possible to carry out at slightly increased pressure, for example up to 1200 mbar. It is also possible to operate at significantly increased pressures, for example up to 10 bar. Reaction at atmospheric pressure is preferred.

In the process of the present invention, the reaction time is usually 10 minutes to 25 hours, preferably 30 minutes to 10 hours, particularly preferably 1 to 8 hours.

Once the reaction is complete, the highly functional hyperbranched polyesters can be easily isolated, for example by filtering and concentrating the mixture to remove the catalyst, where the concentration process is usually carried out under reduced pressure. Another post-treatment method with good suitability is precipitation after addition of water, followed by washing and drying.

Component B22 can also be prepared in the presence of an enzyme or degradation product of an enzyme (according to DE-A 101 63163). For the purposes of the present invention, the term acidic organic catalyst does not include dicarboxylic acids reacted according to the present invention.

Preference is given to using lipases or esterases. Lipases and esterases with excellent suitability include Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis, croida Chromobacterium viscosum, Geotrihum viscosum, Geotrihum candidum, Mucor javanicus, Mucor mihei, Pig interest , Pseudomonas spp., Pseudomonas fluorescens, Pseudomonas cepacia, Rhizopus arrhizus, Rhizopus delemarpus, Rhizopus delezopus, Rhizopus delezopus niveus), Rizopus oryzae, Aspergillus niger, Penicillium roquefoti rtii), Penicillium camembertii, or esterases from Bacillus subspecies and Bacillus thermoglucosidasius. Candida antartica lipase B is particularly preferred. Enzymes listed are, for example, Novozyme Biotech Inc., Denmark. (Novozymes Biotech Inc.).

The enzyme is preferably used in immobilized form, for example on silica gel or Lewatit®. Processes for immobilizing enzymes are described, for example, in Kurt Faber, "Biotransformations in organic chemistry", 3rd edition 1997, Springer Verlag, Chapter 3.2 "Immobilization" pp. 345-356, per se. Immobilized enzymes are commercially available, for example, from Novozyme Biotech Inc., Denmark.

The amount of immobilized enzyme used is from 0.1 to 20% by weight, in particular from 10 to 15% by weight, based on the total weight of the starting material to be used and reacted.

The process of the invention is carried out at temperatures above 60 ° C. It is desirable to operate at temperatures of 100 ° C. or less. The temperature of 80 degrees C or less is preferable, the temperature of 62-75 degreeC is very especially preferable, and the temperature of 65-75 degreeC is more preferable.

The process of the invention is carried out in the presence of a solvent. Examples of suitable compounds are hydrocarbons such as paraffin or aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene in the form of isomer mixtures, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Other very particularly suitable solvents are ethers such as dioxane or tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

The amount of the solvent added is at least 5 parts by weight, preferably at least 50 parts by weight, particularly preferably at least 100 parts by weight, based on the weight of the starting material to be used and reacted. The amount of solvent that is more than 10,000 parts by weight is not preferable because the reaction rate is significantly reduced at significantly low concentrations, resulting in an uneconomically long reaction time.

The process of the invention is carried out at pressures above 500 mbar. Preference is given to reactions at atmospheric pressure or slightly increased pressure, for example up to 1200 mbar. It is also possible to operate at significantly increased pressures, for example pressures up to 10 bar. Reaction at atmospheric pressure is preferred.

In the process of the invention the reaction time is usually 4 hours to 6 days, preferably 5 hours to 5 days, particularly preferably 8 hours to 4 days.

Once the reaction is complete, highly functional hyperbranched polyesters can be easily isolated, for example by filtering and concentrating the mixture to remove enzymes, which concentration process is typically carried out under reduced pressure. Another post-treatment method with good suitability is precipitation after addition of water, followed by washing and drying.

The highly functional hyperbranched polyesters obtainable by the process of the invention are characterized by particularly low content of discolored and resinized materials. The definition of hyperbranched polymers is also described in P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and A. Sunder et al., Chem. Eur. J. 2000, 6, no. 1, 1-8]. However, in the context of the present invention, "highly functional hyperbranched" means the degree of branching, ie the sum of the average number of dendritic linkages and terminal groups per molecule, which is 10 to 99.9%, preferably 20 to 99% , Particularly preferably 30 to 90% (see in this regard H. Frey et al. Acta Polym. 1997, 48, 30).

The molecular weight M _w of the polyesters of the present invention is 500 to 50,000 g / mol, preferably 1000 to 20,000 g / mol, particularly preferably 1000 to 19,000 g / mol. The polydispersity is 1.2 to 50, preferably 1.4 to 40, particularly preferably 1.5 to 30, very particularly preferably 1.5 to 10. It is usually very soluble, i.e. up to 50% by weight, in some cases even up to 80% by weight, using the inventive polyester in tetrahydrofuran (THF), n-butyl acetate, ethanol and many other solvents, visually Clear solutions can be prepared without detectable gel particles.

The highly functional hyperbranched polyesters of the present invention are carboxy-terminated, carboxy- and hydroxy-terminated, preferably hydroxy-terminated.

The ratio of components B21: B22 is preferably 1:20 to 20: 1, in particular 1:15 to 15: 1, very particularly 1: 5 to 5: 1, if a mixture thereof is used.

The hyperbranched polycarbonate B21 / polyester B22 used is 20-500 nm size particles. These nanoparticles are finely distributed in the polymer blend and the size of the particles in the blended material is 20 to 500 nm, preferably 50 to 300 nm.

Blended materials of this type are commercially available, for example in the form of Ultradur® high speeds.

Shock- Reformed  Polymer D

As component D, plastic component B may comprise from 1 to 40% by weight, preferably from 1 to 20% by weight of impact-modifying polymers (often also referred to as elastomeric polymers or elastomers).

Preferred elastomeric polymers are olefin based polymers consisting of the following components.

At least one α-olefin having from 2 to 8 carbon atoms, from 40 to 100% by weight of D1, preferably from 55 to 79.5% by weight,

D2 0-90% diene,

D 3 0-45% by weight, preferably 20-40% by weight of C ₁ -C ₁₂ -alkyl esters of acrylic acid or methacrylic acid, or mixtures of such esters,

D4 0-40% by weight, preferably 0.5-20% by weight, ethylenically unsaturated mono- or dicarboxylic acid, or functional derivatives of such acids,

D5 monomer containing 0 to 40% by weight of epoxy groups,

D6 0 to 5% by weight of other monomers capable of free-radical polymerization,

However, component D is not an olefin homopolymer, since the same beneficial effect is not achieved with the use of such a material, for example polyethylene.

The first preferred series is a series of rubbers known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers, preferably having a ratio of ethylene units to propylene units ranging from 40:60 to 90:10.

Mooney viscosity (MLI + 4/100 ° C.) of its non-crosslinked EPM or EPDM rubber (generally less than 1% by weight gel content) (large rotor after operation at 100 ° C. for 4 minutes) Measured according to DIN 53 523), preferably in the range from 25 to 100, in particular from 35 to 90.

EPM rubbers generally have substantially no double bonds left, while EPDM rubbers can have from 1 to 20 double bonds per 100 carbon atoms.

Examples of diene monomers D2 for EPDM rubbers include conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5- Hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, and also alkenylnor Bornennes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and Tricyclodienes such as 3-methyltricyclo [5.2.1.0.2.6] -3,8-decadiene or mixtures thereof. Preference is given to 1,5-hexadiene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubber is preferably from 0.5 to 50% by weight, in particular from 2 to 20% by weight, particularly preferably from 3 to 15% by weight, based on the total weight of the olefin polymer.

EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or derivatives thereof. Particular mention may be made of acrylic acid, methacrylic acid and derivatives thereof, and also maleic anhydride.

An example of a particularly preferred component D is an MBS rubber consisting of:

65 to 99% by weight of core

D2 90-100 wt% diene and 0-10 wt% other crosslinkable monomer,

And 1 to 35% by weight of shell

D7 1-30% by weight of styrene or unsaturated styrene, or mixtures thereof, and

D8 70-100% by weight of one or more unsaturated nitriles.

Suitable monomers D7 are styrenes or substituted styrenes of the formula VIII, or mixtures thereof.

&Lt; Formula (VIII)

Wherein R is a C ₁ -C ₈ -alkyl radical, preferably methyl or ethyl, or hydrogen, R ¹ is a C ₁ -C ₈ -alkyl radical, preferably methyl or ethyl, n is 1, 2 Or three.

Another group of preferred olefin polymers are α-olefins having 2 to 8 carbon atoms, in particular copolymers of ethylene with C ₁ -C ₁₈ -alkyl esters of acrylic acid and / or methacrylic acid.

In principle, any of primary, secondary, or tertiary C ₁ -C ₁₈ -alkyl esters of acrylic acid or methacrylic acid is suitable, but esters having from 1 to 12 carbon atoms, in particular from 2 to 10 carbon atoms Is preferred.

Examples thereof are methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, octyl and decyl (meth) acrylate. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are especially preferable.

The proportion of methacrylic acid ester and acrylic acid ester D3 in the olefin polymer is 0 to 60% by weight, preferably 10 to 50% by weight, in particular 30 to 45% by weight.

Other monomers that may be present in place of or in addition to ester D3 in the olefin polymer are monomers having acid functionality and / or monomers with latent acid functionality, which contain ethylenically unsaturated mono- or dicarboxylic acid D4, or epoxy groups. Derived from monomer D5.

Examples of monomers D4 that may be mentioned are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate, and dicarboxylic acids such as maleic acid and fumaric acid, or derivatives of such acids, and also Its monoesters.

Monomers with latent acid functional groups are compounds which form free acid groups under the conditions of the polymerization process or during the introduction of the olefin polymer into the molding composition. Examples that may be mentioned twice are anhydrides of dicarboxylic acids having up to 20 carbon atoms, in particular maleic anhydride, and tertiary C ₁ -C ₁₂ -alkyl esters of the abovementioned acids, in particular tert-butyl acrylate And tert-butyl methacrylate.

The monomer having an acid function or a latent acid function, and the monomer containing an epoxy group, are preferably introduced into the olefin polymer through the addition of the compounds of the formulas (XI) to (XII) to the monomer mixture.

<Formula IX>

(X)

(XI)

(XII)

Wherein the radicals R ¹ -R ⁹ are hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer from 0 to 20 and n is an integer from 0 to 10.

R ¹ -R ⁷ are preferably hydrogen, m is preferably 0 or 1 and n is preferably 1. Corresponding compounds are maleic acid, fumaric acid, maleic anhydride D4, or alkenyl glycidyl ether or vinyl glycidyl ether D5.

Preferred compounds of formula (IX), (X), (XI) and (XII) are, as component D4, epoxy-containing esters of maleic acid and maleic anhydride and acrylic acid and / or methacrylic acid, particularly preferably glycidyl acrylate and glycidyl meta Acrylate (as component D5).

The proportion of each component D4 and D5 is from 0.07 to 40% by weight, in particular from 0.1 to 20% by weight, particularly preferably from 0.15 to 15% by weight, based on the total weight of the olefin polymer.

Particular preference is given to olefin polymers consisting of:

50 to 98.9 weight percent, especially 55 to 65 weight percent of ethylene,

0.1 to 20% by weight, in particular 0.15 to 10% by weight of glycidyl acrylate and / or glycidyl methacrylate, acrylic acid, and / or maleic anhydride,

1 to 45% by weight, in particular 25 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate, and

0-10% by weight of maleic anhydride or fumaric acid, in particular 0.1-3% by weight, or mixtures thereof.

Other preferred esters of acrylic acid and / or methacrylic acid are methyl, ethyl, propyl, isobutyl and tert-butyl esters.

Examples of other monomers D6 are vinyl esters and vinyl ethers.

If such olefin polymers are used, their proportions are preferably from 0 to 20% by weight, in particular from 4 to 18% by weight and very particularly from 5 to 15% by weight, based on the total weight of all components.

The ethylene copolymers described above can be prepared via known processes, preferably by random copolymerization at high pressures and elevated temperatures.

The melt index of ethylene copolymers generally ranges from 1 to 80 g / 10 min (measured at 190 ° C. and 2.16 kg loads).

Also preferred is an acrylate rubber D consisting of:

a) 70 to 90% by weight, preferably 75 to 85% by weight of crosslinked elastomeric core, consisting of:

1) Copolymer (I) of 20 to 90% by weight of an n-alkyl acrylate, or mixture of alkyl acrylates, wherein the alkyl group has 5 to 12 carbon atoms, preferably 5 to 8 carbon atoms The number of carbon atoms in the straight or branched alkyl group is in the range of 2 to 12, preferably 4 to 8); A core consisting of a multifunctional crosslinker, wherein the molecule has an unsaturated group, in particular one or more CH ₂ = C <groups of the vinyl type, and optionally a polyfunctional grafting agent, wherein the molecule is an unsaturated group, in particular Having at least one CH ₂ ═CH—CH ₂ — group of the allyl type, wherein the core contains from 0.05 to 5%, preferably from 0.5 to 1.5% by weight of a molar amount of crosslinker and optionally a grafting agent,

2) copolymers of n-alkyl acrylates in which 80 to 10% by weight of alkyl groups have 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms, or a mixture of alkyl acrylates as defined in 1) (II); And a shell consisting of a multifunctional grafting agent, wherein the molecule has an unsaturated group, in particular one or more CH ₂ ═CH—CH ₂ — groups of the allyl type, wherein the shell is 0.05 to 2.5%, preferably 0.5 to 1.5 weight Containing a molar amount of grafting agent in%), and

b) 30 to 10% by weight, preferably 25 to 15% by weight, of an alkyl methacrylate polymer grafted onto the core and having an alkyl group having from 1 to 4 carbon atoms, or having from 1 to 4 alkyl groups Random copolymers of alkyl methacrylates with carbon atoms and alkyl acrylates in which the alkyl groups have 1 to 8 carbon atoms (the molar amount of alkyl acrylates present is in the range of 5 to 40%, preferably 10 to 20%) Shell consisting of.

As examples of n-alkyl acrylates that can be used to form copolymer (I) according to the invention, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, in particular n-octyl acrylate can be used. have.

Examples of n-alkyl acrylates that can be used to form copolymer (II) according to the invention are n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, in particular n- Octyl acrylate.

The n-alkyl acrylates that can be used to form copolymers (I) and / or (II) can be the same or different.

As examples of straight or branched chain alkyl acrylates which can be used to form mixtures of alkyl acrylates in copolymers (I) and / or (II) according to the invention, ethyl acrylate, n-propyl acrylate, n- Butyl acrylate, amyl acrylate, 2-methylbutyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-dodecyl acrylate and 3,5 , 5-trimethylhexyl acrylate can be used.

If a mixture of alkyl acrylates is used to form copolymers (I) and / or (II), the proportion of n-alkyl acrylates used is at least 10% by weight of the mixture of alkyl acrylates, preferably 20 to 80 It must be in the% range.

As mentioned above, the same or different mixtures of alkyl acrylates can be used to prepare copolymers (I) and / or (II).

According to the invention, preference is given to using n-alkyl acrylates, in particular n-octyl acrylate, for preparing copolymers (I) and (II).

If a mixture of alkyl acrylates is used to form copolymers (I) and / or (II), the amount used is preferably 20 to 80% by weight of n-octyl acrylate, preferably 80 to 20% by weight of n -Butyl acrylate.

Examples of alkyl methacrylates that can be used to form grafted shells on crosslinked elastomeric cores according to the present invention include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate; n-butyl methacrylate, isobutyl acrylate, especially methyl methacrylate.

The crosslinkers used to form copolymer (I) are according to the invention, in particular from derivatives having at least two vinyl type double bonds, or at least one vinyl type double bond and at least one allyl type double bond. You can choose. Preference is given to using compounds in which the molecule contains predominantly double bonds of the vinyl type.

As examples of such crosslinkers, divinylbenzene, (meth) acrylates of polyalcohols, for example trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, alkylene chains Diacrylates or methacrylates of alkylene glycols having 2 to 10 carbon atoms in them, in particular ethylene glycol diacrylate, ethylene glycol dimethacrylate, butane-1,4-diol diacrylate, butane-1, 4-dimethacrylate, hexene-1,6-diol diacrylate, hexane-1,6-dimethacrylate, diacrylate or dimethacrylate of polyoxyalkylene glycols of the formula:

(Wherein X is hydrogen or methyl, n is an integer from 2 to 4, p is an integer from 2 to 20),

In particular, mention may be made of polyacrylates having a molecular weight of about 400 (in the formula given above, n = 2 and p = 9) diacrylates or dimethacrylates of polyoxyethylene glycol).

The grafting agent used to prepare copolymer (II) is selected according to the invention in particular from two or more allyl type double bonds, or derivatives having at least one allyl type double bond and at least one vinyl type double bond. Can be.

Preference is given to using compounds in which the molecule contains predominantly allyl type double bonds.

Examples of such grafting agents that can be used are diallyl maleate, diallyl itaconate, allyl acrylate, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate and triallyl tri It is mesate.

The preferred proportion of impact modifier introduced into the thermoplastic polymer is in the range of 1 to 30% by weight, preferably 5 to 10% by weight, based on 100% by weight of the thermoplastic polymer used.

The molecular weight of the impact modifier can be evaluated by defining a melt viscosity with variations in the same range. Melt viscosity can be within a fairly wide range, provided good dispersion of impact modifiers is ensured during operation of the resin composition and the modifier use. Suitable parameters representing this melt viscosity include a 50 g impact modifier and are operated at a temperature of 200 ° C. with a rotor rotational speed of 40 rpm and a torque model of resistance in a Brabender rheometer measured at 200 ° C. after 20 minutes. The value of the comment. Suitable values for the melt viscosity of the impact modifier correspond to values in the range of 600 to 4000 Nm for the torque mentioned above. In resin compositions wherein the thermoplastic polymer is a polymer with at least 80% by weight polymerized vinyl chloride, the preferred value for the melt viscosity of the impact modifier corresponds to a torque value in the range of 800 to 3000 Nm, in particular in the range of 1000 to 2500 Nm.

EP-A 776 915 discloses a manufacturing process for this component D.

Graft  Polymer E

In one embodiment, graft copolymers or mixtures of various graft copolymers in an amount of 1 to 60% by weight, based on the total amount of all components, are used as component E in plastic component B. Preferred molding compositions of the invention comprise 2 to 50% by weight, particularly preferably 3 to 40% by weight, of at least one graft copolymer E which differs from the elastomeric polymer used as impact modifier D.

Graft polymer E consists of:

E1: 20 to 80% by weight, preferably 50 to 70% by weight, of a graft base consisting of an alkyl acrylate based elastomeric polymer having a glass transition temperature of less than 0 ° C. and having 1 to 8 carbon atoms in the alkyl radical. ,

E2: 20 to 80% by weight, preferably 30 to 50% by weight, graft consisting of:

E21: 60 to 95% by weight, preferably 70 to 85% by weight of styrene or substituted styrene of formula (XIII), or mixtures thereof

&Lt; Formula (XIII)

Wherein R is a C ₁ -C ₈ -alkyl radical, preferably methyl or ethyl or hydrogen, R ¹ is a C ₁ -C ₈ -alkyl radical, preferably methyl or ethyl, n is 1, 2 Or 3), and

E22: 5 to 40% by weight, preferably 15 to 30% by weight of one or more unsaturated nitriles, preferably acrylonitrile or methacrylonitrile, or mixtures thereof.

Polymers that can be used for the graft base E1 are those having a glass transition temperature of less than 10 ° C, preferably less than 0 ° C, particularly preferably less than -20 ° C. Examples thereof are elastomers based on C ₁ -C ₈ -alkyl esters of acrylic acid, which may include other comonomers, if desired.

Preferred graft base E1 consists of the following.

E11: 70 to 99.9% by weight, preferably 99% by weight of at least one alkyl acrylate having 1 to 8 carbon atoms in the alkyl radical, preferably n-butyl acrylate and / or 2-ethylhexyl acrylic Rates, in particular n-butyl acrylate as the sole alkyl acrylate,

E12: 0 to 30% by weight, in particular 20 to 30% by weight, of another copolymerizable monoethylenically unsaturated monomer, for example butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate or vinyl methyl ether, or mixture,

E13: 0.1 to 5% by weight, preferably 1 to 4% by weight, copolymerizable, polyfunctional, preferably 2- or trifunctional monomers which cause crosslinking.

Suitable 2- or polyfunctional crosslinking monomers E13 here preferably comprise two, or optionally three or more ethylene-based double bonds which are capable of non-conjugated copolymerization at the 1,3-position. Examples of suitable crosslinking monomers are divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate or triallyl isocyanurate. It was found that the acrylic acid ester of tricyclodecenyl alcohol is a particularly advantageous crosslinking monomer (see DE-A 12 60 135).

This type of graft base is known per se and is described in the literature, for example in DE-A 31 49 358.

Of the grafts E2, it is preferred that E21 is styrene or α-methylstyrene or mixtures thereof, and E22 is acrylonitrile or methacrylonitrile. Preferred monomer mixtures used are in particular styrene and acrylonitrile or α-methylstyrene and acrylonitrile. Grafts are obtainable through copolymerization of components E21 and E22.

Graft base E1 of graft polymer E consists of components E11, if necessary E12, and E22, also referred to as ASA rubber. Its preparation is known per se and is described for example in DE-A 28 26 925, DE-A 31 49 358 and DE-A 3414 118.

Graft polymer E can be produced, for example, by the method described in DE-C 12 60 135.

The construction of the graft (graft shell) of the graft polymer may comprise one or two steps.

In the case of the single-stage construction of the graft shell, a mixture of monomers E21 and E22 in the desired weight ratio in the range of 95: 5 to 50:50, preferably 90:10 to 65:35, is prepared in a known manner ( See, eg, DE-A 28 26 925), preferably in the presence of elastomer E1 in an emulsion.

In the two-stage configuration of graft shell E2, the first stage generally forms 20 to 70% by weight, preferably 25 to 50% by weight, based on E2. In the preparation thereof, preferably only styrene or substituted styrene, or mixtures thereof (E11) are used.

The second step of the graft shell generally forms in each case 30 to 80% by weight, in particular 50 to 75% by weight, based on E2. For their preparation, mixtures of monomers E21 and nitrile E22 are used, in which the weight ratio of E21 / E22 is generally 90:10 to 60:40, in particular 80:20 to 70:30.

The choice of conditions for the graft polymerization process preferably has a particle size of 50 to 700 nm (d ₅₀ of integral mass distribution). Value). Measurement methods for this purpose are known and are described, for example, in DE-A 2826925.

Seed latex processes can be used directly to prepare coarse-particle rubber dispersions.

In order to obtain products of maximum toughness, it is often advantageous to use mixtures of two or more graft polymers of different particle sizes.

To achieve this, the particles of rubber are enlarged in a known manner, for example via agglomeration, to give the latex a beekeeping (50-180 nm and 200-700 nm) composition.

In one preferred embodiment the particle diameters of 50 to 180 nm and 200 to 700 nm respectively (d ₅₀ of the integral mass distribution Value), a mixture of two graft polymers in a 70:30 to 30:70 weight ratio is used.

The chemical structure of the two graft polymers is preferably the same, but the shell of the coarse-particle graft polymer may in particular also consist of two steps.

Mixtures of components in which the latter graft polymer comprises coarse- and fine-particle graft polymers are described, for example, in DE-A 36 15 607. A mixture of the latter comprising components comprising a two-stage graft shell is known from EP-A 111 260.

The molding compositions of the present invention may comprise, as component F, from 0 to 60% by weight, based on the total amount of all components, of one or more copolymers of styrene or substituted styrene based and unsaturated nitrile based. Preferred molding compositions of the invention comprise a proportion of component F of 1 to 45% by weight, in particular 2 to 40% by weight, based on the total amount of all components.

According to the invention, copolymer F consists of:

F1: 60 to 95% by weight, preferably 70 to 85% by weight of styrene or substituted styrene of formula (XIII), or mixtures thereof, and

F2: 5 to 40% by weight, preferably 15 to 30% by weight of one or more unsaturated nitriles, preferably acrylonitrile or methacrylonitrile or mixtures thereof.

Copolymer F is resin-like, thermoplastic and rubber-free. Particularly preferred copolymers F are styrene and acrylonitrile, α-methylstyrene and acrylonitrile, or consist of styrene, α-methylstyrene and acrylonitrile. It is also possible to use two or more copolymers described simultaneously.

Copolymer F is known per se and can be prepared via free-radical polymerization, in particular via emulsion, suspension, solution or bulk polymerization. It has a viscosity number ranging from 40 to 160, which corresponds to an average molecular weight M _w (weight-average) of 40,000 to 2,000,000.

Halogenation Flame retardant  G

Plastic components A1, A2 and / or B may comprise, as component G, 1 to 30% by weight, preferably 2 to 25% by weight, in particular 5 to 20% by weight, of a flame retardant combination consisting of: .

G1: 20 to 99% by weight, preferably 50 to 85% by weight of halogen-containing flame retardant, and

G2: 1 to 80% by weight, preferably 15 to 50% by weight of antimony oxide.

Preferred oxides G2 are antimony trioxide and antimony pentoxide. For better dispersion, oxide G2 is known as ash (concentrate) and can be introduced into polymer A1, A2 or B and the polymers used in these concentrates are for example component A1, A2 or B It may be the same as or different from each component A1, A2 or B. Preference is given to concentrates of G2 in polyolefins, preferably polyethylene.

Suitable flame retardants G1 are preferably brominated compounds such as brominated diphenyl ethers, brominated trimethylphenylindanes (FR 1808 from DSB), tetrabromobisphenol A and hexabromocyclododecane.

Suitable flame retardants G1 are preferably brominated compounds, for example brominated oligocarbonates (BC 52 or BC 58 from Great Lakes) of the structure:

Polypentabromobenzyl acrylate where n> 4, for example FR 1025 from the Dead Sea Bromine (DSB) of formula:

Is also suitable.

Another preferred brominated compound is an oligomeric reaction product (n> 3) derived from tetrabromobisphenol A of the formula: and epoxides (e.g. FR # 2300 and 2400 (DSB)).

The average degree of polymerization (water-average) of the brominated oligostyrenes preferably used as flame retardant is 3 to 90, preferably 5 to 60, as measured by vapor pressure osmotic method in toluene. Cyclic oligomers are likewise suitable. In one preferred embodiment of the invention, the brominated oligomeric styrene used has the general formula XIV, wherein R is hydrogen or an aliphatic radical, in particular an alkyl radical such as CH ₂ Or C ₂ H ₅ , n is the number of repeat units in the chain. R 'may be a fragment of H or else bromine or other conventional free-radical generator.

<Formula XIV>

The value of n may be 1 to 88, preferably 3 to 58. The brominated oligostyrene contains 40 to 80 weight percent bromine, preferably 55 to 70 weight percent. Preference is given to products consisting mainly of polydibromostyrene. The material can be melted without decomposition, for example tetrahydrofuran-soluble. It can be prepared via ring bromination of-optionally aliphatic hydrogenated-styrene oligomers, which can be obtained, for example, via thermal polymerization of styrene (according to DT-A 25 37 385) or free-radical oligomers of suitable brominated styrene It is obtainable through the oxidation. Flame retardants can also be prepared via bromination after the ionic oligomerization of styrene. The amount of brominated oligostyrene required to provide the polyamide flame retardant depends on the bromine content. The content of bromine in the molding composition of the present invention is 2 to 20% by weight, preferably 5 to 12% by weight.

The brominated polystyrene of the present invention is obtained mainly by the following process described in EP-A 47 549.

The brominated polystyrenes obtainable and commercially available in this process are mainly ring-substituted tribromination products. n '(see XVI) generally has a value of 125 to 1500 and corresponds to a molecular weight of 42,500 to 235,000, preferably 130,000 to 135,000.

The bromine content is generally at least 50% by weight, preferably at least 60% by weight, in particular at least 65% by weight (based on the content of ring-substituted bromine).

Commercially available flour products have a glass transition temperature of generally 160 to 200 ° C., for example the name of HP 7010 from Albemarle and the name of Pyrocheck PB 68 from Ferro Corporation. Available.

It is also possible to use mixtures of brominated oligostyrenes and brominated polystyrenes in any desired mixing ratios in the molding compositions of the invention.

Chlorine-containing flame retardant D1 is also suitable, and Deklorane ® plus from Oxychem is preferred.

halogen -Free  Flame Retardant H

Plastic components A1, A2 and / or B are, as component H, 1 to 40% by weight, preferably 2 to 30% by weight, in particular 5 to 20% by weight, nitrogen-containing or phosphorus-containing compounds or P / Halogen-free flame retardants selected from the group of N condensates, or mixtures thereof.

Melamine cyanurate which is preferably suitable according to the invention as halogen-free flame retardant H is preferably the reaction product of melamine (formula XVI) and cyanuric acid or isocyanuric acid (formula (XVIa and XVIb)) in an equimolar amount.

This is obtained, for example, through the reaction of an aqueous solution of the starting compound at 90 to 100 ° C. Commercially available products are white powders with an d ₅₀ average grain size of 1.5 to 7 μm.

Other suitable compounds (also often referred to as salts or adducts) include melamine, melamine borate, melamine oxalate, melamine phosphate (primary), melamine phosphate (secondary) and melamine pyrophosphate (secondary), melamine neopentyl Glycol borate and polymeric melamine phosphate (CAS No. 56386-64-2).

Suitable guanidine salts are as follows.

For the purposes of the present invention the compounds include both benzoguanamine itself and its adducts or salts, and also derivatives substituted on nitrogen and adducts or salts thereof.

Still other suitable compounds include ammonium polyphosphate (NH ₄ PO ₃ ) _n where n is about 200 to 1000, preferably 600 to 800, and tris (hydroxyethyl) isocyanurate of formula XVII THEIC):

(XVII)

Or a reaction product thereof with an aromatic carboxylic acid Ar (COOH) _m , wherein Ar is a 1-, 2- or trinuclear aromatic 6-membered ring system, and m is 2, 3 or 4, if necessary Is a mixture of.

Examples of suitable carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, benzene-1,3,5-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, pyromellitic acid, melanoic acid, prenite Acids, 1-naphthoic acid, 2-naphthoic acid, naphthalenedicarboxylic acid and anthracenecarboxylic acid.

It is prepared by reacting tris (hydroxyethyl) isocyanurate with an acid or an alkyl ester thereof or a halide thereof according to the process of EP-A 584 567.

Reaction products of this type are also mixtures of monomeric and oligomeric esters which may have crosslinking. The degree of oligomerization is usually 2 to about 100, preferably 2 to 20. Preference is given to using reaction products thereof, in particular (NH ₄ PO ₃ ) _n or melamine pyrophosphates or polymeric melamine phosphates, which are mixtures with THEIC and / or phosphorus-containing nitrogen compounds. For example, the mixing ratio of (NH ₄ PO ₃ ) _n to THEIC is preferably 90-50: 10-50% by weight, in particular 80-50: 50, based on a mixture of component H of this type -20% by weight.

Another suitable compound is benzoguanamine of formula XVIII.

&Lt; Formula XVIII &

Wherein R and R 'are adducts with straight or branched chain alkyl radicals having 1 to 10 carbon atoms, preferably hydrogen, in particular with phosphoric acid, boric acid and / or pyrophosphoric acid.

Allantoin Compound of Formula XIX

(XIX)

(Wherein R and R 'are as defined in formula XVIII),

And also salts thereof with phosphoric acid, boric acid and / or pyrophosphoric acid, and also with glycoluril of the formula

&Lt; Formula (XX)

Wherein R is as defined in formula XVIII

This is preferred.

Suitable products are commercially available or obtainable according to DE-A 196 14 424.

Cyanoguanidine (formula XXI) which can be used according to the invention is obtained, for example, by reacting calcium cyanamide with carbonic acid, and the resulting cyanamide is dimerized at a pH of 9 to 10 to obtain cyanoguanidine. to provide.

Commercially available products are white powders having a melting point of 209 ° C to 211 ° C.

Preferred phosphorus-containing compounds are phosphinic acid salts of formula XXII and / or diphosphinic acid salts of formula XXIII and / or polymers thereof.

<Formula XXII>

<Formula XXIII>

Here, the substituents are defined as follows.

R ¹ and R ² are hydrogen, linear or branched C ₁ -C ₆ -alkyl, preferably C ₁ -C ₄ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tert -Butyl, n-pentyl; Phenyl; Wherein at least one radical R ¹ or R ² is preferably hydrogen, in particular R ¹ and R ² are hydrogen;

R ³ is linear or branched C ₁ -C ₁₀ -alkylene, for example methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene;

Arylene such as phenylene, naphthylene;

Alkylarylenes such as methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene;

Arylalkylenes such as phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene;

M is an alkaline earth metal or an alkali metal, Al, Zn, Fe, Bor;

m is an integer from 1 to 3;

n is an integer of 1 to 3,

x is 1 or 2.

Particular preference is given to compounds of the general formula (XXIII) in which R ¹ and R ² are hydrogen and M is preferably Zn or Al, with calcium phosphinate being very particularly preferred.

Products of this type are commercially available, for example as calcium phosphinate.

Only one radical R ¹ Or suitable salts of formula XXII or XXIII wherein R ² is hydrogen are, for example, salts of phenylphosphinic acid, with Na and / or Ca salts thereof being preferred.

The phosphorus-containing compound of component H is preferably an organic or inorganic phosphorus-containing compound in which the valence state of phosphorus is -3 to +5. For the purposes of the present invention, valence states are described in Lehrbuch der Anorganischen Chemie, by A.F. Hollemann and E. Wiberg, Walter des Gruyter and Co. (1964, 57th to 70th edition), pages 166-177. Compounds with valence states of -3 to +5 include phosphine (-3), diphosphine (-2), phosphine oxide (-1), elemental phosphorus (+0), hypophosphoric acid (+1), phosphorous acid (+3), hypophosphoric acid (+4) and phosphoric acid (+5).

Only a few examples of many phosphorus-containing compounds will be mentioned.

Examples of phosphine series phosphorus compounds having a valence state of -3 are, in particular, aromatic phosphines such as triphenylphosphine, tritolylphosphine, trinonylphosphine, trinaphthylphosphine and trisnonylphenylphosphine . Triphenylphosphine is particularly suitable.

Examples of diphosphine series phosphorus compounds having a valence state of -2 are especially tetraphenyldiphosphine and tetranaphthyldiphosphine. Tetranaphthyldiphosphine is particularly suitable.

Compounds having a valence state of -1 are derived from phosphine oxide.

Phosphine oxides of the general formula (XXIV) are suitable.

(XXIV)

Wherein R ¹ , R ² and R ³ are the same or different and are alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 carbon atoms.

Examples of phosphine oxides include triphenylphosphine oxide, tritolylphosphine oxide, trisnonylphenylphosphine 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 And phenylbis (n-hexyl) phosphine oxide. Other preferred compounds are oxidized reaction products of phosphines and aldehydes, in particular tert-butylphosphine and glyoxal. Particular preference is given to using triphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-octyl) phosphine oxide or tris (cyanoethyl) phosphine oxide.

Other suitable compounds are derivatives thereof as described above for triphenylphosphine sulfide and phosphine oxide.

Phosphorus with valence state + 0 is elemental phosphorus. Red and black are possible, red is preferred.

Examples of compounds having an oxidation state of +1 are hypophosphites of pure organic type, for example organic hypophosphites such as cellulose hypophosphite esters and hypophosphoric acid with diols, for example 1,10-dodecyldiol. ester. It is also possible to use substituted phosphinic acids and their anhydrides such as diphenylphosphinic acid. Other possible compounds are diphenylphosphinic acid, di-p-tolylphosphinic acid and dicresylphosphinic anhydride. In particular, compounds such as bis (diphenylphosphonic) esters of hydroquinone, ethylene glycol and propylene glycol can also be used. Other suitable compounds are aryl (alkyl) phosphinamides such as dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives of diphenylphosphinic acid such as p-tolylsulfonamidodiphenylphosphinic acid. Preference is given to using bis (diphenylphosphinic) esters of hydroquinone or ethylene glycol or bis (diphenylphosphinate) of hydroquinone.

Phosphorus compounds with an oxidation state of +3 are derived from phosphorous acid. Suitable compounds are, for example, cyclic phosphonates derived from pentaerythritol, neopentyl glycol or pyrocatechol.

<Formula XXV>

Wherein R is a C ₁ -C ₄ -alkyl radical, preferably a methyl radical, and x is 0 or 1 (Amgard® P 45 from Albright & Wilson).

Phosphorus having a valence +3 may also be triaryl (alkyl) phosphite, such as triphenyl phosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite and phenyl It is also present in didecyl phosphite. However, it is also possible to use diphosphites such as propylene glycol 1,2-bis (diphosphite) or cyclic phosphites derived from pentaerythritol, neopentyl glycol or pyrocatechol.

Neopentyl glycol methylphosphonate and neopentyl glycol methylphosphite, and also pentaerythritol dimethyldiphosphonate and dimethyl pentaerythritol diphosphite are particularly preferred.

Phosphorus compounds which can be used with an oxidation state of +4 are in particular hypodiphosphates such as tetraphenyl hypodiphosphate and bisneopentyl hypodiphosphate.

Phosphorus compounds which can be used with an oxidation state of +5 are especially alkyl- and aryl-substituted phosphates. Examples thereof include phenyl bisdodecyl phosphate, phenylethyl hydrogenphosphate, phenylbis (3,5,5-trimethylhexyl) phosphate, ethyldiphenyl phosphate, 2-ethylhexylditolyl phosphate, diphenyl hydrogenphosphate, bis ( 2-ethylhexyl) -p-tolyl phosphate, tritolyl phosphate, bis (2-ethylhexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogenphosphate, dididodecyl-p-tolyl phosphate, p-tolylbis (2,5,5-trimethylhexyl) phosphate and 2-ethylhexyldiphenyl phosphate. Particularly suitable phosphorus compounds are those in which each radical is aryloxy. Very particularly suitable compounds are triphenyl phosphate and resorcinol bis (diphenyl phosphate) and their ring-substituted derivatives of formula XXVI (RDP).

<Formula XXVI>

Wherein R ⁴ -R ⁷ is an aromatic radical having 6 to 20 carbon atoms, preferably phenyl, which may be substituted with an alkyl group having 1 to 4 carbon atoms, preferably methyl,

R ⁸ is a divalent phenol radical, preferably

또는

이고,

or

ego,

The mean value of n is 0.1 to 100, preferably 0.5 to 50, especially 0.8 to 10, very particularly 1 to 5.

Due to the process used for its production, trade name Fyroflex® Or Fyrol® RDP products sold as -RDP (Akzo) and also CR 733-S (Daihachi) have about 85% RDP (n = 1) and about 2.5% triphenyl phosphate and also about 12.5 % Of oligomeric fraction, most of which is a mixture of oligomeric fractions.

It is also possible to use cyclic phosphates. Of these, diphenyl pentaerythritol diphosphate and phenylneopentyl phosphate are particularly suitable.

In addition to the low molecular weight phosphorus compounds mentioned above, it is also possible to use oligomeric or polymeric phosphorus compounds.

Polymeric, halogen-free organic phosphorus compounds of this type with phosphorus in the polymer chain are prepared during the preparation of pentacyclic unsaturated phosphine dihalides, as described, for example, in DE-A 20 36 173. The molecular weight of polyphospholine oxide as measured by vapor osmosis in dimethylformamide should be in the range from 500 to 7000, preferably from 700 to 2000. Wherein the oxidation state of phosphorus is -1.

It is also possible to use inorganic coordination polymers of aryl (alkyl) phosphinic acid, such as poly-β-sodium (I) methylphenylphosphinate. Its recipe is given in DE-A 31 40 520. The oxidation number of phosphorus is +1.

Halogen-free polymeric phosphorus compounds of this type also include phosphonic acid chlorides such as phenyl-, methyl-, propyl-, styryl- or vinylphosphonyl dichloride and dihydric phenols such as hydroquinone, resorcinol, 2, It can be prepared by the reaction of 3,5-trimethylhydroquinone, bisphenol A or tetramethylbisphenol A.

Other halogen-free polymeric phosphorus compounds that may be present in the novel molding compositions are the reaction of phosphorus oxytrichloride or phosphoric ester dichloride with a mixture of mono-, di- or trivalent phenols and other compounds with hydroxy groups (Houben-Weyl-Mueller, Thieme-Verlag, Stuttgart, Germany, Organische Phosphorverbindungen Part II (1963)). The polymeric phosphonates can also be reacted by transesterification of phosphonate esters with dihydric phenols (see DE-A 29 25 208) or by reaction of phosphonate esters with diamines or diamides or hydrazides ( US Pat. No. 4,403,075). Inorganic compound poly (ammonium phosphate) may also be used.

Oligomeric pentaerythritol phosphites, pentaerythritol phosphates and pentaerythritol phosphonates, for example Mobil Antiblaze® 19 (registered trademark of Mobil Oil) according to EP-B 8 486 It is also possible to use.

Preference is also given to phosphorus compounds of the general formula (XXVII).

<Formula XXVII>

Substituents are defined as follows.

R ¹ -R ²⁰ are, independently from each other, hydrogen, a linear or branched alkyl group having up to 6 carbon atoms,

n has an average value of 0.5 to 50,

X is a single bond, C═O, S, SO ₂ , C (CH ₃ ) ₂ .

Preferred compounds H are those in which R ¹ to R ²⁰ are, independently of one another, hydrogen and / or methyl radicals. When R ¹ -R ²⁰ are independently of each other a methyl radical, ^one radical of the radicals R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ , R ²⁰ in the ortho-position to the oxygen of the phosphate group Compound H which is the above methyl radical is preferable. Preference is furthermore given to compounds H in which one methyl group per aromatic ring is present, preferably in the ortho-position and the other radical is hydrogen.

Particularly preferred substituents for X in formula (XXVII) are SO ₂ and S, very particular preference is given to C (CH ₃ ) ₂ .

1이다.The mean value of n is preferably 0.5 to 5, in particular 0.7 to 2, in particular

1.

Describing n as the average value is the result of the preparation process for the compounds listed above, the degree of oligomerization is mainly less than 10 and the content of triphenyl phosphate present is very small (mainly less than 5% by weight), which varies from batch to batch. Compound H is marketed as CR-741 from Daihachi.

P / N condensates, in particular those described in WO 2002/96976, are also suitable.

Particularly preferred combination H is a mixture of phosphorus- and nitrogen-containing compounds, with a preferred mixing ratio of 1:10 to 10: 1, preferably 1: 9 to 9: 1.

Supplement C

Plastic components A1, A2 and / or B may comprise, as component C, from 0 to 60% by weight, in particular up to 50% by weight, of other additives and processing aids different from D, E, F, G and H. .

The molding compositions of the present invention are, as component C, saturated with 0 to 5% by weight, preferably 0.05 to 3% by weight, in particular 0.1 to 2% by weight, 10 to 40, preferably 16 to 22 carbon atoms. Or at least one ester or amide of an unsaturated aliphatic carboxylic acid with a saturated aliphatic alcohol or amine having 2 to 40, preferably 2 to 6 carbon atoms.

The carboxylic acid may be monobasic or dibasic. Examples that may be mentioned are pelagonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, particularly preferably stearic acid, capric acid and also montanic acid (30-40 carbon atoms) Mixture of fatty acids).

Aliphatic alcohols may be mono- to tetravalent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preferably glycerol and pentaerythritol.

The aliphatic amine may be mono-, di- or triamine. Examples thereof are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, preferably ethylenediamine and hexamethylenediamine. Correspondingly, preferred esters or amides are glyceryl distearate, glyceryl tristearate, ethylenediamine distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobehenate and pentaerythritol tetrastea Rate.

It is also possible to use various esters or amides, or combined esters and amides, where the mixing ratio is the desired value.

Fibrous or particulate fillers C which may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silica, asbestos, calcium silicates, calcium metasilicates, magnesium carboxes, used in amounts of up to 50% by weight, in particular up to 40% by weight. Carbonate, kaolin, chalk, powdered quartz, mica, barium sulphate and feldspar.

Preferred fibrous fillers which may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, particularly preferably glass fibers in the form of E glass. It can be used as a roving or as a commercially available form of chopped glass.

In order to improve compatibility with thermoplastics, fibrous fillers may be surface-pretreated with silane compounds.

Suitable silane compounds have the formula

Where

, HO-이고,X is NH _2- ,

, HO-,

n is an integer of 2 to 10, preferably 3 to 4,

m is an integer of 1 to 5, preferably 1 to 2,

k is an integer of 1-3, Preferably it is 1.

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes containing a glycidyl group as substituent X.

The amount of silane compound generally used for surface-coating is from 0.05 to 5% by weight, preferably from 0.5 to 1.5% by weight, in particular from 0.8 to 1% by weight (based on C).

Needle mineral fillers are also suitable.

For the purposes of the present invention, needle-like mineral fillers are mineral fillers with strongly developed needle-like characteristics. One example is needle-shaped wollastonite. The L / D (length to diameter) ratio of the minerals is preferably 8: 1 to 35: 1, preferably 8: 1 to 11: 1. Mineral fillers may be pretreated with the above-mentioned silane compounds, if desired, but pretreatment is not necessary.

Other fillers that may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk.

As component C, the thermoplastic molding compositions of the present invention may be prepared by conventional processing aids such as stabilizers, oxidation retardants, agents, lubricants and mold release agents, colorants such as dyes and pigments, corresponding to decomposition by thermal and decomposition by ultraviolet radiation, Nucleating agents, plasticizers, and the like.

Examples of oxidation retardants and heat stabilizers that may be mentioned are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenyl at concentrations of up to 1% by weight, based on the weight of the thermoplastic molding composition. Amines, various substituted members of such groups, and mixtures thereof.

Mention may be made, and UV stabilizers generally used in amounts of up to 2% by weight based on the molding composition are the various substituted resorcinols, salicylates, benzotriazoles and benzophenones.

Colorants that may be added are inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, and also organic pigments such as phthalocyanine, quinacridone and perylene, and also dyes such as nigrosine and anthraquinone.

Nucleating agents that can be used are sodium phenylphosphinate, alumina, silica, preferably talc.

Other lubricants and release agents are commonly used in amounts up to 1% by weight. Long chain fatty acids (eg stearic acid or behenic acid), salts thereof (eg calcium stearate or zinc stearate) or montan wax (mixture of straight chain saturated carboxylic acids having a chain length of 28 to 32 carbon atoms), or Calcium montanate or sodium montanate, or low molecular weight polyethylene wax or low molecular weight polypropylene wax is preferred.

Examples of plasticizers that may be mentioned are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils and N- (n-butyl) benzenesulfonamide.

The molding composition of the present invention may also comprise 0 to 2 percent by weight of fluorine-containing ethylene polymer. It is a polymer of ethylene having a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.

Examples thereof include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer and tetrafluoroethylene air having relatively small proportions (typically up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. It is coalescing. This is described, for example, in Childknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484-494 and by Wall in "Fluoropolymers" (Wiley Interscience, 1972).

Such fluorine-containing ethylene polymers have a homogeneous distribution in the molding composition and preferably have a particle size d ₅₀ (number average) in the range from 0.05 to 10 μm, in particular from 0.1 to 5 μm. This small particle size is particularly preferably achieved by using an aqueous dispersion of fluorine-containing ethylene polymer and introducing it into the polyester melt.

The thermoplastic molding compositions of the present invention may be prepared by known methods of mixing the starting components in a conventional mixing device such as a screw extruder, Brabender mixer or Banbury mixer and then extruding them. The extrudate can then be cooled and comminuted. It is also possible to premix individual components and then add the remaining starting materials individually and / or likewise into the mixture. The mixing temperature is generally 230 to 290 ° C.

Components and Manufacturing Methods

Examples of components are plastic casing types with mechatronic components or plug-in contacts, which are used in electronics.

An example of an insert enclosed by plastic jackets is a forged electrode plate. In this case, the component can be used, for example, as a plug connector. The insert can also be a wire, a circular conductor, a flat conductor, a flexible foil, or a printed circuit board.

If the component is used in the automotive industry, the insert may also be for example a retaining strap, door latch, lock, threaded bush, anti-friction bearing, panel, wire for stabilizer, or It may be a component consisting of die casting zinc or die casting aluminum for the door-holding unit. It is also possible for the component to be a knife, scissors, scalpel or other blade of a screwdriver.

The insert is preferably made from metal. Examples of suitable metals for making inserts are copper and copper-containing alloys such as CuSn 6, CuSn 0, 15, CuBe, CuFe, CuZn 37, CuSn 4 Zn 6 Pb 3 -C-GC (bronze) or CuZn 39 Pb 3 (brass), aluminum and aluminum-containing alloys, For example AlSi12Cu1, AlSi10Mg, titanium, stainless steel, lead-free metals, and metal alloys or tin coatings.

The present invention

(a) A11: 5 to 80% by weight, based on the total weight of components A11 and A12, of at least one polyester based on aliphatic and aromatic dicarboxylic acids and on aliphatic dihydroxy compounds;

A12: 20 to 95% by weight, based on the total weight of components A11 and A12, derived from polylactide (PLA), polycaprolactone, polyhydroxyalkanoate, and aliphatic dicarboxylic acids and aliphatic diols At least one homo- or copolyester selected from the group consisting of polyesters; And

A13: a styrene-based, acrylate-based and / or methacrylate-based copolymer containing from 0.05 to 15% by weight of a) epoxy groups, based on the total weight of components A11 and A12, b) bisphenol A epoxide, Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups

With the first plastic component A1 or

A21: 10 to 100% by weight of at least one thermoplastic styrene (co) polymer, based on the total weight of components A21 and A22,

A22: 0 to 90% by weight of at least one thermoplastic (co) polyester, based on the total weight of components A21 and A22,

A23: a styrene-based, acrylate-based and / or methacrylate-based copolymer containing from 0.05 to 15% by weight of a) epoxy groups, based on the total weight of components A21 and A22, b) bisphenol A epoxide, Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups

Covering the insert with a first plastic component A2 consisting of; And

(b) B1: 10 to 99.99% by weight of one or more thermoplastic polyesters,

B2: 0.01-50% by weight,

B21: one or more highly branched or hyperbranched polycarbonates having an OH value of 1 to 600 mg KOH / g polycarbonate (according to DIN 53249, part 2), or

B22: type A _x B _y At least one highly branched or hyperbranched polyester, wherein x is at least 1.1 and y is at least 2.1, or

Its mixture

Forming an outer sheath consisting of a second plastic component B consisting of

/ RTI &gt;

The first plastic component A1 or the first plastic component A2 and / or the second plastic component B

C: 0 to 60% by weight of one or more additional adjuvants

It is additionally possible to include,

Here, in order to form the sheath of the insert, the insert is first covered with the first plastic component A1 or A2 and then the second plastic component B is applied, or the outer sheath B is first molded and then the first plastic component A1 or Filling A2 into a cavity between the outer sheath consisting of the second plastic component B and the insert,

There is further provided a method of making a component comprising an insert and a plastic jacket consisting of two or more plastic components.

Suitable and preferred polymers as the first plastic component A1, the first plastic component A2, and the second plastic component B have already been described above.

In one preferred embodiment, an injection-molding process is used for coating the insert with the first plastic component A1 or A2 in step (a). For this purpose, the insert is placed in an injection mold. Once the insert is placed, the mold is closed and the plastic molding composition is injected into the mold. The plastic molding composition at least partially covers the insert and forms an adhesive bond with the insert. The result is a leaktight coupling between the insert and the plastic component A1 or A2. The injection of the plastic molding composition here is generally carried out at the usual pressure in injection molding. However, if, for example, non-uniform injection around the insert can cause deformation, the maximum pressure at which injection of component A1 or A2 is carried out in the mold is preferably less than 900 bar, more preferably less than 600 bar. to be. Due to the low injection pressure, deformation of the insert is avoided when material is injected around the insert. Once the material is injected around the insert, the first plastic component A1 or A2 is cured and becomes solid. A further advantage of injecting the first plastic component A1 or A2 around the insert is that the insert is stabilized by the plastic jackets.

A wide variety of shapes can be realized when covering the insert with the first plastic component A1 or A2. For example, it is possible to realize rectangular, rhombic, pentagonal, octagonal, circular or elliptical cross sections. If the plastic jacket consisting of the first plastic component A1 or A2 has an edge, it can also be a rounded edge.

The joints between the faces of the sheaths of the first plastic component A1 or A2 can be obtuse, acute or round joints. There may also be a distinct melt lip, ie a thin protruding region, consisting of the first plastic component A1 or A2. It then melts and deforms when the second plastic component B is injected onto the material. This creates a matched bond.

There may also be a projecting area designed on the material injected around the insert and consisting of the first plastic component A1 or A2. For example, the first plastic component A1 or A2 may surround the insert having a double T-shaped cross section. Engagement coupling can be achieved through the protruding areas when the first plastic component A1 or A2 is injected in this way around the material. Since the injection of the second plastic component B onto the first plastic component A1 or A2 generally causes an initial melting of the electrons, the processing temperature of the second plastic component B is such that the melting point of the first plastic component A1 or A2 Or, if it is higher than the softening point, the shape of the material consisting of the first injected plastic component A1 or A2 can generally vary. It is also possible that the material consisting of the first plastic component A1 or A2 previously injected is deformed through the pressure of the injected melt when the second plastic component B is injected around the material. For example, the sharp edge of the material consisting of the first plastic component A1 or A2 previously injected can be rounded.

Once the insert is covered with the first plastic component A1 or A2, the covered insert is covered with the second plastic component B. The coating with the second plastic component B is preferably carried out via an injection-molding process as well. The injection-molding process here is generally carried out at pressures conventional in injection molding. If the plastic molding composition is injected at a low injection pressure, the pressure in the mold is generally higher than the maximum pressure in the mold in step (a). During injection of the second plastic component B, the surface of the cured first plastic component A1 or A2 is preferably initially melted to give particularly good adhesion between the first plastic component A1 or A2 and the second plastic component B Create

The coating of the insert with the first plastic component A1 or A2 in step (a) and the molding of the outer coating consisting of the second plastic component B in step (b) can be carried out in the same injection mold. To this end, it is necessary for the injection mold to initially enclose a cavity corresponding to the shape of the insert with the sheath made of the first plastic component A1 or A2. The mold must then be opened in such a way that the unfilled shape corresponds to the shape of the finished component. Those skilled in the art are aware of suitable molds.

However, as an alternative, the coating of the insert with the first plastic component A1 or A2 in step (a) is carried out in the first mold and the shaping of the outer coating consisting of the second plastic component B in step (b) It is also possible to carry out the silver in the second mold. In such a case, it is necessary to remove the insert covered with the first plastic component A1 or A2 from the first mold and put it in the second mold before injecting the second plastic component B around the material. If it is intended to avoid deformation of the covering of the insert consisting of the first plastic component A1 or A2, then the first plastic component A1 or A2 has sufficient mechanical resistance to the approaching flow of the melt of the second plastic component B. It is necessary to carry. This requires sufficient rigidity and strength, which depends on the degree of cure of the first plastic component A1 or A2 and the injection pressure of the second plastic component B.

To change the material, in order to eliminate the need to clean the injection-molding machine after every injection process, it is recommended to use two different injection-molding machines or plasticizing units for the first plastic component A1 or A2 and the second plastic component B. desirable. If the shaping of the coating in step (a) and the outer coating in step (b) is carried out in the same mold, it is possible for the mold to be connected simultaneously to both injection-molding machines. An alternative possibility is to connect the mold to an injection-molding machine which injects the first plastic component A1 or A2, and then the second plastic component B around the insert with a sheath made of the first plastic component A1 or A2. The mold is connected to an injection-molding machine that injects. An example of a conventional injection-molding machine used for this purpose is an injection-molding machine with a turntable mold. It has, for example, an opposing arrangement of cylinders, in which case the mold rotates towards the cylinder into which the next material is to be injected. If two different molds are used, each of them is preferably connected to an injection-molding machine. Suitable injection-molding machines here are any desired injection-molding machines known to those skilled in the art.

In step (b) it is possible for the second plastic component B to cover only a part of the insert covered with the first plastic component A1 or A2. In this case, it is preferable that the peripheral area of the area into which the second plastic component B is injected is an area having an outer surface, since the coating with the second plastic component B ensures molding with dimensional stability. Another possible alternative is, of course, to inject the second plastic component B around the entire insert with a sheath consisting of the first plastic component A1 or A2.

First forming an outer sheath of the second plastic component B, wherein some areas of the insert are not covered, and in a second step, the uncovered area of the insert is replaced by the first plastic component A1. In a process of coating with A2, a preferred method for covering the insert with the second plastic component B is for the component to cover the insert in the region where the outer surface is present. The region on which the first plastic component A1 or A2 is cast preferably does not have an outward facing portion. This method ensures that the resulting components have geometric and dimensional stability.

The coating of the insert with the second plastic component B is preferably carried out via an injection-molding process. For this purpose, after inserting the insert into the injection mold, the second plastic component B is injected around it. In order to avoid penetration of the second plastic component B into the area where it should be excluded, the mold is in contact with this area of the insert. Once the insert is covered with the second plastic component B, the area to be covered with the first plastic component A1 or A2 is accessible. To this end, a movable part that initially forms an exclusion is provided in the mold and then accessible to the exclusion for casting into the first plastic component A1 or A2, or around which a second plastic component B is injected. It is possible to remove the insert from the mold and to insert the insert into the second mold where the area to be covered with the first plastic component A1 or A2 is available.

Coating with the first plastic component A1 or A2 is preferably carried out via an injection-molding process as well. This is usually done at conventional pressures in the injection-molding process. For example, if non-uniform injection around the insert can cause deformation, an injection-molding process for the first plastic component A1 or A2 is used to inject the second plastic component B around the insert. Preference is given to performing at lower pressures than in the injection-molding process used. The pressure for the coating of the insert with the first plastic component A1 or A2 is preferably less than 900 bar, more preferably less than 600 bar.

A preferred method of achieving a leak-tight bond between the first plastic component A1 or A2 and the second plastic component B is that the melt of the first plastic component A1 or A2 causes initial melting on the surface of the plastic component B, For example, interdiffusion results in a particularly good adhesion between the first plastic component A1 or A2 and the second plastic component B. Further chemical and / or mechanical bonding between the first plastic component A1 or A2 and the second plastic component B is further possible. The chemical bonding is for example through the reaction of the polymer component of the first plastic component A1 or A2 with the polymer component of the second plastic component B, for example the first plastic component A1 or A2 or the first plastic. It can be produced by forming a covalent bond between one component of component A1 or A2 and one component of second plastic component B or second plastic component B. Another possibility that is always available is to design the process in such a way that it provides not only good adhesion between the first plastic component A1 or A2 and the second plastic component B, but also engagement engagement.

The melt temperature of the first plastic component A1 or A2 during the first injection of the material around the insert is preferably within the range of the usual processing temperature of the underlying polymer by injection molding. If the first plastic component A1 or A2 is a mixture of two polymers, the melt temperature is chosen high enough so that both components are liquid.

Higher processing temperatures result in a more free-flowing melt that can provide better wetting of the surface of the insert, enabling the achievement of higher bond strengths between the material of the insert and the material of the first plastic component A1 or A2. do. However, excessively high melt temperatures can cause thermal decomposition of the first plastic component A1 or A2 or its components A11 or A12 or A21 or A22.

Then, when the second plastic component B is injected over the component, the melt temperature of the second plastic component B is preferably within the range of the usual processing temperature of the underlying polymer by injection molding. If the second plastic component B is a mixture of two polymers, the melt temperature is chosen high enough so that the two components are liquid.

Higher processing temperatures result in a more free-flowing melt that can provide better wetting and / or initial melting of the surface of the coating consisting of the first plastic component A1 or A2, resulting in the second plastic component B and the first plastic. It is possible to achieve higher bond strengths between components A1 or A2. As a function of the thermodynamic compatibility of the two components, the boundary layers of various thicknesses can lead to improved leak-proof properties through interdiffusion and provide a mating bond between the plastic component A1 or A2 and the second plastic component B. The melt temperature of the second plastic component B is preferably not set high so that the coating made of the first plastic component A1 or A2 is completely melted and removed. It is also preferred to select the injection pressure of the second plastic component B in such a way that the coating made of the first plastic component A1 or A2 is not excessively deformed or, in the worst case, removed.

The components of the invention are, for example, the type of plastic parts used in electronics. It is also possible that the component is a plastic casing with mechatronic component or plug-in contacts. Components of this type are for example as sensors, for example oil sensors, wheel-rotation-speed sensors, pressure sensors, etc., as electronic casings, as control casings, for example ABS sectors, ESP sectors, transmissions -In the system sector or in the airbag sector, or in the engine-control system of an automobile. The component can also be used, for example, as a window-lifter module or in a headlamp control system. The components of the invention can also be used outside the automotive industry, for example as sensors, as fill-level indicators, or as pipeline units. Another suitable example of a component of the invention is an electronic component in a household appliance. Examples of suitable components are relays, windings, switch parts, solenoid valves, electric hand tools, plug devices or plug connectors.

A feature of the component of the invention consisting of an insert having a sheath of first plastic component A1 or A2 and an outer sheath of second plastic component B is characterized by two interfaces: the insert and the first plastic component A1 or Leaking along the interface between the sheath of A2 and the interface between the first plastic component A1 or A2 and the second plastic component B. Leak-proof couplings here mean that the leak rate is less than 0.5 cm ³ / min in tests under climate change conditions using more than 200 cycles of alternating components to be tested at temperatures of -40 ° C and + 150 ° C. Leak rates are measured primarily by the pressure differential method at a test pressure of 0.5 bar.

Example

The specimen was made from an insert consisting of CuSn ₆ coated with a first plastic component A1 or A2 and a second plastic component B, wherein the first plastic component A is the plastic component A1 or A2 described above.

To prepare the specimen, the insert was first punched out of a strip of CuSn ₆ using a punching die. The insert has a rectangular frame, which also has a central fillet connecting the opposing short sides of the frame. The length of the produced insert is 30 mm, its width is 10.5 mm, and its height is 0.5 mm. The length of the groove between the outer fillet and the center fillet of the frame is 25 mm and the width of the groove is 3 mm.

After the punching process, the punched portion was washed with acetone to remove oil and impurities. Specimens (Allrounder 270S from Arburg) were made using an injection-molding machine with a screw diameter of 18 mm. The clamping force of the mold is 500 kN and the injection pressure is 1500 bar. A parallelepiped material was injected around the central region of the insert with three fillets, with the result that the sheath of the second plastic component B completely surrounded the first plastic component A. The length of the sheath of the first plastic component A is 15 mm, its width is 4.5 mm and its thickness is 1.5 mm, while the sheath of the second plastic component B completely surrounds the first plastic component A. The length is 20 mm, the width thereof is 13 mm, and the thickness thereof is 4.5 mm. The injection of the first plastic component A onto the insert and the injection of the second plastic component B onto the insert covered with the first plastic component A took place approximately at the mold-division line.

To test the material, temperature-impact stressing was applied using up to 500 cycles to a component having a coating of first plastic component A and a component having a coating of second plastic component B. Here the following schedule was applied to each temperature-shock cycle: storage at 150 ° C. for 15 minutes, temperature change to −40 ° C. within 10 seconds, storage at −40 ° C. for 15 minutes and temperature change to 150 ° C. within 10 seconds. The temperature-shock treatment was carried out in a VT 7030S2 temperature-shock cabinet from Voetsch. Leakage resistance was measured by means of the pressure difference method before stressing and also 100, 200 and, optionally, 500 cycles.

For pressure differential testing, equal pressure was applied to both volumes, namely the test volume and the control volume. If the test volume is not leakproof, a pressure differential occurs and can be measured directly. As an alternative, the pressure drop per unit time can be measured. In this embodiment, the outer periphery of the specimen is tightened securely to the holder and pressure is applied to the underside of the specimen. The system was sealed with a rubber seal ring. Using a blinding test using a solid specimen of component B1, the leak causing the leak from the test volume may be directed solely in the direction of the insert, between the insert and the sheath of the first plastic component A, or It has been demonstrated that it comes out between a sheath consisting of plastic component A and a sheath consisting of second plastic component B. The test medium used was air. The test volume V _test was 36 ml. The time required to fill the volume with a test pressure of 0.5 bar was 5 seconds. After 10 seconds of political time, the pressure drop Δt _test = Measured for 5 seconds. The volume was then vacuumed in 2 seconds. Pressure drop increments were used in the Boyle-Marriotte equation to calculate the leak rate.

Table 1 compares the results.

In the table, components A1 to A4 represent the various overall components of component A.

Components B1 and B2 are different injections, component B1 is an outer jacket according to the prior art, and B2 is component B according to the invention.

TSC stands for temperature shock cycle.

Component A1 comprises monomeric styrene (40% by weight), α-methylstyrene (30% by weight) and acrylonitrile, including butadiene phase (10% by weight), having an elastic modulus of 2400 MPa and a Vicat softening temperature of 115 ° C. (20% by weight) of the copolymer.

Component A2 has a melting point of 110 to 120 ° C. (according to ISO 11357-3 in DSC), Shore D hardness of 32 (according to ISO 868), 90% by weight of component A1 and 10% by weight of terephthalic acid ( 25 mol%), 1,4-butanediol (50 mol%) and adipic acid (25 mol%) are blends of random copolyesters. Vicat softening temperature is 91 ° C., measured according to EN ISO 306: 2004.

Component A3 is a mixture of epoxy-functionalized styrene-acrylic acid copolymers of 97% by weight of component A1 and 3% by weight, having a molecular weight M _w of 6800 g / mol and a degree of functionalization of more than 4 epoxy groups per molecular chain. . The glass transition temperature is 54 ° C.

Component A4 consists of 45% by weight of random aliphatic-aromatic copolyester and 45% by weight of polylactide (PLA) produced from terephthalic acid (25mol%), adipic acid (25mol%) and butanediol (45mol%) It is a blend. The blend has two melting points of 110-120 ° C. and 140-155 ° C. (measured by DSC), the Vicat softening temperature (VST A 50) is 68 ° C. (according to ISO 306: 2004) and Shore D hardness of 59 (According to ISO 868), the modulus of elasticity is 750 MPa (according to ISO 527) on a blown film having a thickness of 50 μm.

Component B1 is a polybutylene terephthalate with 30% by weight glass fibers having a viscosity number of 102 g / ml as measured in a 0.5% solution in phenol / o-dichlorobenzene (1: 1) according to ISO 1628. It also contains 0.1 weight percent furnace black with a mean particle size of 10-35 nm (CILAS) and a BET surface area of 110-120 m ² / g (ISO 9277) and 0.5 weight percent pentaerythritol tetrastearate as lubricant. Include. The elastic modulus of the material is 10,000 MPa (ISO 527-2) and the melting point range is 220-225 ° C. (according to ISO 11357-3 in DSC). The diameter of glass fiber is 10 micrometers.

Component B2 is a mixture comprising 99.5% by weight of component B1 and 0.5% by weight of hyperbranched polycarbonate. Hyperbranched polycarbonates form an equimolar mixture of trimethylpropane x 3 ethylene oxide and diethyl carbonate as a polyfunctional alcohol in a three necked flask equipped with a stirrer, reflux condenser and internal thermometer, 250 ppm as catalyst Prepared by adding K ₂ CO ₃ (based on the amount of alcohol). The mixture was then heated to 100 ° C. with stirring and stirred at this temperature for 2 hours. As the reaction time progressed, the temperature of the reaction mixture decreased due to the onset of evaporative cooling of the released monoalcohol. Thereafter, the reflux condenser was switched to the descending condenser and the ethanol was distilled off, and the temperature of the reaction mixture slowly increased to 160 ° C.

The ethanol removed by distillation was collected in a cooled round bottom flask, weighed and the conversion measured as a percentage of the theoretically possible complete conversion. The amount of ethanol in the distillate for full conversion is 90 mol%.

The reaction product was subsequently analyzed by gel permeation chromatography using dimethylacetamide as eluent and polymethyl methacrylate (PMMA) as reference.

The number-average molecular weight M _n of the hyperbranched polycarbonate is 2500 g / mol and the weight-average molecular weight M _w is 4100 g / mol. The viscosity at 23 ° C. is 4020 mPas and the OH number according to DIN 53240, part 2 is 310 mg KOH / g.

From examples using external injections of component B according to the prior art, and from examples using external component B according to the invention, highly branched or hyperbranched polycarbonates and / or highly branched or hyperbranched Compared to external injection components that do not contain polyester, it can be seen that a better seal, ie, a slower leak rate, is always measured after the temperature treatment.

Even with freshly injected components, i.e. without performing temperature treatment, the leak rates measured for component B of the invention as the main injection were likewise equal or slow (except for the combination of A2 and B).

Claims (13)

An insert, and a plastic jacket consisting of two or more plastic components, wherein the insert is surrounded by a first plastic component A1 or a first plastic component A2, wherein the first plastic component A1 is
A11: 5 to 80% by weight of at least one semiaromatic polyester based on aliphatic and aromatic dicarboxylic acid and aliphatic dihydroxy compound based on the total weight of components A11 and A12;
A12: 20 to 95% by weight, based on the total weight of components A11 and A12, derived from polylactide (PLA), polycaprolactone, polyhydroxyalkanoate, and aliphatic dicarboxylic acids and aliphatic diols At least one homo- or copolyester selected from the group consisting of polyesters; And
A13: 0.05 to 15% by weight, based on the total weight of components A11 and A12, a) styrene-based, acrylate-based and / or methacrylate-based copolymers containing epoxy groups, b) bisphenol A epoxides Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups
Lt; / RTI &gt;
The first plastic component A2
A21: 10 to 100% by weight of one or more thermoplastic styrene (co) polymers, based on the total weight of components A21 and A22,
A22: 0 to 90% by weight of at least one thermoplastic (co) polyester, based on the total weight of components A21 and A22, and
A23: 0.05 to 15% by weight, based on the total weight of components A21 and A22, a) styrene-based, acrylate-based and / or methacrylate-based copolymers containing epoxy groups, b) bisphenol A epoxides Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups
Lt; / RTI &gt;
The first plastic component A1 or the first plastic component A2 is surrounded by the second plastic component B, and the second plastic component B is
B1: 10 to 99.99% by weight of one or more thermoplastic polyesters, and
B2: 0.01-50% by weight,
B21: one or more highly branched or hyperbranched polycarbonates having an OH value of 1 to 600 mg KOH / g polycarbonate (according to DIN 53249, part 2), or
B22: one or more highly branched or hyperbranched polyesters of the form A _x B _y , wherein x is at least 1.1 and y is at least 2.1, or
Its mixture
Lt; / RTI &gt;
The first plastic component A1 or the first plastic component A2 and / or the second plastic component B is
C: 0 to 60% by weight of one or more additional adjuvants
It is further possible to include a component. 2. The component of claim 1, wherein the plastic component B further comprises 1 to 40% by weight of the impact-modified polymer D. 3. The plastic component of claim 1, wherein the plastic component B is
E1: graft base comprising a rubber-elastic polymer based on alkyl acrylate having a glass transition temperature of less than 10 ° C. of 20 to 80% by weight and having 1 to 8 carbon atoms in the alkyl radical,
E2: 20 to 80% by weight,
E21: 60 to 95% by weight of styrene or substituted styrene of formula (I)
(I)

(Wherein R is an alkyl radical having 1 to 8 carbon atoms or hydrogen, R ¹ is an alkyl radical having 1 to 8 carbon atoms, n has a value of 1, 2 or 3), and
E22: 5-40 wt% unsaturated nitrile
Grafts, and
F: 0 to 60% by weight,
F1: 60-95% by weight of styrene or substituted styrene of formula (I), or mixtures thereof, and
F2: 5 to 40% by weight of one or more unsaturated nitriles
Copolymer of
The component further comprises 1 to 60% by weight of one or more graft polymers E. The plastic component of claim 1, wherein the plastic component B is
G1: 20 to 99% by weight halogen-containing flame retardant, and
G2: 1 to 80 wt% antimony oxide
And flame retardant combination G 1 to 30% by weight (based on the total mass of plastic component B). The halogen-free flame retardant according to any one of claims 1 to 3, wherein the plastic component B is selected from the group consisting of phosphorus-containing or nitrogen-containing compounds or P / N condensates or mixtures thereof. Further comprising weight percent. The process according to claim 1, wherein the at least one additional adjuvant C is a processing aid, stabilizer, oxidation retardant, anti-decomposition agent for thermal decomposition and degradation by ultraviolet light, lubricants and mold release agents, colorants. , Nucleating agent, plasticizer, and fibrous or particulate filler. 7. The particulate filler according to claim 6, wherein the particulate filler is carbon fiber, glass fiber, glass beads, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulphate, feldspar And a mixture of two or more of these materials. The component according to claim 1, wherein the first plastic component A comprises 0.1 to 40% by weight of glass beads, based on the total mass of the first plastic component A. 9. 9. The second plastic component B according to claim 1, wherein the second plastic component B comprises from 0.1 to 50% by weight of fibrous fillers, more particularly glass fibers, based on the total mass of the second plastic component B. 10. Component. 10. The insert according to claim 1, wherein the insert is made from any material having a copper, copper-containing alloy, aluminum, aluminum-containing alloy, titanium, stainless steel, lead-free metal or metal alloy or tin coating. Component. The component according to claim 1, which is a plastic casing, mechatronic component or plastic casing with plug-in contacts used in electronics. The following steps:
(a) A11: 5 to 80% by weight, based on the total weight of components A11 and A12, of at least one polyester based on aliphatic and aromatic dicarboxylic acids and on aliphatic dihydroxy compounds;
A12: 20 to 95% by weight, based on the total weight of components A11 and A12, derived from polylactide (PLA), polycaprolactone, polyhydroxyalkanoate, and aliphatic dicarboxylic acids and aliphatic diols At least one homo- or copolyester selected from the group consisting of polyesters; And
A13: 0.05 to 15% by weight, based on the total weight of components A11 and A12, a) styrene-based, acrylate-based and / or methacrylate-based copolymers containing epoxy groups, b) bisphenol A epoxides Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups
With the first plastic component A1, or
A21: 10 to 100% by weight of at least one thermoplastic styrene (co) polymer, based on the total weight of components A21 and A22,
A22: 0 to 90% by weight of at least one thermoplastic (co) polyester, based on the total weight of components A21 and A22, and
A23: 0.05 to 15% by weight, based on the total weight of components A21 and A22, a) styrene-based, acrylate-based and / or methacrylate-based copolymers containing epoxy groups, b) bisphenol A epoxides Or c) fatty acid amides, fatty acid esters or natural oils containing epoxy groups
Covering the insert with a first plastic component A2 consisting of; And
(b) B1: 10 to 99.99% by weight of one or more thermoplastic polyesters, and
B2: 0.01-50% by weight,
B21: one or more highly branched or hyperbranched polycarbonates having an OH value of 1 to 600 mg KOH / g polycarbonate (according to DIN 53249, part 2), or
B22: one or more highly branched or hyperbranched polyesters of the form A _x B _y , wherein x is at least 1.1 and y is at least 2.1, or
Its mixture
Forming an outer sheath consisting of a second plastic component B consisting of
Lt; / RTI &gt;
The first plastic component A1 or the first plastic component A2 and / or the second plastic component B is
C: 0 to 60% by weight of one or more additional adjuvants
It is further possible to include,
Here, in order to form the sheath of the insert, the insert is first covered with the first plastic component A1 or A2 and then the second plastic component B is applied, or the outer sheath B is first molded and then the first plastic component A1 Or filling A2 into a cavity formed between the insert and the outer sheath of the second plastic component B,
A method of making a component comprising an insert and a plastic jacket consisting of two or more plastic components. 13. A method according to claim 12, wherein the coating of the insert as the first plastic component A and the coating consisting of the second plastic component B are produced via an injection-molding process.