KR20000029504A - Heat-insulated transport containers - Google Patents

Abstract

PURPOSE: A transport container is provide which has a dimensional stability, a heat resistance and a weather resistance, and which is heat-insulated. CONSTITUTION: A thermoplastic moulding materials which are different from ABS and which, in relation to the sum of the quantities of components A and B and optionally C and/or D resulting in a total of 100wt%, contain (a) 1-99wt%, preferably 15-60 wt%, in particular 25-50wt% of a particulate emulsion polymer with a glass transition temperature of less than 0°C and a mean particle size of 50-1000nm, preferably 50-500nm as component A, (b) 1-99wt%, preferably 40-85wt%, in particular 50-75wt% of at least one amorphous or semi-crystalline polymer as component B, (c) 0.50wt% polycarbonate as component C and (d) 0-50wt% of fiber or particulate filling materials or their mixtures as component D. The materials are used for producing heat-insulated transport containers.

Description

Heat Insulated Transport Containers

The present invention relates to an adiabatic transport container. In particular, the present invention relates to an adiabatic transport container which is dimensional stability and heat resistance and excellent in weatherability.

Insulated transport containers are used, for example, when instant hot or refrigerated foods have to be transported to consumers. Therefore, the fields in which they are used are the welfare sector and the food service and food sector. As the supply of packaged hot instant meals from manufacturers to consumers increases, there is an increasing demand for suitable insulated transport containers with a characteristic profile for these applications.

Transport Containers Various materials are used to produce, for example, adiabatic transport containers for transporting foodstuffs, especially hot manufactured foods.

For example, polypropylene is used, but it has a low glass transition temperature and shows significant softening even at temperatures of about 50 ° C. Thus, for food products, the dimensional stability is not sufficient at the temperature of the insulation, which may be, for example, about 80 ° C. In addition, polypropylene has a poor toughness / rigidity ratio. After prolonged exposure to heat, the mechanical strength is poor and unsuitable. Insulated transport containers made of polypropylene have poor scratch resistance and dimensional accuracy of the parts.

HIPS (high impact polystyrene) is used as additional material. However, since the strength decreases as the heat storage proceeds, the mechanical strength is insufficient to be exposed to heat for a long time. In addition, there is a lack of weather resistance.

It is an object of the present invention to provide an insulated transport container which is dimensional stability and which exhibits good dimensional accuracy.

It is another object of the present invention to provide a low weight and stable thermally insulated transport container.

It is a further object of the present invention to provide an insulated transport container which can be exposed to heat without loss of strength.

It is another object of the present invention to provide a thermally insulating container which is very stable against weathering action.

It is still another object of the present invention to provide an insulated transport container which exhibits superior properties over conventionally used transport containers.

In order to manufacture the adiabatic transport container,

(a) As component A, 1 to 99% by weight of the granular emulsion polymer having a glass transition temperature of 0 ° C. or less and a particle size (median value) of 50 to 1000 nm,

(b) component B, from 1 to 99% by weight of at least one amorphous or partially crystalline polymer,

(c) 0 to 50% by weight of polycarbonate as component C, and

(d) 0 to 50% by weight of component D, fibrous or particulate filler or mixtures thereof, wherein the composition ratio is based on 100% by weight of the total weight of components A and B and, if necessary, C and / or D It has been found that the above object can be achieved by using a thermoplastic molding composition, which is different from ABS.

The adiabatic transport container according to the present invention has dimensional stability, heat resistance, and excellent weather resistance. They are light in weight and very stable. In addition, they are excellent in chemical resistance and high scratch resistance.

Thermoplastic molding compositions used to prepare adiabatic transport containers according to the invention are known per se. Molding compositions that can be used according to the invention are, for example, DE-A-12 60 135, DE-C-19 11 882, DE-A-28 26 925, DE-A-31 49 358, DE-A- 32 27 555 and DE-A-40 11 162.

In one embodiment, the molding composition, other than ABS, used to prepare the adiabatic transport container according to the present invention comprises components A and B, further defined below, and C and / or D, as required. That is, the composition

(a) As component A, 1 to 99% by weight of a granular emulsion polymer having a glass transition temperature of 0 ° C. or lower and a particle size (median) of 50 to 1000 nm, preferably 50 to 500 nm, preferably 15 to 60 Weight percent, especially 25-50 weight percent,

(b) as component B, from 1 to 99% by weight, preferably from 40 to 85% by weight, in particular from 50 to 75% by weight, of at least one amorphous or partially crystalline polymer,

(c) 0 to 50% by weight of polycarbonate as component C, and

(d) component D, comprising 0 to 50% by weight of fibrous or particulate filler or mixtures thereof, wherein the composition ratio is based on 100% by weight of the total weight of components A and B, and C and / or D do.

The present invention is described in more detail below.

First, the components constituting the molding composition used to prepare the adiabatic transport container according to the present invention are described.

<Component A>

Component A is a granular emulsion polymer having a glass transition temperature of 0 ° C. or less and a particle size (median) of 50 to 1000 nm.

Component A is preferably

(a1) 1 to 99% by weight, preferably 55 to 80% by weight, in particular 55 to 65% by weight of the graft base A1 having a glass transition temperature of 0 ° C. or less,

(a2) (a21) As component A21, 40 to 100% by weight of vinylaromatic monomers, preferably styrene, substituted styrene or (meth) acrylate units or mixtures thereof, in particular styrene and / or α-methylstyrene units , Preferably 65 to 85% by weight (based on A2), and

(a22) As component A22, prepared from ethylenically unsaturated monomers, preferably acrylonitrile or methacrylonitrile, in particular up to 60% by weight, preferably from 15 to 35% by weight (based on A2) of acrylonitrile units Graft copolymer A2 prepared from 1 to 99% by weight, preferably 20 to 45% by weight, in particular 35 to 45% by weight.

The graft component A2 above comprises at least one graft shell and the particle size (median) of the total graft copolymer A is 50 to 1000 nm.

In one embodiment of the invention, component A1 is

(a11) 80 to 99.99 wt%, preferably 95 to 99.9 wt% of C ₁ -C ₈ -alkyl acrylate, preferably n-butyl acrylate and / or ethylhexyl acrylate, as component A11, and

(a12) As component A12, it consists of at least one multifunctional crosslinking monomer, preferably diallyl phthalate and / or 0.01 to 20% by weight, preferably 0.1 to 5.0% by weight of DCPA.

In one embodiment of the invention, the particle size (median) of component A is between 50 and 800 nm, preferably between 50 and 600 nm.

In another embodiment of the invention the particle size distribution of component A has two maximums and 60 to 90% by weight, based on the total weight of component A, has a particle size (median) of 50 to 200 nm, 10 To 40% by weight has a particle size (median) of 50 to 400 nm.

The given particle size (median) and particle size distribution are the sizes determined by the integral weight distribution. The particle size (median) according to the invention is in all cases the weight average of the particle size. They are determined based on the method of W. Scholtan and H. Lange (Kolloid-Z. And Z.-polymere 250 (1972), pp. 782-796). Integral weight distribution of sample particle diameters is obtained by ultracentrifuge measurement. From this it can be deduced the weight percent of the particles having a diameter equal to or less than a certain size. The average particle diameter, also called d ₅₀ of the integral weight distribution, is defined as the particle diameter having a diameter smaller than ₅₀ % by weight of the particles corresponding to d ₅₀ . This is such that ₅₀ % by weight of the particles have a diameter greater than d ₅₀ . When describing the particle size distribution width of the rubber particles, the d ₁₀ and d ₉₀ values given by the integral weight distribution are used together with the d ₅₀ value (average particle diameter). The d ₁₀ and d ₉₀ of the integral weight distribution differ only on the basis of 10% and 90% by weight of the particles, respectively, and are defined similarly to d ₅₀ . The following equation 1 determines the particle size distribution width.

It is preferred that the emulsion polymer A, which can be used as component A according to the invention, has a Q of less than 0.5, in particular less than 0.35.

The glass transition temperature of the emulsion polymer A and other components used according to the invention is determined using DSC (Differential Scanning Calorimetry) according to ASTM 3418 (Midpoint Temperature).

In one embodiment of the invention, emulsified polymer A which can be used is epichlorohydrin rubber, ethylene / vinyl acetate rubber, polyethylene chlorosulfone rubber, silicone rubber, polyether rubber, hydrogenated diene rubber, polyalkenamer rubber, acrylic Commonly related rubbers such as late rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, butyl rubber and fluorine rubber. Preferred are acrylate rubbers, ethylene / propylene (EP) rubbers and ethylene / propylene / diene (EPDM) rubbers, in particular acrylate rubbers.

Pure butadiene rubber used in ABS cannot be used as the only component A.

In one embodiment, the diene based units in the emulsion polymer A are kept very low so that unreacted double bonds remain in the polymer as much as possible. In one embodiment, there is no diene based unit in the emulsion polymer A.

The acrylate rubber is preferably an alkyl acrylate prepared from at least one C ₁ -C ₈ -alkyl acrylate, preferably C ₄ -C ₈ -alkyl acrylate, and preferably butyl, hexyl, octyl or 2-ethylhexyl acrylic It is preferred to use at least some rate of the rate, in particular n-butyl and 2-ethylhexyl acrylate. These alkyl acrylate rubbers may comprise, as comonomers, up to 30% by weight of monomers forming hard polymers such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate or vinyl ether. Can be.

In one embodiment of the present invention, the acrylate rubber further comprises 0.01 to 20% by weight, preferably 0.1 to 5% by weight of a multifunctional monomer (crosslinkable monomer) having a crosslinking action. Examples of these are monomers which contain at least two copolymerizable double bonds which are preferably not conjugated in positions 1,3.

Examples of suitable crosslinkable monomers include divinylbenzene, diallyl malate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, Dihydrodicyclopentadienyl acrylate, triallyl phosphate, allyl acrylate and allyl methacrylate. Dicyclopentadienyl acrylate (DCPA) has proven to be a particularly useful crosslinkable monomer (see DE-C 12 60 135).

Examples of suitable silicone rubbers are crosslinked silicone rubbers comprising units of the formulas R ₂ SiO, RSiO _3/2 , R ₃ SiO _1/2 and SiO _2/4 , where R is a monovalent radical. The amount of the individual siloxane units is such that, for each of the formula R ₂ SiO 100 units, RSiO _3/2 0 to 10 mole units, R ₃ SiO _1/2 0 to 1.5 mole units and SiO _2/4 0 to 3 mole units are present. Decide R may be a group prone to attack by monovalent saturated hydrocarbon radicals having 1 to 18 carbon atoms, phenyl or alkoxy, or free radicals such as vinyl or mercaptopropyl. It is preferred that at least 80% of the R radicals are methyl radicals. Particular preference is given to combinations of methyl and ethyl or phenyl radicals.

Preferred silicone rubbers are those which incorporate units of free radicals, in particular vinyl, allyl, halo or mercapto groups, in amounts of 2 to 10 mol%, based on all radicals R. For example, they can be prepared as described in EP-A-0 260 558.

In some cases it may be useful to use emulsion polymer A made of uncrosslinked polymers. Monomers that can be used to prepare such polymers are all of the monomers described above. Examples of preferred uncrosslinked emulsion polymers A are homopolymers and copolymers of acrylates, in particular n-butyl and ethylhexyl acrylates and homopolymers of ethylene, propylene, butylene, isobutylene and poly (organosiloxane) And copolymers. In all cases they may be linear or branched.

<Core-shell emulsion polymer A>

Emulsifying polymer A may also be a polymer constructed in one or more stages (having a core-shell form). For example, the elastomeric core (T _g <0 ° C.) may be encapsulated with a hard shell (T _g > 0 ° C.) or vice versa.

In a particularly preferred embodiment of the invention, component A is a graft copolymer. The graft copolymer A of the molding composition according to the invention has a particle size (median) d ₅₀ of 50 to 1000 nm, preferably 50 to 600 nm, particularly preferably 50 to 400 nm. These particle sizes can be achieved when using particle size 50 to 350 nm, preferably 50 to 300 nm, particularly preferably 50 to 250 nm as the graft base A1 of component A.

Graft copolymer A generally has one or more steps, that is to say a polymer composed of one core and one or more shells. This polymer comprises a base (graft core) A1 and one, preferably more, of step A2 (known as a graft, graft step or graft shell) grafted thereon.

One or more graft shells may be applied to the rubber particles via simple graft or multistage graft. Each graft shell can have various combinations. In addition, the graft monomers and together with the graft monomers can be grafted with polyfunctional crosslinkable monomers or monomers containing reactive groups (e.g. EP-A-0 230 282, DE-A-36 01 419 and EP-A-0 269 861).

In a preferred embodiment, component A consists of a graft copolymer consisting of one or more steps, wherein the graft is generally made from a resin forming monomer and has a glass transition temperature T _g of at least 30 ° C., preferably at least 50 ° C. Structures having one or more steps act in particular to achieve some degree of compatibility of rubber particles A and thermoplastic B.

Graft copolymer A is prepared by, for example, grafting one or more monomers A1 described below onto one or more graft bases (or graft core materials) A1 described below. Suitable graft bases A1 for the molding compositions according to the invention are any of the polymers described above for emulsion polymer A.

In one embodiment of the invention, the graft base A1 is made from 15 to 99% by weight of acrylate rubber, 0.1 to 5% by weight crosslinker and 0 to 49.9% by weight of one of the other monomers or rubbers mentioned.

Suitable monomers for forming the graft component A2 are, for example, styrene and its substituted derivatives (e.g., α-methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, pt-butylstyrene, o- and p- Divinylbenzene and p-methyl-α-methylstyrene) and C ₁ -C ₈ -alkyl (meth) acrylates (eg, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n Vinyl aromatic monomers such as -butyl acrylate and s-butyl acrylate) and mixtures thereof. Preferred are styrene, α-methylstyrene and methyl methacrylates, in particular styrene and / or α-methylstyrene and acrylic and methacrylic compounds (eg acrylonitrile, methacrylonitrile, acrylic acid and methacrylic acid) , Methyl acrylate, ethyl acrylate, n-propyl and isopropyl acrylate, n-butyl and isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl and isopropyl methacrylate, n-butyl and isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate) and maleic esters, maleic acid diesters and Maleic anhydrides such as maleimide and derivatives thereof (e.g. alkyl- and arylmaleimides such as methyl-phenylmaleimide) Butyl-series unsaturated monomer. Preferred are acrylonitrile and methacrylonitrile, in particular acrylonitrile.

Other (co) monomers that may be used include styrene compounds, vinyl compounds, acrylic or methacrylic compounds (eg, styrene substituted with C ₁ -C ₁₂ -alkyl radicals, halogen or halomethylene radicals as required; vinyl; Naphthalene, vinylcarbazole; vinyl ether with C ₁ -C ₁₂ ether radicals; vinylimidazole, 3- (4) -vinylpyridine, dimethylaminoethyl (meth) acrylate, p-dimethylaminostyrene, acrylonitrile , Methacrylonitrile, acrylic acid, methacrylic acid, butyl acrylate, ethylhexyl acrylate and methyl methacrylate and fumaric acid, maleic acid or itaconic acid or anhydrides thereof, amides, nitriles or 1 to 22 carbon atoms, preferably Preferably an ester with an alcohol having from 1 to 10 carbon atoms.

In one embodiment of the present invention, component A comprises 50 to 90% by weight of graft base A1 described above and 10 to 50% by weight of graft A2 described above, based on the total weight of component A.

In one embodiment of the invention, a crosslinked acrylate polymer having a glass transition temperature of 0 ° C. or less is used as the graft base A1. The crosslinked acrylate polymer should preferably have a glass transition temperature of -20 ° C or below, in particular -30 ° C or below.

In a preferred embodiment, the graft A2 comprises at least one graft shell, of which the outermost graft shell has a glass transition temperature of at least 30 ° C., and the polymer formed with this graft A2 monomer has a glass transition temperature of at least 80 ° C.

Regarding the glass transition temperature, particle size (median) and Q value described for the emulsion polymer A, it is also applicable to the graft copolymer A.

Graft copolymer A can also be prepared by grafting a preformed polymer on a suitable graft homopolymer. Examples are products obtained from the reaction of a base containing rubber with a copolymer containing maleic anhydride groups or acid groups.

Suitable methods for preparing graft copolymer A are emulsion, solution, bulk and suspension polymerization. Graft copolymer A is particularly prepared by free-radical emulsion polymerization using water-soluble or fat-soluble initiators such as peroxodisulfate or benzoyl peroxide or with the help of redox initiators at temperatures of 20-90 ° C. in the presence of component A1 lattice. desirable. Redox initiators are also suitable for polymerization up to 20 ° C.

Suitable emulsion polymerization processes are described in DE-A-28 26 925 and 31 49 358 and DE-C-12 60 135.

The graft shell is preferably prepared by emulsion polymerization method as described in DE-A-32 27 555, 31 49 357, 31 49 358 and 34 14 118. Specifically adjusting the particle size to 50 to 1000 nm in accordance with the present invention is described in DE-C-12 60 135 and DE-A-28 26 925 and Applied Plymer Science, Vol. It is preferable to carry out by the method of 9 (1965), page 2929. The use of polymers with different particle sizes is known, for example, from DE-A-28 26 925 and US 5,196,480.

According to DE-C-12 60 135, the graft base A1 is first used in a manner known per se in acrylates used in one embodiment of the invention in an aqueous emulsion at a temperature of 20 to 100 ° C., preferably 50 to 80 ° C. The polyfunctional monomer causing crosslinking (s) and crosslinking is prepared, if necessary, by polymerization with other comonomers. Conventional emulsifiers can be used, such as alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or resin soaps. Preference is given to using sodium salts of alkylsulfonates or fatty acids having 10 to 18 carbon atoms. In one embodiment, the amount of emulsifier used is from 0.5 to 5% by weight, in particular from 1 to 2% by weight, based on the monomers used to prepare the graft base A1. The weight ratio of water to monomer is generally 2: 1 to 0.7: 1. The polymerization initiator used is, in particular, conventional persulfates such as potassium persulfate. However, redox systems can also be used. The initiator generally uses from 0.1 to 1% by weight, based on the monomers used to prepare the graft base A1. Other polymerization aids that may be used for the polymerization include conventional buffering materials, such as sodium bicarbonate and sodium pyrophosphate, and molecular weight controlling agents such as mercaptans, terpinol or dimers, which can adjust the pH to 6-9. α-methylstyrene may be 0 to 3% by weight.

The precise polymerization conditions, in particular the type, method of addition and amount of emulsifier, range from d ₅₀ of the resulting latex of the crosslinked acrylate polymer to about 50 to 1000 nm, preferably 50 to 150 nm, particularly preferably 80 to 100 nm. To be individually determined within the ranges given above. At this time, the particle size distribution is preferably narrow. The value of Equation 1 below should be <0.5, preferably <0.35.

<Equation 1>

In a subsequent step, the graft polymer A is prepared by polymerizing a monomer mixture prepared from styrene and acrylonitrile in the presence of the latex of the crosslinked acrylate polymer produced in one embodiment of the invention, in which one embodiment of the invention In an embodiment, the weight ratio of styrene to acrylonitrile in the monomer mixture should be in the range of 100: 0 to 40:60, preferably 65:35 to 85:15. Graft copolymerization of styrene and acrylonitrile on a crosslinked polyacrylate polymer that acts as a graft base is advantageously carried out in an aqueous emulsion under the conventional conditions described above. The graft copolymerization may be useful to be carried out in a system used in emulsion polymerization for preparing the graft base A1, to which an emulsifier and an initiator may be further added, if necessary. In one embodiment of the invention, the mixture of styrene and acrylonitrile monomers to be grafted can be added to the reaction mixture at once, in small portions in one or more steps, or preferably in succession during the polymerization. have. Graft copolymerization of a mixture of styrene and acrylonitrile in the presence of a crosslinkable acrylate polymer is in the range of 1 to 99% by weight, preferably 20 to 45% by weight, in particular 35 to 45% by weight, based on the total weight of component A To obtain a graft diagram of. Since the graft yield of the graft copolymer is not 100%, the amount of the mixture of styrene and acrylonitrile monomers to be used for the graft copolymerization is greater than that corresponding to the desired graft degree. The graft yield in graft copolymerization and thus the graft diagram of the finished graft copolymer A will be familiar to those skilled in the art. For example, it can be achieved by metering rate of monomer or by addition of a control agent (see Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329, below). Emulsified graft copolymerization generally provides about 5 to 15% by weight of the grafted free styrene-acrylonitrile copolymer based on the graft copolymer. The proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method described above.

The preparation of graft copolymers by the emulsification method allows for a reproducible change in particle size, for example by agglomerating the particles at least to some extent to form larger particles, in addition to the advantages of the technical method described above. This means that polymers of different particle sizes may also be present in the graft copolymer A.

In particular, component A consisting of the graft base and the graft shell (s) is ideally suited for the respective use, in particular in particle size.

Graft copolymer A is generally 1 to 99% by weight, preferably 55 to 80% by weight, particularly preferably 55 to 65% by weight of graft base A1 and 1 to 99% by weight, based on the total graft copolymer Preferably 20 to 45% by weight, particularly preferably 35 to 45% by weight of graft A2.

<Component B>

Component B is an amorphous or partially crystalline polymer.

Component B is preferably

(b1) 40 to 100% by weight, preferably 60, of vinylaromatic monomers, preferably styrene or substituted styrene or (meth) acrylates or mixtures thereof, in particular styrene and / or α-methylstyrene units To 70 weight percent, and

(b2) As component B2, copolymers containing ethylenically unsaturated monomers, preferably acrylonitrile or methacrylonitrile, in particular up to 60% by weight, preferably 30 to 40% by weight of acrylonitrile units.

In a preferred embodiment of the invention, the viscosity number of component B is between 50 and 90, preferably between 60 and 80.

The amorphous or partially crystalline polymer of component B of the molding composition used to prepare the adiabatic transport container according to the invention is preferably a partially crystalline polyamide, a partially aromatic copolyamide, a polyolefin, an ionomer, a polyester At least one polymer selected from the group consisting of polyether ketones, polyoxyalkylenes, polyarylene sulfides and polymers prepared from vinylaromatic monomers and / or ethylenic monomers. It is also possible to use polymer mixtures.

Suitable polyamides as component B of the molding compositions used to prepare the adiabatic transport containers according to the invention are partially crystalline and preferably linear polyamides, for example nylon-6, nylon-6,6, nylon -4,6 and nylon 6,12 and partially crystalline copolyamides thereof. The acid component is partially or wholly adipic acid and / or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or dodecanedicarboxylic acid and (Or) cyclohexanedicarboxylic acid, the diamine component being partly or wholly or partially of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and Formulations consisting of (or) 2,4,4-trimethyl-hexamethylenediamine and / or isophoronediamine and conforming to its principles are known from the prior art (see Encyclopedia of Polymers, Vol. 11, p. 315 p.) Partially crystalline polyamides can also be used.

Examples of other polymers suitable as component B of the molding compositions used to prepare the adiabatic transport containers according to the invention are partially crystalline polyolefins, preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1 Homopolymers and copolymers of olefins such as -heptene, 3-methyl-1butene, 4-methyl-1-butene, 4-methyl-1-pentene and 1-octene. Suitable polyolefins are polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene. Polyethylene (PE) is generally further divided into high density PE (HDPE), low density PE (LDPE) and linear low density PE (LLDPE).

In another embodiment of the invention the ionomer is component B. These generally comprise the polyolefins described above, in particular polyethylene, as condensed monomers having acid groups, for example acrylic acid, methacrylic acid groups and, if necessary, other copolymerizable monomers. The acid groups are generally ionic by metals such as Na ⁺ , Ca ²⁺ , Mg ²⁺ and Al ³⁺ , and if necessary, are converted into ionically crosslinked polyolefins, which are still processed by thermal plasticization. (See, eg, US 3,264,272; 3,404,134; 3,355,319 and 4,321,337). However, it is not essential to convert polyolefins containing acid groups using metal ions. Polyolefins containing free acid groups are also suitable as component B according to the invention. These generally have rubber properties and to some extent include other copolymerizable monomers such as (meth) acrylates.

In addition, polyesters, preferably aromatic / aliphatic polyesters, can also be used as component B. Examples thereof include, for example, polyalkylenes based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis (hydroxymethyl) cyclohexane Terephthalates, and polyalkylene naphthalates.

Also, for example, GB 1 078 234, US 4,010,147, EP-A-0 135 938, EP-A-0292 211, EP-A-0 275 035, EP-A-0 270 998 and EP 165 406, and The polyether ketones described in publications such as CK Sham, Polymer 29/6, (1988), 1016-1020 can be used as component B.

Polyoxyalkylenes, such as polyoxymethylene and oxymethylene polymers, can also be used as component B of the molding compositions used to prepare the adiabatic transport containers according to the invention.

Other polymers useful as component B are polyarylene sulfides, in particular polyphenylene sulfides.

In one embodiment of the invention component B consists of 50 to 99% by weight of vinylaromatic monomers and 1 to 50% by weight of one or more other given monomers.

Component B is preferably the amorphous polymer described above in the form of graft A2. In one embodiment of the invention, component B is a copolymer of styrene and / or α-methylstyrene with acrylonitrile. The acrylonitrile content in the copolymer of component B is 0 to 60% by weight, preferably 30 to 40% by weight, based on the total weight of component B. Free grafted styrene-acrylonitrile copolymers produced during the graft copolymerization to prepare component A are also included as component B. Depending on the conditions selected for the graft copolymerization to prepare the graft copolymer A, a sufficient proportion of component B may have already been produced during the graft copolymerization. In general, however, the product obtained from the graft copolymerization must be blended with the additional component B prepared separately.

The additional component B prepared separately is preferably a styrene-acrylonitrile copolymer, an α-methylstyrene-acrylonitrile copolymer or an α-methylstyrene-styrene-acrylonitrile terpolymer. These copolymers can be used in component B as individual polymers or as a mixture, so that separately prepared additional component B of the molding compositions used according to the invention can be used, for example, with styrene-acrylonitrile copolymers and α- It may be a mixture of methylstyrene-acrylonitrile copolymers. When component B of the molding composition used according to the invention consists of a mixture of a styrene-acrylonitrile copolymer and an α-methylstyrene-acrylonitrile copolymer, the acrylonitrile content in both copolymers is By weight, they should differ from each other by preferably at most 10% by weight, preferably at most 5% by weight. However, component B of the molding composition used according to the present invention is a single component if the starting material for the preparation of further component B prepared separately from the starting material of the graft copolymerization for preparing component A is the same monomer mixture of styrene and acrylonitrile. It should consist only of styrene-acrylonitrile copolymers.

Additional component B prepared separately can be obtained by conventional methods. Therefore, in one embodiment of the present invention, the copolymerization of styrene and / or α-methylstyrene with acrylonitrile can be carried out in bulk, solution, suspension or aqueous emulsion. Component B preferably has a viscosity number of 40 to 100, more preferably 50 to 90, in particular 60 to 80. The viscosity number is dissolved in 0.5 g of material in 100 ml of dimethylformamide and determined according to DIN 53 726.

Components A and B and, if desired, C and D can be mixed in any desired manner using any known method. For example, if components A and B were prepared by emulsion polymerization, the polymer dispersions obtained can be mixed with each other, and then the polymer and polymer mixture precipitated together can be worked up. However, blending of components A and B is carried out by extruding, kneading or rolling the components together. If desired, the components are first isolated from the aqueous dispersion or solution obtained in the polymerization. In addition, the product (component A) of the graft copolymer obtained in the aqueous dispersion can be partially dehydrated and mixed with component B in the form of moist debris. In this case, the graft copolymer is completely dried during mixing.

In a preferred embodiment, the molding composition used to prepare the adiabatic transport container according to the invention comprises in addition to components A and B additional components C and / or D and other additives as described below, as required.

<Component C>

Suitable polycarbonate C is known per se. They preferably have a molar mass (weight average M _w , determined using gel permeation chromatography in tetrahydrofuran on a polystyrene basis) in the range of 10,000 to 60,000 g / mol. These can be obtained, for example, by the method of DE-B-1 300 266 by interfacial polycondensation or by the method of DE-A-1 495 730 in which diphenyl carbonate and bisphenol are reacted. Preferred bisphenols are 2,2-di (4-hydroxyphenyl) propane generally and hereinafter referred to as bisphenol A.

Other aromatic dihydroxy compounds instead of bisphenol A, especially 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4 '-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenyl methane, 1,1-di (4-hydroxyphenyl) ethane, 4, 4-dihydroxydiphenyl or dihydroxydiphenyl cycloalkane, preferably dihydroxydiphenyl cyclohexane or dihydroxycyclopentane, in particular 1,1-bis (4-hydroxyphenyl) -3,3 , 5-trimethylcyclohexane or a mixture of these dihydroxy compounds can be used.

Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A in which the aromatic dihydroxy compound is mixed up to 80 mol%.

It is also possible to use copolycarbonates according to US 3,737,409. Copolycarbonates based on bisphenol A and di (3,5-dimethyldihydroxyphenyl) sulfone are of particular interest here and have high heat resistance. It is also possible to use mixtures of various polycarbonates.

According to the invention, the average molar mass of polycarbonate C (weight average M _{w as} determined using gel permeation chromatography in tetrahydrofuran on a polystyrene basis) ranges from 10,000 to 64,000 g / mol. It is preferably in the range of 15,000 to 63,000 g / mol, in particular 15,000 to 60,000 g / mol. This means that polycarbonate C has a relative solution viscosity of 1.1 to 1.3, preferably 1.15 to 1.33 when measured at 25 ° C. with 0.5% by weight strength in dichloromethane. The relative solution viscosity of the polycarbonates used should preferably not differ by more than 0.05, in particular not more than 0.04.

Polycarbonate C can be used as ground material or pellets. They are present as component C in an amount of 0 to 50% by weight, preferably 10 to 40% by weight, based on the total molding composition.

In one embodiment of the present invention, the addition of polycarbonate increases the thermal stability and the crack resistance of the molding compositions used for producing the thermally insulating containers, in particular according to the present invention.

<Component D>

Preferred thermoplastic molding compositions for use in the production of adiabatic transport containers according to the invention are as component D 0 to 50% by weight, preferably 0 to 40% by weight, in particular 0 to 30% by weight, based on the total molding composition, or Particulate fillers or mixtures thereof. These are preferably commercially available products.

Reinforcing agents such as carbon fibers and glass fibers are typically used in amounts of from 5 to 50% by weight, based on the total molding composition.

The glass fibers used can be made from E, A or C glass and are preferably equipped with a sizing agent and a coupling agent. The diameter is generally 6-20 μm. Continuous fibers (roving) or chopped glass fibers (staples) of 1 to 10 μm in length, preferably 3 to 6 μm in length, can be used.

It is also possible to use fillers or reinforcing materials such as glass beads, mineral fibers, whiskers, alumina fibers, mica, quartz powders and wollastonite.

In addition, metal plates (e.g., alumina plates from Transmet Corp.), metal powders, metal fibers, metal cladding fillers, e.g. nickel coated glass fibers and additives which block electromagnetic waves are described herein. May be mixed with the molding composition used to prepare the adiabatic transport container. Alumina flakes (K 102, transmet) are particularly suitable for EMI (electromagnetic shielding) purposes. The composition may also be mixed with carbon fibers, carbon blacks, especially conductive black or nickel coated carbon fibers.

The molding compositions used to prepare the adiabatic transport containers according to the invention may also comprise other additives which are typically and commonly used in polycarbonate or SAN polymers or graft copolymers or mixtures thereof. Examples of this type of additive include dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve thermal stability, stabilizers to increase light stability and stabilizers to increase hydrolysis and chemical resistance, pyrolysis Inhibitors, in particular lubricants useful for making shaped articles. These other additives may be added at any stage of the production method, but an initial bonding step is preferred to take advantage of the stabilizing effect (or other specific effect) of the additive early. Thermal stabilizers or oxidation inhibitors are typically metal halides (chlorides, bromide or iodides) derived from Group 1 metals of the Periodic Table of Elements, for example Li Na, K or Cu.

Suitable stabilizers are conventional hindered phenols or vitamin E and / or compounds of similar structure. HALS stabilizers (sterically hindered amine light stabilizers), benzophenones, resorcinols, salicylates, benzotriazoles and other compounds are also suitable (for example Irganox®, Tinuvin®, For example, Tinuvin® 770 (HALS absorbent, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate) or Tinuvin® P (UV absorber (2H-benzo) Triazol-2-yl) -4-methylphenol), Topanol®). They are usually used in amounts of up to 2% by weight (based on the total mixture).

Suitable lubricants and release agents are stearic acid, stearyl alcohol, stearate and / or common higher fatty acids, their derivatives and fatty acid mixtures containing 12 to 30 carbon atoms. The amount of this additive is in the range of 0.05 to 1% by weight.

Other possible additives are silicone oils, oligomeric isobutylene or similar materials, typically added in amounts of 0.05 to 5% by weight. It is also possible to use pigments, dyes and color varnishes such as ultramarine blue, phthalocyanine, titanium dioxide, cadmium sulfide and perylenetetracarboxylic acid derivatives.

Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are typically used in amounts of 0.01 to 5% by weight, based on the total molding composition.

The thermoplastic molding compositions used to prepare the adiabatic transport containers according to the invention can be prepared by mixing the components by methods known per se. It may be advantageous to premix individual components. It is also possible to mix the components in the solution and remove the solvent.

Suitable organic solvents are, for example, mixtures of chlorobenzene, chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons such as toluene.

Removal of the solvent from the solvent mixture can be carried out in a diverging extruder.

Mixing the dry components can be carried out by any known method, for example. However, it is preferred that all the components are rolled, kneaded or extruded to mix, preferably at a temperature of 180 to 400 ° C. If desired, the components can be isolated in advance from the solution obtained during the polymerization or from the aqueous dispersion.

The components can then be weighed together or separately / continuously.

In one embodiment of the present invention, the adiabatic transport container can be prepared from the thermoplastic molding composition used according to the invention by known thermoplasticization processes. In particular, they can be produced by thermoforming, extrusion, injection molding, calendering, blow molding, compression molding, pressure sintering, or sintering, preferably by extrusion blow molding.

The adiabatic transport containers that can be prepared from the thermoplastic molding compositions described above in accordance with the present invention have scratch resistance, stability and chemical resistance and excellent dimensional accuracy. In addition, they are low in density and low in weight.

In one embodiment of the invention, the adiabatic transport containers according to the invention are multi-walled, in particular double-walled structures. The outer wall surface and preferably the inner wall surface comprise the molding composition according to the invention. The inner wall surface forms an empty space for storing the object to be transported. The intermediate space between the outer and inner walls is insulated. For this purpose, the intermediate space may be vacuum or filled with a gas, for example air or rare gas, liquid or adiabatic solids or foams.

In a preferred embodiment, the empty space is filled with a large filler, preferably a foam polymer. Thus, a sandwich structure is formed therefrom, wherein the layer of thermoplastic molding composition according to the invention is applied to both sides of the foam polymer. It is desirable to form all surface coatings with the thermoplastic molding compositions of the present invention. Insulated transport containers according to the present invention may take any useful shape. Thus, the container may have a sphere, cube, parallelepiped, cylinder or other useful shape. Containers are designed so that one or more sides can be opened for shipment and removal of objects to be transported or insulated. The container is a parallelepiped and preferably acts as a door or a cover that allows for thermal insulation of the interior with one side closed.

The temperature range that must be maintained inside the adiabatic transport container depends on the object to be stored. In one embodiment of the invention, the temperature range is -50 to 100 ° C, preferably -30 to 80 ° C. These temperature ranges are particularly the case where they are used for food transportation, wherein the food products are instant hot refrigerated foods. The adiabatic transport containers according to the invention are also suitable for storing and temperature-controlling liquids or beverages in the form of packaged drinks, such as cans or bottled drinks.

The adiabatic transport containers of the present invention may also be used for the transport of body organs that must be used for drug or transplantation or have to be transported from an organ donor to a suitable transplant site.

The internal capacity of a typical adiabatic transport container according to the invention is 1 to 500 l, preferably 10 to 50 l.

The transport container according to the invention is used for transporting a stored object between different places. According to one embodiment of the invention, the transport container is at least partly used externally (outdoor). This is the case, for example, in the case of food transport, which conventionally transports cooked food from the manufacturer to the consumer. The transport container according to the invention is exposed to external weathering for various times. Therefore, they must have good stability against weathering and this stability must be maintained even during exposure to permanent heat.

Other suitable uses of the insulating container according to the invention are known to those skilled in the art.

Transport containers used for the transport of organs, drugs or foodstuffs must be kept particularly clean and they often come into contact with chemicals or cleaning compositions. Insulated transport containers according to the invention have good resistance to chemicals, especially in environments which are further exposed to moisture (eg water vapor).

In particular, adiabatic transport containers made from molding compositions comprising polycarbonate as component C are high in heat resistance and can maintain heat resistance for a long time. At this time, the addition of polycarbonate as component C further improves the heat resistance and impact strength of the adiabatic transport container. These adiabatic transport containers also have a balanced ratio of toughness to stiffness, good dimensional stability, good aging heat resistance and good yellowing resistance when placed under heat stress and exposed to UV light.

The use of an adiabatic transport container is another embodiment of the present invention.

Adiabatic transport containers made from molding compositions comprising components A and B have a good surface finish and can be prepared without further surface treatment. The appearance of the finished surface of the adiabatic transport container can be modified to suit the shape of the rubber to give a glossy or matte surface finish. When exposed to weathering or UV light, the adiabatic transport container of the present invention exhibits little graying and / or yellowing, thus maintaining surface properties. Other advantages of the adiabatic transport container of the present invention are high weather resistance when exposed to UV light and thermal stress, excellent heat resistance, high yellowing resistance, and especially stress-cracking resistance when exposed to chemicals, electrostatic The prevention performance is excellent. This adiabatic transport container also has a high level of color fastness due to, for example, to some extent excellent yellowing resistance and crack resistance. Insulated transport containers made from the thermoplastic molding compositions used according to the present invention show no significant loss in toughness or impact strength after prolonged exposure to low temperatures or to heat, and this property is maintained even after exposure to UV light. Tensile strength is also maintained. In addition, the ratio of rigidity / toughness is balanced.

According to the present invention, it is possible to reuse the thermoplastic molding compositions previously used for producing adiabatic transport containers. The molding compositions used according to the invention have very good stability upon recycling due to their high color stability, weather resistance and aging resistance. At this time, the ratio of recycled molding composition may be high. For example, the previously used molding composition mixed with the molding composition used according to the invention in a 30% by weight pulverized form significantly changes the fluidity, the Vicat softening point and the impact strength of the molding composition and the adiabatic transport container produced therefrom. Don't let that happen. Similar results were obtained from the investigation of weatherability. Impact strength was also constant over time, even when reusable thermoplastic molding compositions were used (Lindenschmidt, Ruppmich, Hoven-Nievelstein, International Body Engineering Conference, Sept. 21-23, 1993, Detroit, Michigan, USA, Interior and Exterior Systems, see pages 61-64. Yellowing resistance was also maintained.

The following examples illustrate the invention in detail.

<Example 1>

Preparation of Particulate Graft Copolymer (A)

(a1) 16 parts of butyl acrylate and 0.4 parts of tricyclodecenyl acrylate in 150 parts of water were added 1 part of C ₁₂ -C ₁₈ paraffin sulfonate sodium salt, 0.3 parts of potassium persulfate, 0.3 parts of sodium hydrocarbon and 0.15 parts of sodium pyrophosphate. Was added and heated to 60 ° C. with stirring. Ten minutes after the initiation of the polymerization reaction, a mixture of 82 parts of butyl acrylate and 1.6 parts of tricyclodecenyl acrylate was added over 3 hours. After the addition of the monomer was terminated, the reaction proceeded further for 1 hour. The latex of the resulting crosslinked butyl acrylate polymer had a solids content of 40% by weight. Particle size (median) (weight average) was determined to be 76 nm. The particle size distribution was narrow. (Index Q = 0.29).

(a2) 150 parts of polybutyl acrylate latex obtained in (a1) are mixed with 40 parts of a mixture of styrene and acrylonitrile (weight ratio 75:25) and 60 parts of water, further 0.03 parts of potassium persulfate and lauroyl fur After adding 0.05 parts of oxide, it was heated to 65 ° C. for 4 hours with stirring. After the graft copolymerization was terminated, the polymer product was precipitated from the dispersion using calcium chloride solution at 95 ° C., washed with water and dried in a warm air stream. The graft degree of the graft copolymer was 35%.

<Example 2>

Preparation of Coarse-Granular Graft Copolymer (A)

(a1) 50 parts of water and 0.1 part of potassium persulfate were added to 2.5 parts of the latex prepared in step (a1) of Example 1. A mixture of 49 parts butyl acrylate and 1 part tricyclodecenyl acrylate and second, a solution of 0.5 parts C ₁₂ -C ₁₈ paraffin sulfonate sodium salt in 25 parts water was incorporated at 60 ° C. After the feed was completed, the polymerization was allowed to proceed for 2 hours. The latex of the resulting crosslinked butyl acrylate polymer had a solids content of 40% by weight. Particle size (median) (weight average of latex) was determined at 288 nm. The particle size distribution was narrow. (Q = 0.1).

(a2) 150 parts of the above latex is mixed with 40 parts of a mixture of styrene and acrylonitrile (weight ratio 75:25) and 110 parts of water, and further 0.03 parts of potassium persulfate and 0.05 parts of lauroyl peroxide are added. Heated at 65 ° C. for 4 hours with stirring. The polymer product obtained in the graft copolymerization was precipitated from the dispersion using a calcium chloride solution at 95 ° C., washed with water and dried in a warm air stream. The graft degree of the graft copolymer was determined to be 27%.

<Example 3>

Preparation of Coarse-Granular Graft Copolymer (A)

(a1) 16 parts of butyl acrylate and 0.4 part of tricyclodecenyl acrylate are added to 150 parts of water and 0.5 parts of sodium C ₁₂ -C ₁₈ paraffin sulfonate salt, 0.3 parts of potassium persulfate, 0.3 parts of sodium hydrocarbon and sodium pyrophosphate The mixture was heated to 60 ° C. while stirring incorporating 0.15 parts. Ten minutes after the initiation of the polymerization reaction, a mixture of 82 parts of butyl acrylate and 1.6 parts of tricyclodecenyl acrylate was added over 3 hours. After the addition of the monomer was terminated, the reaction proceeded further for 1 hour. The latex of the resulting crosslinked butyl acrylate polymer had a solids content of 40% by weight. Particle size (median) (weight average) was determined to be 216 nm. The particle size distribution was narrow. (Index Q = 0.29).

(a2) 150 parts of polybutyl acrylate latex obtained in (a1) were mixed with 20 parts of styrene and 60 parts of water, and further 0.03 parts of potassium persulfate and 0.05 parts of lauroyl peroxide were added, followed by 3 hours at 65 ° C. Heated while stirring. After the first step of the graft copolymer was terminated, the graft degree of the graft copolymer was 17%. This graft copolymer dispersion was polymerized without further additives with 20 parts of a mixture of styrene and acrylonitrile (weight ratio 75:25) for an additional 3 hours. After the graft copolymerization was complete, the product was precipitated from the dispersion using calcium chloride solution at 95 ° C., washed with water and dried in a warm air stream. The graft degree of the graft copolymer was 35% and the particle size (median) of the latex particles was 238 nm.

<Example 4>

Preparation of Coarse-Granular Graft Copolymer (A)

(a1) 50 parts of water and 0.1 part of potassium persulfate were added to 2.5 parts of the latex (component A) prepared in Example 3. A mixture of 49 parts butyl acrylate and 1 part tricyclodecenyl acrylate and second, a solution of 0.5 parts C ₁₂ -C ₁₈ paraffin sulfonate sodium salt in 25 parts water was incorporated at 60 ° C. After the feed was completed, the polymerization was allowed to proceed for 2 hours. The latex of the resulting crosslinked butyl acrylate polymer had a solids content of 40% by weight. The particle size (median) (weight average) of the latex was determined to be 410 nm. The particle size distribution was narrow. (Q = 0.1).

(a2) 150 parts of polybutyl acrylate latex obtained in (a1) were mixed with 20 parts of styrene and 60 parts of water, and further 0.03 parts of potassium persulfate and 0.05 parts of lauroyl peroxide were added, followed by 3 hours at 65 ° C. Heated while stirring. The dispersion obtained in this graft copolymerization was then further polymerized with 20 parts of a mixture of styrene and acrylonitrile (weight ratio 75:25) for 4 hours. The polymer product was precipitated from the dispersion using calcium chloride solution at 95 ° C., separated off, washed with water and dried in a warm air stream. The graft degree of the graft copolymer was determined to be 35% and the particle size (median) of the latex was 490 nm.

<Example 5>

Preparation of Coarse-Granular Graft Copolymer (A)

(a1) 98 parts of butyl acrylate and 2 parts of tricyclodecenyl acrylate were stirred for 3 hours in 154 parts of water at 65 ° C., and 0.5 parts of sodium dioctyl sulfosuccinate (70% strength) and potassium persulfate as emulsifiers The polymerization was carried out with addition. This gave a 40% strength dispersion. The particle size (median) of the latex was about 100 nm.

2.5 parts of this latex were mixed with 400 parts of water and 0.5 parts of potassium persulfate, and a mixture of 49 parts of butyl acrylate, 1 part of tricyclodecenyl acrylate and 0.38 part of emulsifier was added at 65 ° C. for 1 hour. For an additional 1 hour, a mixture of 49 parts butyl acrylate, 1 part tricyclodecenyl acrylate and 0.76 parts emulsifier was added. After addition of 1 part of potassium persulfate in 40 parts of water, a mixture of 196 parts of butyl acrylate, 4 parts of tricyclodecenyl acrylate and 1.52 parts of emulsifier was added dropwise over 2 hours. The polymerization of the polymer mixture was then further proceeded at 65 ° C. for 2 hours. This gave a dispersion having an average particle diameter of about 500 nm and an intensity of approximately 40%.

When only 100 parts were added instead of 300 parts of the monomers, the obtained latex had an average particle diameter of about 300 nm.

(a2) 465 parts of styrene and 200 parts of acrylonitrile, 2500 parts of polymer latex of (a1) (particle size (median) of 0.1, 0.3 and 0.5 μm, respectively), 2 parts of potassium sulfate, 1.33 parts of lauroyl peroxide and water The polymerization was carried out with stirring at 60 ° C. in the presence of 1005 parts. This gave a 40% strength dispersion, to which a 0.5% strength solution of calcium chloride was added to precipitate the solid product, washed with water and dried.

<Example 6>

Preparation of Copolymer (B)

The monomer mixture of styrene and acrylonitrile was polymerized in solution under conventional conditions. The resulting styrene-acrylonitrile copolymer had an acrylonitrile content of 35 wt% based on the copolymer and a viscosity number of 80 ml / g.

<Example 7>

Preparation of Copolymer (B)

The monomer mixture of styrene and acrylonitrile was polymerized in solution under conventional conditions. The resulting styrene-acrylonitrile copolymer had an acrylonitrile content of 35% by weight based on the copolymer and a viscosity number of 60 ml / g.

<Example 8>

Preparation of Copolymer (B)

The monomer mixture of styrene and acrylonitrile was polymerized in solution under conventional conditions. The resulting styrene / acrylonitrile copolymer had an acrylonitrile content of 30% by weight based on the copolymer and a viscosity number of 80 ml / g.

<Comparative Example 1>

ABS copolymer

A polybutadiene rubber styrene-acrylonitrile copolymer (component (A)) was used and grafted in a styrene-acrylonitrile copolymer matrix (component (B)) was used as a comparative polymer. The content of graft rubber was 23% by weight based on the total weight of the final finished polymer.

<Comparative Example 2>

HIPS copolymer

HIPS polymer (high impact polystyrene) comprising polystyrene containing 6.5% by weight of polybutadiene rubber was used as further molding composition for comparison. The humidification maximum value of mechanical humidification was -75 degreeC. MVI 200/5 is 4 ml / min.

<Comparative Example 3>

PP polymer

About 15% by weight of the block copolymer of PP and ethylene / propylene rubber (melt viscosity MVI 230 / 2.16 = 8 cm 2/10 min) was used as further molding composition for comparison. Humidification maximums are 0 ° C and -50 ° C.

Used in the injection molding process.

<Example 9>

As shown in Table 1 below, given amounts of suitable polymers (A) and (B) or comparative compositions were mixed in a screw extruder at 200-230 ° C. Test specimens were prepared from the resulting molding compositions by the method of DIN 16777. The molding composition and the three comparative molding compositions according to the invention were aged tested at 80 ° C. The transmission energy was then determined (values 0, 0.5, 1 and 2 years later, Nm according to ISO 6603-2). Low transmission energy means poor strength and rapid aging. E modulus was determined according to DIN 53 457 at 23 ° C and 50 ° C. Larger E modulus indicates better dimensional stability. HDT (heat distortion temperature) was also determined according to DIN / ISO 75 under 1.8 and 0.45 MPa.

The results are summarized in the table below.

Molding composition Examples of Ingredients part Transmission energy (Nm) according to ISO 6603-2 aging at 80 ° C E modulus according to DIN 53 457 (MPa) at specific temperatures HDT 0 0.5 years later 1 year later 2 years later 23 ℃ 50 ℃ 1.8 ℃ 0.45 ℃ I A: 1 25 A: 3 10 36 33 32 29 2300 B: 6 10 B: 7 55 Comparative Composition I Comparative Example 1 34 2 2 - 2700 2350 100 104 Comparative Composition II Comparative Example 2 15 1.2 0.8 - 1850 1500 78 89 Comparative Composition III Comparative Example 3 Do not check 1250 700 52 73

The results in the table show that the adiabatic transport containers made from the molding compositions according to the invention have much higher transmission energy after aging than the comparative compositions. That is, the container of the present invention is quite stable against aging and weathering. E modulus and HDT values show that the compositions of the present invention are substantially better in dimensional stability and heat resistance than comparative compositions.

Claims (10)

(a) As component A, 1 to 99% by weight of the granular emulsion polymer having a glass transition temperature of 0 ° C. or less and a particle size (median value) of 50 to 1000 nm, (b) component B, from 1 to 99% by weight of at least one amorphous or partially crystalline polymer, (c) 0 to 50% by weight of polycarbonate as component C, and (d) 0 to 50% by weight of component D, fibrous or particulate filler or mixtures thereof, wherein the composition ratio is based on 100% by weight of the total weight of components A and B and, if necessary, C and / or D For the production of adiabatic transport containers of thermoplastic molding compositions, different from ABS. The compound of claim 1 wherein component A is (a1) 1 to 99 wt% of the granular graft base A1 having a glass transition temperature of 0 ° C. or less, (a2) 40 to 100% by weight of a vinylaromatic monomer unit as component (A21), and (a22) As component A22, 60 weight% or less of ethylenically unsaturated monomeric units Prepared from 1 to 99% by weight of a graft component A2, comprising one or more graft shells, The graft copolymer having a particle size (median) of 50 to 1000 nm. The use according to claim 2, wherein the granular graft base A1 in the molding composition is an acrylate rubber, EP rubber, EPDM rubber or silicone rubber. The method of claim 3 wherein component A1 is (a11) 80 to 99.99% by weight of C ₁ -C ₈ -alkyl acrylate, as component A11, and (a12) Use as component A12, consisting of 0.01 to 20% by weight of at least one multifunctional crosslinking monomer. 5. The particle size distribution of claim 1, wherein the particle size distribution of component A has two maximums, and 60 to 90 wt%, based on the total weight of component A, has a particle size of 50 to 200 nm ( Median) and 10 to 40% by weight has a particle size (median) of 50 to 400 nm. Use according to any of the preceding claims, wherein the transport container is used for storing foodstuffs, in particular instant hot or refrigerated foods. The use according to any one of claims 1 to 5, wherein the transport container is used for containing the drug and / or body organs. 8. Use according to any of the preceding claims, wherein the transport container is used at least partially externally (outdoors). The thermal insulation transport container of the thermoplastic molding composition in any one of Claims 1-5. 10. A transport container according to claim 9, wherein the outer wall surface and the inner wall surface of the thermoplastic molding composition according to any one of claims 1 to 5 and between the outer wall surface and the inner wall surface preferably have a heat insulating intermediate layer comprising a foam polymer. .