KR20090088388A - Low-emission polyester molding materials - Google Patents

Abstract

Thermoplastic molding materials comprising A) from 10 to 98% by weight of at least one polyester a-i) other than polyethylene terephthalate (PET), which comprises from 1 to 50% by weight, based on 100% A), of PET a2), B) from 1 to 40% by weight of talc, C) from 0.01 to 5% by weight of a lubricant, D) from 0.05 to 5% by weight of an alcohol, E) from 0 to 40% by weight of other additives, where the sum of the percentages by weight of components A) to E) adds up to 100%. ® KIPO & WIPO 2009

Description

Low Emission Polyester Molding Material {LOW-EMISSION POLYESTER MOLDING MATERIALS}

The present invention

A) 10 to 98% by weight of one or more polyesters a ₁ ) other than polyethylene terephthalate (PET), wherein the polyester comprises 1 to 50% by weight of PET a ₂ ) based on 100% by weight of A) ),

B) 1 to 40% by weight talc,

C) 0.01 to 5% by weight of lubricant,

D) 0.05-5% by weight of alcohol,

E) 0-40 wt% of other additives

Wherein the total weight percentage of components A) to E) is 100%.

The invention also relates to the use of the molding compositions of the invention for the production of fibers, foils or moldings, and also to any type of moldings produced.

Mineral-filled polyester molding compositions are known. It is also known that the filling prerequisite has a decisive effect on the flowability of the polymer molding composition (C. DeArmitt and M. Hancock, Chapter 8 "Filled Thermoplastics", page 364 in Particulate-filled polymer composites, 2nd edition , editor Professor Roger Rothon, 2003, PAPRA, UK].

One way to improve the flowability of filled or otherwise polyester molding compositions is to chemically alter the molecular weight distribution of the polymer. Firstly, mono- or bi-functional monomers can be used for controlled reduction of the molecular weight of the polymer and hence its viscosity. Secondly, polyfunctional monomers can be used to build polymer structures with some degree of branching, and their flowability can be better than that of the unbranched polymer molding compositions. This is the subject of numerous textbooks and is known to those skilled in the art (in this regard, "Praktische Rheologie der Kunststoffe und Elastomere" [Practical rheology of plastics and elastomers], Prof. Dr. Pahl, Dr. Gleissle, Dr. Laun, VDI-Verlag GmbH, Duesseldorf 1991, chapter 13).

Reactive monomers capable of changing the molecular weight of the polyester include, for example, monohydric or polyhydric alcohols, acids, amines or low molecular weight esters. The chemical properties of ester compounds are likewise the subject of many standard textbooks (see, eg, "Organikum" [Practical organic chemistry], H. G. O. Becker et al., Barth Verlagsgesellschaft mbH, Deutcher Verlag der Wissenschaften, Leipzig, 1993).

WO 2004/106 405 teaches the use of PBT with a low content of dimeric cyclic systems in applications where emission performance is important. However, the fluidity is not enough.

JP-A 101 905 discloses PBT / polycarbonate molding compositions with inorganic fillers and limited amounts of acid end groups, which have advantageous release performance.

By way of example, the number of (acid) end groups can be achieved through chain-extension of the polymer as described in JP 2004075756-A. However, this reduces the fluidity.

New and complex applications of polyester molding compositions are constantly known. At this time, the molding composition should combine various improved properties. Accordingly, there is an increasing demand for the supply of polyester molding compositions with improved flowability and reduced release properties.

Low release moldings are mainly in accordance with DIN 75201, but under more stringent test conditions than the above DIN standard conditions, specifically after maintaining the temperature of the beaker containing the test specimens and having a cover glass plate at 160 ° C. for 24 hours, When the glass plate is measured by turbidity (wide-angle scattering, haze) with a Byk Gardner Haze-Gard (R) plus tester, its fogging performance is given below. According to the present invention, those exhibiting a haze value of less than 20% or less than 15% or less than 10%.

Accordingly, the primary object of the present invention is to provide a polyester molding composition having good fluidity and reduced release.

Accordingly, the molding composition defined in the introduction has been found. Preferred embodiments can be found in the dependent claims.

The molding compositions of the invention comprise 10 to 97% by weight, preferably 20 to 97% by weight, in particular 30 to 80% by weight, of polyesters other than polyethylene terephthalate (PET) as component A) (wherein said polyester is A) PET, based on 100% by weight, 1 to 50% by weight, preferably 10 to 35% by weight).

Suitable polyethylene terephthalates (a ₂ ) are based on ethylene glycol as aliphatic dihydroxy compound and terephthalic acid as aromatic dicarboxylic acid, wherein up to 10 mol% of the aromatic dicarboxylic acids are contained in other aromatic dicarboxylic acids, such as Can be replaced by 2,6-naphthalenedicarboxylic acid or isophthalic acid or mixtures thereof, or by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, or cyclohexanedicarboxylic acid. . In addition, ethylene glycol in polyethylene terephthalate is 0.75% by weight, based on the total weight of polyethylene terephthalate used, for example, with 1,6-hexanediol and / or 5-methyl-1,5-pentanediol. It may be replaced by the following amount.

The viscosity of the polyethylene terephthalate of the invention is generally in the range of 40 to 120 ml / g, preferably 60 to 100 ml / g (0.5 weight in a (1: 1) mixture of phenol / o-dichlorobenzene at 25 ° C.). Solution according to ISO 1628, in% concentration).

The carboxy end group content of polyethylene terephthalate which can be used is generally 60 meq / kg or less, preferably 40 meq / kg or less, in particular 30 meq / kg or less. Carboxy end group content is usually determined via titration (eg using potentiometric methods).

Polyethylene terephthalates that can also be used are mixtures of such compounds that differ in viscosity and carboxy end group content.

The polyethylene terephthalate of the present invention is obtained by a known method using a transesterification process and, where appropriate, a catalyst which accelerates the polycondensation reaction. Examples of suitable catalysts are Lewis-acid inorganic or organometallic compounds, for example those based on metallic atoms of groups IB, IIB, IVA, IVB, VA, VB or VIIIB of the Periodic Table of Elements. By way of example, organic and inorganic compounds which are catalytically active of titanium, tin and antimony mentioned in US Pat. No. 3,936,421 can be used. Organo tin and titanium compounds are particularly suitable and are tetraethyltin, dibutyltin dichloride, dibutyltin malate or dibutyltin laurate, or tetrabutyl ortho titanate, tetraoctyl titanate, or triethanolamine titanate Is an example.

It is also advantageous to use PET recycled materials (also called scrap PET) in mixtures with polyesters such as polyalkylene terephthalates, for example PBT.

Recyclable materials generally are:

1) Those known as post-industrial recycling materials: these are production waste during polycondensation or processing, for example sprues from injection molding, starting materials from injection molding or extrusion, or extrusion Edge trim from sheet or film.

2) Post-consumer recycled materials: These are plastic items that have been collected and disposed of by the end consumer. Blown-molded PET bottles for mineral water, soft drinks and juices are clearly dominant in quantity.

Both types of recycled materials can be used as ground material or in the form of pellets. In the latter case, the crude recycled material is separated and purified, then melted and pelletized using an extruder. This typically facilitates handling and free flow, and measurement at additional steps in processing.

The recycled materials used may be pelletized or in the form of ground materials. The edge length should then be 6 mm or less, preferably less than 5 mm.

Since the polyester is hydrolytically cleaved (due to traces of moisture) during processing, it is reasonable to dry the recycled material in advance. The residual moisture content after drying is preferably less than 0.2%, in particular less than 0.05%.

Polyesters a ₁ ) other than PET based on aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds are generally used.

Preferred polyesters of the first group are polyesters which are preferably polyalkylene terephthalates having 2 to 10 carbon atoms in the alcohol moiety.

Such polyalkylene terephthalates are known per se and are described in the literature. Their backbone includes aromatic rings derived from aromatic dicarboxylic acids. The aromatic ring can also be, for example, by halogen, such as chlorine and bromine, or by C ₁ -C ₄ -alkyl groups such as methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl It may be substituted by a group.

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

Preferred dicarboxylic acids which may be mentioned are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and mixtures thereof. 30 mol% or less, preferably 10 mol% or less of aromatic dicarboxylic acid is added to aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanediic acid and 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 and neopentyl glycol, and mixtures thereof.

Polyalkylene terephthalates derived from alkanediols having 3 to 6 carbon atoms can be mentioned as particularly preferred polyesters (A). Among these, polypropylene terephthalate and polybutylene terephthalate, and mixtures thereof are particularly preferable. In addition, PPT and / or PBT comprising 1,6-hexanediol and / or 2-methyl-1,5-pentanediol in an amount of up to 1% by weight, preferably 0.75% by weight or less as further monomer units are preferred. Do.

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

Particular preference is given to polyesters having a carboxy end group content of at most 100 meq / kg of polyester, preferably at most 60 meq / kg of polyester, in particular at most 50 meq / kg of polyester. Such polyesters can be produced, for example, by the method of DE-A 44 01 055. Carboxy end group content is usually determined via titration (eg potentiometric method).

In a particularly preferred embodiment of A), the PBT: PET ratio is preferably 3: 1 to 1.5: 1, in particular 2.5: 1 to 2: 1.

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

Suitable aromatic dicarboxylic acids are the compounds mentioned above for the polyalkylene terephthalates. The mixture preferably 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 20 to about 50% isophthalic acid.

The aromatic dihydroxy compound preferably has the following formula.

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 atom or a sulfur atom, or a chemical bond, and m is 0 to 2. In addition, the phenylene group of the compound may be substituted by C ₁ -C ₆ -alkyl or alkoxy groups and fluorine, chlorine or bromine.

Examples of parent compounds of such compounds are

Dihydroxybiphenyl,

Di (hydroxyphenyl) alkanes,

Di (hydroxyphenyl) cycloalkane,

Di (hydroxyphenyl) sulfide,

Di (hydroxyphenyl) ether,

Di (hydroxyphenyl) ketone,

Di (hydroxyphenyl) sulfoxide,

α, α'-di (hydroxyphenyl) dialkylbenzene,

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

Resorcinol, and

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

Among these,

4,4'-dihydroxybiphenyl,

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

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

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

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

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 fully aromatic polyesters. These generally comprise from 20 to 98% by weight of polyalkylene terephthalates and from 2 to 80% by weight of fully aromatic polyesters.

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. In addition, such products are commercially available, for example as Hytrel® (DuPont).

The polyester molding composition comprises talc 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, as component B).

The talc used is in particular a hydrated magnesium silicate whose composition is Mg ₃ [(OH) ₂ / Si ₄ O ₁₀ ] or 3MgO.4SiO ₂ .H ₂ O. This compound is known as a three-layered layered silicate, has a triclinic, monoclinic or tetragonal crystal structure and has a plate-like property. Traces of other elements that may be present are Mn, Ti, Cr, Ni, Na and K, where the OH group may be replaced to some extent by fluoride.

It is particularly preferred that 99.5% of the particle size of the talc used is less than 20 μm. Particle size distribution is usually measured via sedimentation analysis, preferably

99.5% by weight is less than 20 μm,

99 wt% is less than 10 μm,

85 wt% is less than 5 μm,

60 wt% is less than 3 μm,

43 weight% is less than 2 micrometers.

This type of product is a micro-talk eye tea. Commercially available in the form of Micro-Talc I.T.extra (Norwegian Talc Minerals).

The polyester molding composition comprises, as component C), at least one lubricant in an amount of 0.01 to 5% by weight, preferably 0.05 to 1% by weight, in particular 0.1 to 0.5% by weight. Preferred lubricants are esters of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22 carbon atoms, and saturated aliphatic alcohols or amines having 2 to 40, preferably 2 to 6 carbon atoms. Or amide.

The carboxylic acid may be monovalent or divalent. Examples that may be mentioned are pelagonic acid, palmitic acid, lauric acid, margaric acid, dodecaneic acid, behenic acid, particularly preferably stearic acid, capric acid, and also montanic acid (30-40 carbons). Mixtures of fatty acids with atoms).

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

Aliphatic amines may be mono-, di- or triamines. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Thus, preferred esters or amides are glyceryl distearate, glyceryl tristearate, ethylenediamine distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobehenate and pentaerythritol tetrastearate .

It is also possible to use mixtures of various esters or amides, or esters in combination with amides, where the mixing ratio is as desired.

The molding compositions of the present invention comprise, as component D), 0.05 to 5% by weight of alcohol, preferably 0.1 to 2% by weight, in particular 0.1 to 1% by weight. It is possible to use monohydric or polyhydric alcohols. Especially preferred are trihydric or dihydric polyhydric alcohols.

It is also possible to use mixtures of monohydric or polyhydric alcohols.

It is also possible to use polymeric alcohols.

It is also possible to use compounds having additional functional groups as well as hydroxy groups, for example acid groups or amine groups. However, the number of hydroxy end groups must exceed the number of residual functional groups. Preferred are compounds which contain only hydroxy groups as reactive groups.

Preference is given to monohydric or polyhydric alcohols having a boiling point at atmospheric pressure above 100 ° C., preferably above 150 ° C., particularly preferably above 200 ° C.

Examples of diols used according to the invention are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol , 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,5-hexadiene-3,4-diol, 1,2- and 1,3-cyclopentanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1,1-, 1 , 2-, 1,3- and 1,4-bis (hydroxymethyl) cyclohexane, 1,1-, 1,2-, 1,3- and 1,4-bis (hydroxyethyl) cyclohexane, Neopentyl glycol, (2) -methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5 -Hexanediol, 2,2,4-trimethyl-1,3-pentanediol, blood Cole, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols _{HO (CH 2 CH 2 O)} n -H or polypropylene glycols _{HO (CH [CH 3] CH} 2 O) n -H ( Wherein n is an integer and is 4 or more), polyethylene polypropylene glycol (where the order of ethylene oxide units or propylene oxide units may take the form of blocks or may be random), polytetramethylene glycol ( Preferably molar mass is 5000 g / mol or less), poly-1,3-propanediol (preferably molar mass is 5000 g / mol or less), polycaprolactone, or mixtures of two or more examples of the compounds to be. One of the aforementioned diols, or alternatively two hydroxy groups, may be replaced by an SH group. Preferred diols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1 , 2-, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-bis (hydroxymethyl) cyclohexane, and also diethylene glycol, triethylene glycol, dipropylene glycol, and Tripropylene glycol.

In addition, the dihydric alcohol optionally comprises additional functional groups, such as carbonyl, carboxy, alkoxycarbonyl or sulfonyl (eg dimethylolpropionic acid or dimethylolbutyric acid), and also C ₁ -C ₄ -alkyl esters thereof. Although it is possible, it is preferable that alcohol B ₂ does not have an additional functional group.

Trihydric or higher alcohols include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl ) Amines, pentaerythritol, diglycerol, triglycerol, or higher condensates of glycerol, di (trimethylolpropane), di (pentaerythritol), trishydroxymethyl isocyanurate, tris (hydroxyethyl) iso Cyanurate (THEIC), tris (hydroxypropyl) isocyanurate, inositol or sugars such as glucose, fructose or sucrose, sugar alcohols such as sorbitol, mannitol, traceol, erythritol, arcitol Donitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol, isomalt, and at least trihydric alcohols and based on ethylene oxide, propylene oxide and / or butylene oxide 3 teeth Polyetherols on the bed.

Wherein glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, tris (hydroxyethyl) isocyanurate, and also ethylene oxide and / Or their polyetherols based on propylene oxide, and also 1,1,1-tris (hydroxymethyl) propane, stearyl alcohol, ethylene glycol, propylene glycol, and neopentyl glycol.

The molding compositions of the invention may comprise as additives E) additional additives and processing aids other than B) and / or C) and / or D) from 0 to 40% by weight, in particular up to 20% by weight.

Examples of conventional additives E) are elastomeric polymers (often referred to as impact modifiers, elastomers or rubbers) in amounts of up to 40% by weight, preferably up to 15% by weight.

They are very generally preferred in ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylate and / or methacrylate monomers having 1 to 18 carbon atoms in the alcohol component. It is a copolymer consisting of two or more.

Polymers of this type are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, 1961), pages 392 to 406 and the monograph by C.B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).

Preferred types of some of these elastomers are described below.

Preferred types of such elastomers are those known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally do not actually have residual double bonds, while EPDM rubbers can have 1 to 20 double bonds per 100 carbon atoms.

Non-conjugated dienes such as isoprene and butadiene, unconjugated dienes having 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexa, may be mentioned for EPDM rubbers. Dienes, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene And also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene , And tricyclodienes such as 3-methyl-tricyclo [5.2.1.0. ^2,6 ] -3,8-decadiene, and 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 1 to 8% by weight, based on the total weight of the rubber.

In addition, EPM and EPDM rubbers can preferably be grafted with reactive carboxylic acids or derivatives thereof. Examples of these are acrylic acid, methacrylic acid and derivatives thereof such as glycidyl (meth) acrylate, and also maleic anhydride.

Copolymers of ethylene with acrylic acid and / or methacrylic acid and / or esters of such acids are another group of preferred rubbers. The rubber may also comprise dicarboxylic acids such as maleic acid and fumaric acid, or derivatives of such acids, such as esters and anhydrides, and / or monomers comprising epoxy groups. Such monomers comprising a dicarboxylic acid derivative or comprising an epoxy group preferably comprise a monomer having a dicarboxylic acid group and / or an epoxy group in the monomer mixture and having the formula (I), (II), (III) or (IV) It adds to rubber | gum by adding.

Wherein R ¹ to R ⁹ are hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer from 0 to 20, g is an integer from 0 to 10, and p is an integer from 0 to 5.

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

Preferred compounds of formulas (I), (II) and (IV) include (meth) acrylates including maleic acid, maleic anhydride and epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and esters with tertiary alcohols such as tert-butyl acrylate. The latter do not have free carboxyl groups, but their aspects are similar to those of free acids, and are therefore called monomers with latent carboxyl groups.

The copolymer advantageously consists of monomers comprising 50 to 98% by weight of ethylene, 0.1 to 20% by weight of epoxy groups and / or methacrylic acid and / or monomers comprising anhydride groups, the remainder being (meth) Acrylate.

50 to 98% by weight, in particular 55 to 95% by weight of ethylene,

0.1-40% by weight, in particular 0.3-20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid, and / or maleic anhydride, and

1 to 45% by weight, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate

Copolymers of are particularly preferred.

Other preferred (meth) acrylates are methyl, ethyl, propyl, isobutyl and tert-butyl esters.

In addition to these, comonomers that can be used are vinyl esters and vinyl ethers.

Said ethylene copolymers can be prepared by methods known per se, preferably by random copolymerization at high pressures and elevated temperatures. Suitable methods are well known.

Another preferred elastomer is an emulsion polymer, the preparation of which is described, for example, by Blackley in the monograph "Emulsion Polymerization". Emulsifiers and catalysts that can be used are known per se.

In general, it is possible to use homogeneous structures of the elastomer or else having shell structures. The shell structure is determined by the order of addition of the individual monomers. In addition, the form of the polymer is affected by this order of addition.

Monomers that may be mentioned by way of example only for the preparation of rubber fractions of elastomers are acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene, and also their Mixture. Such monomers may be copolymerized with other monomers such as styrene, acrylonitrile, vinyl ether and with other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate.

The soft or rubber phase of the elastomer (glass transition temperature is below 0 ° C.) can be a core, sheath or intermediate shell (for elastomers having more than two shells in its structure). Also, elastomers having more than one shell can have more than one shell composed of rubber.

In addition to the rubbery phase, if at least one hard component (glass transition temperature exceeds 20 ° C.) is included in the elastomeric structure, these are generally the main monomers, styrene, acrylonitrile, methacrylonitrile, α-methylstyrene , p-methylstyrene, or acrylates or methacrylates, such as methyl acrylate, ethyl acrylate or methyl methacrylate. In addition to these, it is also possible to use relatively small proportions of other comonomers.

In some cases, it has proven advantageous to use emulsion polymers having reactive groups on the surface. Examples of this type of group are epoxy, carboxy, latent carboxy, amino and amide groups, and also functional groups which can be introduced simultaneously using monomers of the formula:

In the above formula, the substituent may be defined as follows.

R ¹⁰ is hydrogen or a C ₁ -C ₄ -alkyl group,

R ¹¹ is hydrogen or a C ₁ -C ₈ -alkyl group or an aryl group, especially phenyl,

R ¹² is hydrogen, a C ₁ -C ₁₀ -alkyl group, a C ₆ -C ₁₂ -aryl group or -OR ¹³ ,

R ¹³ is a C ₁ -C ₈ -alkyl group or a C ₆ -C ₁₂ -aryl group (if appropriate substituted by a group containing O- or N-),

이고,X is a chemical bond or a C ₁ -C ₁₀ -alkylene group or a C ₆ -C ₁₂ -arylene group, or

ego,

Y is O-Z or NH-Z,

Z is a C ₁ -C ₁₀ -alkylene group or a C ₆ -C ₁₂ -arylene group.

The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups to surfaces.

Other examples that may be mentioned include acrylamide, methacrylamide and substituted acrylates or methacrylates such as (N-tert-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, ( N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) ethyl acrylate.

In addition, the rubbery particles may be crosslinked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also compounds described in EP-A 50 265.

It is also possible to use graft-linked monomers, ie monomers known as monomers having two or more polymerizable double bonds which react at different rates during the polymerization. It is preferred to use compounds of this type where one or more reactive groups polymerize at approximately the same rate as other monomers, while other reactive groups (or reactive groups) polymerize significantly slower, for example. Different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If another phase is grafted to this type of rubber, then at least some of the double bonds present in the rubber react with the graft monomers to form chemical bonds, ie the phase grafted above may have some degree of chemical bond to the graft substrate. Have

Examples of graft-linked monomers of this type are allyl esters of monomers comprising allyl groups, in particular ethylene-unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl malate, diallyl Fumarate and diallyl itaconate, and corresponding monoallyl compounds of such dicarboxylic acids. In addition to these, there are a wide variety of other suitable graft-linked monomers. More specifically, reference may be made to this application, for example, US Pat. No. 4,148,846.

The proportion of such crosslinking monomers in the impact-control polymer is generally 5% by weight or less, preferably 3% by weight or less, based on the impact-control polymer.

Some preferred emulsion polymers are listed below. In the present application, first of all, mention may be made of a graft polymer having a core and at least one outer shell and having the structure:

type Monomer for Core Outer shell monomer I 1,3-butadiene, isoprene, n-butyl acrylate, ethylhexyl acrylate or mixtures thereof Styrene, Acrylonitrile, Methyl Methacrylate II Same as I, but simultaneously using crosslinking agent Same as I III Same as I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, 1,3-butadiene, isoprene, ethylhexyl acrylate IV Same as I or II Same as I or II, but simultaneously using monomers having reactive groups as described herein V Styrene, acrylonitrile, methyl methacrylate or mixtures thereof The first sheath consists of monomers as described in I and II for the core and the second sheath is as described in I or IV for the sheath.

Such graft polymers, in particular ABS polymers and / or ASA polymers, are preferably used in admixture with polyethylene terephthalate in an amount of up to 40% by weight, if appropriate, up to 40% by weight for impact-control of the PBT. Blend products of this type are obtainable under the trademark Ultraradur® S (formerly Ultrablend® S; BASF AG).

In addition, instead of graft polymers having more than one shell, the structure consists of 1,3-butadiene, isoprene and n-butyl acrylate, or a homogeneous, ie single-shell elastomer, from copolymers thereof. It is possible to use. Such products can also be prepared using crosslinking monomers or monomers having reactive groups simultaneously.

Examples of preferred emulsion polymers are n-butyl acrylate- (meth) acrylic acid copolymer, n-butyl acrylate-glycidyl acrylate or n-butyl acrylate-glycidyl methacrylate copolymer, n-butyl acrylic Enveloped graft polymers composed of a rate or of an internal core based on butadiene and the aforementioned copolymers, and copolymers of ethylene and comonomers supplying reactive groups.

The elastomers described can also be prepared by other conventional methods, for example by suspension polymerization.

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

It is of course also possible to use mixtures of the rubbers of the types listed above.

Fibrous or particulate fillers E) which may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silica, asbestos, calcium silicate, calcium metasilicate, carbonic acid, used in amounts of up to 20% by weight, in particular up to 10% by weight. Magnesium, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar.

Preferred mixing ratios with component B) are 40 to 70% by weight of component B) and 65 to 25% by weight of filler E), with a preferred mixing ratio B) to E) of 100: 1 to 2: 1.

Preferred fibrous fillers which may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, with glass fibers in the form of E glass being particularly preferred. These can be used as rovings or in the form of commercially available cut glass.

Particular preference is given to a mixture of glass fibers E) and component B) in a ratio of 1: 100 to 1: 2, preferably 1:10 to 1: 3.

Fibrous fillers can be surface-treated with silane compounds to improve compatibility with thermoplastics.

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 corresponding silanes comprising 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 E).

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

The thermoplastic molding compositions of the invention comprise components (E) which are conventional processing aids such as stabilizers, oxidation retardants, agents for preventing thermal degradation and degradation by ultraviolet radiation, lubricants and mold release agents, colorants such as dyes and pigments, 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 diphenylamine at concentrations of up to 1% by weight, based on the weight of the thermoplastic molding composition. , 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 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.

Typical amounts of lubricants and release agents other than C) are 1% by weight or less. Long chain fatty acids (e.g. stearic acid or behenic acid), salts thereof (e.g. potassium 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.

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

In addition, the molding compositions of the present invention may comprise 0 to 2 weight percent fluorine-comprising ethylene polymer. These are polymers of ethylene having a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.

Examples of these are tetrafluoroethylene air with polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers and relatively small proportions (typically up to 50% by weight) of copolymerizable ethylene-unsaturated monomers. It is coalescing. These are described, for example, in "Sinliknecht" "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484-494 and in Wall "Fluoropolymers" (Wiley Interscience, 1972).

Such fluorine-comprising 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. Such small particle sizes can be particularly preferably achieved by the use of aqueous dispersions of fluorine-comprising ethylene polymers and their incorporation into polyester melts.

The thermoplastic molding compositions of the invention can be prepared by mixing the starting components in conventional mixing equipment, such as screw extruders, Brabender mixers or Banbury mixers, and then extruding them by methods known per se. Can be. 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 in a mixture. The mixing temperature is generally 230 to 290 ° C.

In another preferred method, components B), C) and / or D) can be mixed with the polyester prepolymer, compounded and pelletized. The resulting pellets are then condensed in a solid phase under inert gas continuously or batchwise at a temperature below the melting point of component A) until the desired viscosity is achieved.

The thermoplastic molding compositions of the invention are characterized by good flowability and reduced release.

The molding compositions described are particularly suitable for applications in which the use temperature exceeds 50 ° C.

Headlamp parts, lamp parts, panels or components thereof, headlamp panels or components thereof, lamp panels or components thereof, side cladding, paneling, lighting systems, or external lighting fixtures or components thereof, or Particular preference is given to the use in the manufacture of lighting elements selected from structural parts of the boat body, lawn mower frames, and motorcycle parts (including lighting elements).

The above use is very particularly preferably characterized in that the lighting element is a headlamp part of an automobile.

The present invention also provides moldings, foils, fibers and foams composed of the thermoplastic molding compositions of the invention. The molding is preferably an illumination element.

The molding is particularly preferably used in which the lighting element is a headlamp component, lamp component, panel or component thereof, headlamp panel or component thereof, lamp panel or component thereof, side cladding, paneling, lighting system, or external lighting. Moldings selected from the plant or components thereof, or structural parts of the boat body, lawn mower casting, and motorcycle parts (including lighting elements).

The moldings are very particularly preferably those in which the lighting element is a headlamp part of an automobile.

Car interior uses, for example

Steering Column Module

-Switch, button

-Framework for radio, GPS and air-conditioning systems

-Frame (Fuse Box)

-The frame of the motor that lifts the window

Instrument parts

-Sunroof Parts / Sunroof Frames

Seat adjustment mechanism

This is a further use.

Component a ₁ )

Polybutylene terephthalate with a VN of 105 ml / g and a carboxy end group content of 33 meq / kg. Ultradur® B 2550, a product commercially available from BASF, was used.

Component a ₂ )

PET with VN of 100 ml / g (VN measured in a 0.5 wt% solution consisting of a 1: 1 mixture of phenol / o-dichlorobenzene at 25 ° C.). RT 51, a product commercially available from Invista, was used.

Component B)

Talc (Haiti Extra Talc from Omya GmbH)

Component C)

Pentaerythritol tetrastearate. Loxiol® EP 861, a product commercially available from Cognis, was used.

D1) 1,1,1-tris (hydroxymethyl) propane (CAS 77-99-6) from Acros Organics, purity 98% or more

D2) trimesic acid (CAS 554-95-0) from Aldrich, purity 95% or more

D3) adipic acid from Merck (CAS 124-04-9), purity more than 99%

D4) Melamine from ACROS Organics (CAS 108-78-1), 99% purity or more

D5) Dimethyl terephthalate (CAS 120-61-6) from Acros Organics, at least 99% pure.

Components A to D according to the configurations mentioned in Table 2 were homogenized in a ZSK 30 twin-screw extruder from Werner & Pfleiderer at 250 ° C., and the mixture was extruded into a water bath, pelletized and dried. . The pellets were used for injection molding discs, dumbbell-shaped specimens and standard small specimens in an injection molding machine at 260 ° C. melt temperature and 80 ° C. mold surface temperature, and then the moldings were tested.

In order to ensure equality of experiments, the amount of reactive monomers was chosen such that the product of weight ratio x atom / molecular weight is approximately equivalent.

Valence is defined as the number of functional groups. By way of example, hexamethylenediamine is divalent and trimesic acid is trivalent.

For the evaluation of the fog formation performance, discs with a diameter of 80 mm and a thickness of 4 mm were made and their fog formation performance was tested against DIN 75 201 (September 1992), Method A. At this time, the storage time of the disk was 24 hours, the storage temperature was 160 ℃.

Fog-forming glass plates obtained according to the mentioned DIN 75 201 standard were subjected to total permeability with a Haze-Gard plus device from BYK-Gardner GmbH (Gerethsd, Germany). It was tested according to ASTM D1003 for, turbidity and clarity. Turbidity is the diffuse transmittance measurable as wide-angle scattering deflected more than 2.5 degrees from the incident light beam, and transparency is measurable diffusivity as elevation angle scattering with an angle range of less than 2.5 degrees. As the total transmittance value increased, fog formation decreased, the haze value decreased, and the transparency value increased, respectively.

Melt volume velocity MVR was measured at a nominal load of 2.16 kg at a melt temperature of 266 ° C. according to ISO 1133.

VN was measured according to ISO 1628.

The table below provides the measurement results and configuration of the molding composition.

Comparison of Example 1.6V with the rest of the examples shows that in all cases the reactive monomers resulted in a decrease in the viscosity of the molding composition, and an increase in the MVR value, respectively.

However, only the configuration of the present invention shows improved flowability and good release.

Claims (10)

A) 10 to 98% by weight of one or more polyesters a ₁ ) other than polyethylene terephthalate (PET), wherein the polyester comprises 1 to 50% by weight of PET a ₂ ) based on 100% by weight of A) ), B) 1 to 40% by weight talc, C) 0.01 to 5% by weight of lubricant, D) 0.05-5% by weight of alcohol, E) 0-40 wt% of other additives Wherein the total weight percentage of components A) to E) is 100%. The thermoplastic molding composition of claim 1, comprising polyalkylene terephthalate as component a ₁ ). 3. The at least one ester or amide of claim 1, wherein as component C) saturated or unsaturated carboxylic acids having from 10 to 40 carbon atoms and saturated aliphatic alcohols or amines having from 2 to 40 carbon atoms are used. Thermoplastic molding composition comprising. The thermoplastic molding composition according to claim 1, wherein the particle size of 99.5% of component B) is less than 20 μm. The thermoplastic molding composition according to claim 1, comprising a polyhydric alcohol D). 6. The thermoplastic molding composition according to claim 1, comprising at least one trivalent or dihydric alcohol as component D). 7. Use of a thermoplastic molding composition according to claim 1 for the production of fibers, foils or moldings. Moldings obtainable from the thermoplastic molding composition according to claim 1. The molding according to claim 8, which is a lighting element. 10. The device of claim 8 or 9, wherein the lighting element comprises a headlamp component, lamp component, panel or component thereof, headlamp panel or component thereof, lamp panel or component thereof, side cladding, paneling, lighting system, Or an external lighting fixture or component thereof, or a structural part of a boat body, a lawn mower frame, and a motorcycle part (including a lighting element).