CN117642464A

CN117642464A - Transparent acrylic polymer composition with improved tolerance to alcohols and fats

Info

Publication number: CN117642464A
Application number: CN202280049436.2A
Authority: CN
Inventors: R·卡洛夫; W·阿诺尔德; K·伯恩哈德
Original assignee: Roma Usa LLC; Roma Chemical Co ltd
Current assignee: Roma Usa LLC; Roma Chemical Co ltd
Priority date: 2021-07-16
Filing date: 2022-07-14
Publication date: 2024-03-01

Abstract

The present invention relates to transparent acrylic polymer compositions having improved resistance to alcohols, oils and fats. The polymer composition comprises an acrylic polymer a comprising at least one alkyl (meth) acrylate; an olefinic copolymer B comprising at least one olefinic monomer and at least one polar monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids; and a particulate heterophasic graft copolymer C comprising a core and at least one shell comprising at least one alkyl (meth) acrylate.

Description

Transparent acrylic polymer composition with improved tolerance to alcohols and fats

Technical Field

The present invention relates to transparent acrylic polymer compositions having improved resistance to alcohols, oils and fats. In particular, the composition has excellent resistance to water isopropanol mixtures commonly used for disinfection and sterilization of disposable medical devices. In addition, the composition has high transparency, low haze and excellent mechanical properties even after prolonged exposure to commercial disinfectants.

Accordingly, the compositions of the present invention are well suited for use in the manufacture of a variety of medical devices, such as intravenous and catheter attachments, blood processing devices, chest drainage devices, or respiratory ventilation devices. Furthermore, the compositions of the invention are suitable, for example, for the manufacture of household and horticultural articles, electronic parts, sanitary equipment and exterior and interior parts of motor vehicles.

The polymer composition of the present invention comprises an acrylic polymer a comprising at least one alkyl (meth) acrylate; an olefinic copolymer B, preferably a polyolefin graft copolymer, comprising at least one olefinic monomer and at least one polar monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids; and a particulate heterophasic graft copolymer C comprising a core and at least one shell comprising at least one alkyl (meth) acrylate.

Background

The medical grade acrylic polymer composition provides an excellent balance of optical and mechanical properties, can be sterilized using electron beam or gamma radiation and is compatible with biological materials. In addition, such compositions often have excellent thermoplasticity processability and can be advantageously used for injection molding. This allows them to be used in a variety of medical device applications, as well as in medical diagnostic devices. Typical applications of these materials include, inter alia, venous and catheter attachments, blood processing devices, chest drainage devices, respiratory ventilation devices, and the like.

Although commercially available medical grade acrylic polymer compositions already have good chemical resistance to materials such as alcohols, oils and fats, they tend to become cloudy and cracked upon prolonged exposure to water/alcohol mixtures. In addition, such prolonged exposure is detrimental to other mechanical properties of the composition. This behavior becomes particularly problematic when exposed for a long period to isopropanol-water mixtures commonly used today as disinfectants for medical devices, for example for several days. Polymer compositions for medical applications must maintain their mechanical and optical properties when stored for long periods of time at 23 ℃ in the presence of disinfectant solutions. In particular, haze or crack formation should be minimized.

WO 2020/126722 A1 describes transparent acrylic polymer compositions having good resistance to alcohols, oils and fats, wherein the composition comprises a copolymer comprising an alkyl (meth) acrylate, an aromatic vinyl monomer and an anhydride of an unsaturated carboxylic acid; copolymers containing aromatic vinyl monomers and vinyl cyanide monomers; and a particulate core-shell graft copolymer comprising a butadiene-based core as a rubber phase and a copolymer containing an alkyl (meth) acrylate as a hard phase. Even though the polymer composition of WO 2020/126722 A1 has shown good resistance to alcohols, oils and fats, it is still desirable to provide improved transparent polymer materials which show higher chemical resistance, i.e. good stress cracking resistance under more severe conditions, and enhanced mechanical strength, e.g. higher elongation at break, than the prior art.

WO 2008/148595 A1 describes a polymer blend comprising Methyl Methacrylate (MMA), a copolymer of styrene and maleic anhydride, and a styrene-acrylonitrile copolymer (SAN). The polymer blends have good optical and mechanical properties and improved stress crack resistance in the presence of pure isopropanol. WO 2008/148595 A1 does not mention stress crack resistance in the presence of isopropanol-water mixtures commonly used as disinfectants and optical property changes during prolonged exposure to said disinfectants.

U.S. Pat. No. 6,689,827 B1 describes a transparent impact-modified thermoplastic molding composition comprising a matrix of polymethyl methacrylate and SAN copolymer, a graft copolymer as impact modifier having a graft base based on butadiene and/or isoprene, and an additive consisting essentially of at least one 2, 6-disubstituted phenol.

WO 2001/46317 A1 describes a transparent impact-resistant thermoplastic molding composition which comprises a mixture of the following components: methyl methacrylate polymers, styrene/acrylonitrile copolymers and graft copolymers having a bimodal particle size distribution and comprising an elastomeric graft core having a glass transition temperature of less than 0 ℃ and one or more graft shells comprising a (meth) acrylate and optionally a vinylaromatic monomer and/or a crosslinking monomer.

JP H02-272050 A2 describes impact resistant polymer blends comprising: copolymers containing methyl methacrylate, maleic anhydride, styrene and C1-C4-alkyl acrylate; vinyl cyanide/aromatic vinyl copolymer or methyl methacrylate/C1-C4-alkyl acrylate, and copolymers made by grafting vinyl cyanide and an aromatic vinyl compound onto a rubbery polymer. The polymer blend of JP H02-272050 A2 has high heat resistance, impact resistance and transparency and is designed mainly for automotive applications.

US 9,834,645 B2 describes transparent thermoplastic resin compositions having a high resistance to cracking by environmental stress. The resin composition comprises a graft copolymer a, which is preferably obtained by grafting methyl methacrylate/acrylonitrile/styrene on butadiene rubber, and a methyl methacrylate/acrylonitrile/styrene copolymer B.

US 8,524,826 B2 describes transparent acrylic alloy compositions having high chemical resistance and impact resistance. The acrylic alloy comprises a high molecular weight acrylic copolymer, polyvinylidene fluoride, a core-shell impact modifier, and a melt flow processing aid.

Copolymers of olefinic monomers and maleic anhydride, such as polyolefins grafted with maleic anhydride and linear copolymers comprising olefinic monomer units and maleic anhydride units, and their use as compatibilizers in polymer compositions are well known in the art.

Document JP 2001279105A describes a white polymer composition for pharmaceutical packaging comprising two or more resins that are substantially incompatible with each other, for example selected from the group consisting of polyolefin, polystyrene, acrylic resins; and a compatibilizer, for example selected from maleated polypropylene/polystyrene graft copolymers or terpolymers of ethacrylic acid, ethylene and maleic anhydride. Document JP 63268754A describes thermoplastic resins, in particular with good chemical resistance, comprising a blend of polycarbonate and an acrylonitrile-styrene copolymer and a compatibilizer, which is a terpolymer comprising an olefin (e.g. ethylene, propylene), an unsaturated dicarboxylic anhydride (e.g. maleic anhydride) and an unsaturated carboxylic acid alkyl ester (e.g. ethyl acrylate).

For example, WO 2016/010893 A1 describes olefin-maleic anhydride copolymers, preferably alternating 1:1 copolymers of ethylene and maleic anhydride (e.g. from Vertellus Specialties inc.)Products) and their use as compatibilizers in engineering plastics, such as acrylonitrile-styrene-butadiene copolymer (ABS) compositions, polycarbonate compositions or polyamide compositions.

In addition, polyolefin maleic anhydride graft copolymers, such as polyethylene grafted maleic anhydride (PE-g-MAH), are commonly known compatibilizers. Their preparation is described, for example, in WO 95/16718 and WO 2002/093157. For example, US2011/0254204 describes the use of PE-g-MAH as matting agent in plastics materials. Maleic anhydride grafted polyolefins, such as polyethylene grafted with maleic anhydride (PE-g-MAH) and polypropylene grafted with maleic anhydride (PP-g-MAH), are often used in thermoplastic resins, such as polyethylene resins, to improve the compatibility of the polymer matrix with fillers or reinforcing fibers. In general, a wide variety of maleic anhydride grafted polyolefins are commercially available, for example from ChemturaProduct from Arkema +.>Product from BYK ∈>Product and preparation from Mitsubishi Chemical CorpAnd (5) a product.

It is an object of the present invention to provide novel polymer compositions which can be advantageously used for the production of transparent medical devices and which exhibit further improved stress crack resistance, improved mechanical strength and high transparency to alcohol-water based disinfectants, oils and fats even after prolonged exposure to alcohol or oil.

Disclosure of Invention

The present invention is based on the surprising discovery that the long term stress crack resistance of medical grade acrylic polymer compositions to isopropanol-water based disinfectants, oils and fats can be significantly improved by the addition of an olefinic copolymer comprising a polar monomer, in particular a graft copolymer, such as maleic anhydride grafted polyethylene (PE-g-MAH). Furthermore, it has surprisingly been found that transparent thermoplastic polymer compositions or molded parts made therefrom can be obtained if the acrylic polymer is combined with an olefinic copolymer, such as PE-g-MAH, in combination with a particulate heterophasic graft copolymer, such as a known particulate impact modifier. In particular, this finding is surprising because two-component blends of acrylic polymers and olefinic copolymers (e.g., polar grafted polyolefins) do not exhibit transparency. Thus, an advantageous way of incorporating polar olefinic copolymers into acrylic polymers by means of particulate heterophasic graft copolymers has been found. It appears that the particulate heterophasic graft copolymer advantageously affects the dispersion and compatibility of the olefinic copolymer in the acrylic polymer matrix. In this regard, the present invention relates to a synergistic combination of the three polymeric components.

The present invention relates to a polymer composition comprising, based on the weight of the polymer composition, the following components A, B and C:

40.0 to 94.5% by weight, preferably 50.0 to 84.0% by weight, of at least one acrylic polymer comprising at least one alkyl (meth) acrylate;

b.0.5 to 12.0% by weight, preferably 1.0 to 10.0% by weight, of at least one olefinic copolymer B comprising (preferably consisting of) at least one olefinic monomer and at least one polar monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids,

c.5.0 to 40.0 wt%, preferably 10.0 to 36.0 wt%, of at least one particulate heterophasic graft copolymer comprising (preferably consisting of) a core and at least one shell comprising at least one alkyl (meth) acrylate.

For the purposes of the present invention, the term "polymer or copolymer comprising or consisting of monomers" is understood to mean that the polymer or copolymer comprises or consists of said monomer units. As will be appreciated by those skilled in the art, the polymer is obtained by polymerization of the mentioned monomers, wherein at least one unsaturated group of the monomers is preferably free-radically polymerized. In the case where the polymer obtained after the polymerization contains unreacted monomers that are not incorporated into the polymer chain, this is referred to as residual monomers.

For the purposes of the present invention, the term "particulate heterophasic graft copolymer" relates to a crosslinked graft copolymer, which may have a core-shell structure comprising at least one core and at least one shell.

Preferably, the acrylic polymer a forms a polymer matrix and the particulate heterophasic graft copolymer C is dispersed in said polymer matrix. Preferably, the acrylic polymer a forms a polymer matrix with the optional polymer D, and the particulate heterophasic graft copolymer C is dispersed in the polymer matrix. For example, it is possible that the particulate heterophasic graft copolymer C as well as the olefinic copolymer B, for example a polyolefin graft copolymer, are dispersed in a polymer matrix, wherein the olefinic copolymer B and the particulate heterophasic graft copolymer C may form an aggregation.

Preferably, the polymer composition of the invention is a thermoplastic molding composition. Preferably, the polymer composition of the present invention is a transparent polymer composition. For the purposes of the present invention, a "transparent polymer composition" or "transparent molded article" means that the polymer composition or molded article exhibits a haze of equal to or less than 70%, preferably equal to or less than 50%, more preferably equal to or less than 40%, measured according to standard ASTM D1003 at 23 ℃ on injection molded specimens having a thickness of 3 mm.

The polymer compositions of the present invention can be prepared and processed in a relatively simple manner and are particularly suitable for the manufacture of articles, including articles having complex geometries, using injection molding.

Thus, in a further aspect, the present invention relates to a process for manufacturing a molded article from the polymer composition of the present invention, comprising an injection molding step of said composition. Preferably, the molded article made from the polymer composition of the present invention is a transparent molded article.

Still a further aspect of the invention relates to a molded article, in particular a medical molded article, comprising the polymer composition of the invention. Importantly, articles made from the polymer compositions of the present invention not only have excellent resistance to alcohols, alcohol water mixtures, oils and fats, but also exhibit a number of further advantageous properties such as:

excellent optical properties, in particular high transparency

High heat distortion resistance

Excellent mechanical properties, in particular high modulus of elasticity, high elongation at break and high Vicat softening temperature.

Finally, a further aspect of the invention relates to the use of the polymer composition of the invention in medical devices, preferably disposable medical devices, for example selected from the group consisting of medical diagnostic devices, venous and catheter attachments, blood treatment devices, chest drainage devices, respiratory ventilation devices, medical filter housings, permanent device housings, tubes, connectors, fittings and cuvettes. Furthermore, the present invention relates to a component of a household appliance, the polymer composition of the present invention; a component of a communication device; an electronic component; a component of a hobby device; a component of an exercise apparatus; a component of a gardening device; external and internal components of an automobile, a ship or an aircraft; a component for constructing a body component of an automobile, a ship or an aircraft; use in a component in a bathroom fixture.

Detailed Description

The polymer composition of the invention comprises at least one (in particular one or three, preferably exactly one) acrylic polymer a comprising at least one alkyl (meth) acrylate; at least one (in particular one or three, preferably exactly one) olefinic copolymer B, preferably at least one polyolefin graft copolymer, comprising at least one olefinic monomer and at least one polar monomer chosen from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids; and at least one (in particular one or three, preferably exactly one) particulate heterophasic graft copolymer C comprising a core and at least one shell comprising at least one alkyl (meth) acrylate; wherein the acrylic polymer A forms a polymer matrix and the particulate heterophasic graft copolymer C is dispersed in the polymer matrix.

Optionally, the polymer composition of the invention may comprise up to 50.0 wt.%, preferably 1.0 to 50.0 wt.%, more preferably 2.0 to 20.0 wt.%, still more preferably.0 to 10.0 wt.%, based on the total polymer composition, of at least one additional polymer component D, which is preferably selected from

A copolymer D1 comprising at least one monovinylaromatic component, preferably styrene; and at least one carboxylic anhydride component, preferably maleic anhydride; and

A copolymer D2 comprising at least one monovinylaromatic monomer, preferably styrene; and at least one vinyl cyanide monomer, preferably acrylonitrile.

Components A, B and C and optionally components D and E are described in more detail below.

Acrylic Polymer A

The polymer composition of the invention comprises 40.0 to 94.5 wt.%, preferably 50.0 to 84.0 wt.%, more preferably 55.0 to 80 wt.%, based on the total polymer composition, of at least one acrylic polymer a comprising at least one alkyl (meth) acrylate.

The term alkyl (meth) acrylate as used herein may represent a single alkyl (meth) acrylate or as a mixture of different alkyl (meth) acrylates. The term "(meth) acrylate" as used herein refers not only to methacrylates such as methyl methacrylate, ethyl methacrylate, and the like, but also to acrylates such as methyl acrylate, ethyl acrylate, and the like, and mixtures thereof.

Particularly preferred for the purposes of the present invention are C1-C18-alkyl (meth) acrylates, advantageously C1-C10-alkyl (meth) acrylates, in particular C1-C4-alkyl (meth) acrylates. Preferred alkyl methacrylates include Methyl Methacrylate (MMA), ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, isooctyl methacrylate and ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate and cycloalkyl methacrylates, such as cyclohexyl methacrylate, isobornyl methacrylate or ethylcyclohexyl methacrylate. Methyl methacrylate is particularly preferably used. Preferred alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, nonyl acrylate, decyl acrylate and ethylhexyl acrylate, and cycloalkyl acrylates such as cyclohexyl acrylate, isobornyl acrylate or ethylcyclohexyl acrylate.

In a preferred embodiment, the acrylic polymer a comprises 40.0 to 100.0 wt%, preferably 45.0 to 100.0 wt%, more preferably 55.0 to 99.5 wt%, based on the total acrylic polymer a, of at least one alkyl methacrylate monomer (or repeating unit) having 1 to 20, preferably 1 to 12, more preferably 1 to 8, most preferably 1 to 4 carbon atoms in the alkyl group. Alkyl (meth) acrylates.

In a particularly preferred embodiment, the acrylic polymer a comprises from 50.0 to 100.0% by weight, preferably from 65.0 to 100.0% by weight, more preferably from 70.0 to 100.0% by weight, of methyl methacrylate MMA.

Suitable acrylic polymers a may comprise (preferably consist of) monomers such as:

50.0 to 100.0 wt.%, preferably 65 to 99 wt.% of at least one alkyl (meth) acrylate, preferably methyl methacrylate;

0.0 to 20.0 wt%, preferably 0.1 to 4 wt% of at least one alkyl (meth) acrylate other than Methyl Methacrylate (MMA), preferably selected from C1-C10 alkyl acrylates, more preferably selected from methyl acrylate, ethyl acrylate and butyl methacrylate;

0.0 to 40% by weight, preferably 5.0 to 30.0% by weight, of at least one vinylaromatic monomer, preferably styrene; and

0.0 to 20 wt%, preferably 5.0 to 20.0 wt% of one or more other copolymerizable monomers, such as at least one unsaturated carboxylic acid or anhydride of an unsaturated carboxylic acid, or acrylonitrile, preferably at least one anhydride of an unsaturated carboxylic acid, more preferably selected from the group consisting of acrylic anhydride, methacrylic anhydride, maleic anhydride, 1, 2-cyclohexanedicarboxylic anhydride, itaconic anhydride, and even more preferably maleic anhydride;

wherein all amounts are given based on the total weight of acrylic polymer a.

The inventors have further found that the composition of the invention has particularly advantageous environmental chemical stress resistance and optical properties if the acrylic polymer a is a copolymer of the following monomers:

48.0 to 90.0% by weight, preferably 63.0 to 81.0% by weight, of at least one alkyl (meth) acrylate, preferably at least one C1-C10-alkyl (meth) acrylate, more preferably methyl methacrylate;

8.0 to 35.0% by weight, preferably 12.0 to 22.0% by weight, of at least one monovinylaromatic monomer; and

2.0 to 17.0% by weight, preferably 7.0 to 15.0% by weight, of at least one anhydride of an unsaturated carboxylic acid, preferably maleic anhydride;

wherein all amounts are based on the total weight of acrylic polymer a.

Preferably, the acrylic polymer a is obtained by copolymerization of the monomers mentioned. The acrylic polymer a is therefore preferably a copolymer comprising or consisting of the mentioned monomers in the polymer chain, preferably in a nearly random distribution. More preferably, the acrylic polymer a is not a graft polymer.

Examples of suitable monovinylaromatic monomers include styrene; mono-or polyalkylstyrenes, such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene; styrene derivatives having functional groups such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, vinylmethyl benzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene and divinylbenzene; 3-phenylpropene, 4-phenylbutene and alpha-methylstyrene. Of these, styrene is most preferable.

The choice of unsaturated carboxylic acid or anhydride of unsaturated carboxylic acid in the acrylic polymer a is not particularly limited. The carboxylic anhydride may advantageously be selected from methacrylic acid, acrylic anhydride, methacrylic anhydride, maleic acid, 1, 2-cyclohexanedicarboxylic anhydride, cyclohexylmaleimide and itaconic anhydride, with maleic anhydride being particularly preferred.

Suitable acrylic polymers a may comprise (preferably consist of) for example:

50.0 to 90.0 wt%, preferably 65 to 90 wt%, more preferably 70.0 to 83.0 wt% of alkyl (meth) acrylate;

from 5.0 to 30 wt%, preferably from 5.0 to 20.0 wt%, more preferably from 7 to 15 wt% of styrene; and

from 5.0% to 20.0% by weight, preferably from 5.0% to 15.0% by weight, more preferably from 7% to 10% by weight, of maleic anhydride, where all amounts are given based on the total weight of the acrylic polymer a.

In a particularly preferred embodiment of the invention, the acrylic polymer A is a (meth) acrylate-based (co) polymer, which is a copolymer of MMA, styrene and maleic anhydride. Such suitable acrylic polymers A are described, for example, in WO 2020/126722 A1.

Thus, such an acrylic polymer a may comprise (preferably consist of) for example:

50.0 to 90.0 wt.%, preferably 70.0 to 80.0 wt.% MMA,

10.0 to 20.0 wt%, preferably 12.0 to 18.0 wt% of styrene and

From 5.0% to 15.0% by weight, preferably from 8.0% to 12.0% by weight, of maleic anhydride, where all amounts are given based on the total weight of acrylic polymer a.

In order to achieve optimal rheological properties of the polymer composition, the weight average molecular weight Mw of the polymer A is preferably adjusted to 60 to 280 g/mol, more preferably 120 000 to 240 g/mol. The determination of Mw can advantageously be carried out by means of Gel Permeation Chromatography (GPC), for example using PMMA as calibration standard and Tetrahydrofuran (THF) containing 0.2% by volume of trifluoroacetic acid (TFA) as eluent. Instead of using calibration standards, scatter detectors can also be used (see H.F.Mark et al, encyclopaedia of Polymer Science and Engineering, 2 nd edition, volume 10, page 1 and subsequent pages, J.Wiley, 1989). One skilled in the art can readily select an appropriate GPC column. Such columns are available, for example, from PSS Standards Service GmbH company (Mainz, germany) as columns of the PSS SDV series. As one skilled in the art will readily recognize, a combination of several GPC columns may also be used.

Methods suitable for preparing acrylic polymers a are known in the art. For example, DE 1231013B discloses a process for preparing copolymers by bulk polymerization of 1 to 50% by weight of alkylstyrene and 99 to 50% by weight of alkyl methacrylate together with lower amounts of Maleic Anhydride (MAH) and/or methacrylic acid.

US 3,336,267A describes a process for preparing a copolymer comprising from 5 to 95 mol% of a vinylaromatic material, from 5 to 40 mol% of an unsaturated cyclic anhydride and from 0 to 90 mol% of an alkyl (meth) acrylate. Here, the above-mentioned monomer mixture is continuously polymerized together with an inert solvent, and the polymer is continuously discharged from the polymerization mixture.

EP 264590A discloses a process for preparing molding compounds from monomer mixtures comprising methyl methacrylate, vinylaromatic substances, maleic anhydride and optionally lower alkyl acrylates in the presence of non-polymerizable organic solvents and at temperatures in the range from 75 to 150 ℃.

In another preferred embodiment, the acrylic polymer A is a thermoplastic (meth) acrylate polymer comprising (preferably consisting of)

50.0 to 100.0 wt.%, preferably 60.0 to 100.0 wt.%, particularly preferably 75.0 to 100.0 wt.%, in particular 85.0 to 99.5 wt.% of at least one alkyl methacrylate monomer (or repeating unit) having 1 to 20, preferably 1 to 12, more preferably 1 to 8, in particular 1 to 4 carbon atoms in the alkyl group;

0.0 to 40.0 wt.%, preferably 0.0 to 25.0 wt.%, in particular 0.1 to 15.0 wt.% of at least one alkyl acrylate monomer (or repeating unit) having 1 to 20, preferably 1 to 12, advantageously 1 to 8, in particular 1 to 4 carbon atoms in the alkyl group; and

0.0 to 30.0 wt%, preferably 0.0 to 10 wt%, more preferably 0.0 to 8.0 wt% of at least one monovinylaromatic monomer (or repeating unit), such as styrene;

wherein all amounts are based on the total weight of acrylic polymer a.

In particular, the acrylic polymer a is a thermoplastic (meth) acrylate polymer comprising, based on its total weight, 50.0 to 100.0 wt%, preferably 70.0 to 100.0 wt%, more preferably 95.0 to 100.0 wt% MMA, and 0.0 to 20.0 wt%, preferably 0.0 to 10.0 wt%, more preferably 0.0 to 5.0 wt% of a non-MMA alkyl (meth) acrylate. The non-MMA alkyl (meth) acrylate may be selected from essentially any of the preferred alkyl methacrylates and alkyl acrylates mentioned above. For example, the alkyl (meth) acrylate may consist of MMA and ethyl acrylate or of MMA and butyl methacrylate. In a further preferred embodiment, the alkyl (meth) acrylate consists only of MMA.

Olefinic copolymer B

The polymer composition according to the invention comprises, preferably consists of, 0.5 to 12.0 wt.%, preferably 1.0 to 10.0 wt.%, more preferably 2.0 to 8.0 wt.%, based on the total polymer composition, of at least one olefinic copolymer B, preferably at least one polyolefin graft copolymer, comprising at least one olefinic monomer and at least one polar monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids.

The olefinic copolymer B may be chosen from branched or grafted copolymers, for example polyolefins grafted with at least one polar monomer as defined, or from linear copolymers consisting of a single main chain comprising at least one olefinic monomer and at least one said polar monomer, for example statistical, alternating, gradient and block copolymers.

For example, alternating copolymers of ethylene and maleic anhydride are known and can be used asE-400 was purchased from Vertellus Specialties Inc., E400. For example, terpolymers of ethylene, acrylic acid esters and maleic anhydride, for example random terpolymers, are known and can be used as +.>Purchased from SK Functional Polymer.

In a preferred embodiment, the at least one olefinic copolymer B is at least one polyolefin graft copolymer comprising (preferably consisting of) at least one polyolefin base polymer (also referred to as polyolefin backbone polymer) grafted with at least one polar monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids. More preferably, the at least one polar monomer is chosen from anhydrides of unsaturated carboxylic acids. Most preferably, the at least one polar monomer is Maleic Anhydride (MAH).

In a preferred embodiment, the olefinic copolymer B, preferably the polyolefin graft copolymer, comprises from 0.5 to 3.0 wt%, preferably from 0.7 to 2.5 wt%, still more preferably from 1.0 to 2.0 wt% of the at least one polar monomer, based on the weight of the olefinic copolymer B.

In a preferred embodiment, the weight ratio of olefinic copolymer B to particulate graft copolymer C in the polymer composition of the present invention is less than or equal to 0.4 wt.%/wt.%, preferably less than or equal to 0.3 wt.%/wt.%, more preferably less than or equal to 0.2 wt.%/wt.%. Generally, the weight ratio of olefinic copolymer B to particulate graft copolymer C in the polymer composition is greater than 0.05 wt.%/wt.%, preferably greater than 0.1 wt.%/wt.%, more preferably greater than 0.13 wt.%/wt.%. Preferably, the particulate graft copolymer C here has a volume average particle diameter of from 40nm to 600 nm.

In a preferred embodiment, the polyolefin graft copolymer comprises at least one base polyolefin polymer grafted with from 0.5 to 3.0 wt%, preferably from 0.7 to 2.5 wt%, still more preferably from 1.0 to 2.0 wt%, based on the weight of the graft copolymer, of said at least one polar monomer selected from the group consisting of unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids, preferably with at least one anhydride of unsaturated carboxylic acids, more preferably with maleic anhydride.

For the purposes of the present invention, olefinic monomers are understood to be radically polymerizable hydrocarbon monomers having at least one carbon-carbon double bond, preferably at least one carbon-carbon double bond in the primary or alpha-position, and having 2 or more carbon atoms, preferably from 2 to 20 carbon atoms, more preferably from 2 to 8 carbon atoms.

For the purposes of the present invention, polyolefin means a homo-or copolymer comprising at least one olefinic monomer, preferably at least one alpha-olefinic monomer, having at least one carbon-carbon double bond and having 2 or more carbon atoms, preferably from 2 to 20 carbon atoms, more preferably from 2 to 8 carbon atoms. Suitable polyolefins may be selected from:

homopolymers and copolymers of alpha-olefins having 2 or more carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, such as polyethylene, high Density Polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium Density Polyethylene (MDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), polypropylene, 1-polybutene, 1-polymethylpentene, ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-1-decene copolymers, propylene-1-butene copolymers, propylene-4-methyl-1-pentene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers and propylene-1-decene copolymers, propylene/isobutylene copolymers or mixtures thereof;

Copolymers of alpha-olefins having 2 or more carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, with cyclic olefins (e.g. cyclopentene or norbornene);

copolymers of alpha-olefins having 2 or more carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, with dienes (e.g. butadiene, isoprene, hexadiene, dicyclopentadiene), such as ethylene-propylene-diene terpolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers;

copolymers of alpha-olefins having 2 or more carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, with other vinyl monomers, such as styrene, (meth) acrylic monomers or vinyl acetate, for example ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate (EVA) copolymers.

In a preferred embodiment, the olefinic copolymer B is a polyolefin graft copolymer, wherein the base polymer of the polyolefin graft copolymer is selected from polyethylene (preferably HDPE, HDPE-HMW, HDPE-UHMW, MDPE, LDPE, LLDPE); polypropylene; ethylene copolymers (preferably ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers); propylene copolymers (preferably propylene-1-hexene copolymers, propylene-1-octene copolymers and propylene-1-decene copolymers); and polystyrene (preferably sPS). More preferably, the polyolefin base polymer of the graft copolymer B is selected from polyethylene and polypropylene, more preferably from polyethylene, such as HDPE, HDPE-HMW, HDPE-UHMW, MDPE, LDPE, LLDPE.

The polyolefin base polymer (or also referred to as polyolefin backbone polymer) of the polyolefin graft copolymer is grafted with at least one polar monomer selected from the group consisting of unsaturated carboxylic acids, esters of unsaturated carboxylic acids, and anhydrides of unsaturated carboxylic acids by a generally known method.

Typically, unsaturated carboxylic acids and their respective anhydrides include unsaturated monocarboxylic acids (e.g., acrylic acid, methacrylic acid, α -ethacrylic acid or cyanoacrylate), unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, butenylsuccinic acid) and substituted derivatives thereof, wherein the substituted derivatives, preferably mono-or di-substituted derivatives, may be C1-C3 alkyl substituted; C6-C12-aryl-substituted or halogen-substituted derivatives (e.g., 2-methyl-maleic acid, 2-ethyl-maleic acid, 2-phenyl-maleic acid, 2, 3-dimethyl-maleic acid, chloromaleic acid).

Specific preferred examples of the unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, α -ethacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, chloromaleic acid, and its anhydride. More preferred examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and anhydrides thereof. Of these acids and anhydrides, maleic acid and maleic anhydride are most preferred.

The grafting may also be carried out with esters of the monocarboxylic or dicarboxylic acids mentioned, for example with C1-C12-alcohols, such as methanol, ethanol, propanol, butanol, isobutanol. Preferably, the esters of unsaturated carboxylic acids may be selected from esters of acrylic acid and methacrylic acid, such as methyl methacrylate, ethyl acrylate, glycidyl methacrylate, butyl acrylate, hydroxyethyl acrylate.

In a preferred embodiment, the olefinic copolymer B is a polyolefin graft copolymer and comprises (preferably consists of) at least one polyolefin base polymer grafted with at least one (preferably exactly one) polar monomer selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, glycidyl methacrylate, butyl acrylate and hydroxyethyl acrylate; more preferably with at least one (preferably exactly one) polar monomer selected from the group consisting of maleic acid, maleic Anhydride (MAH), acrylic Acid (AA), methacrylic acid (MAA), methyl Methacrylate (MMA), ethyl Acrylate (EA), butyl Acrylate (BA) and hydroxyethyl acrylate, most preferably with Maleic Anhydride (MAH).

The polyolefin graft copolymer may also be grafted with two or more polar monomers as described above selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids. In addition, the polyolefin graft copolymer may be grafted with at least one polar monomer as described above in combination with at least one vinyl aromatic monomer such as styrene.

Examples of suitable polyolefin graft copolymers include those available from BYK/GermanyProducts, and +.about. Mitsubishi Chemical Corp available from>Products, in particular PE-type and PP-type +.>And (5) a product.

In general, the olefinic copolymers B, preferably polyolefin graft copolymers, used in the present invention have a Melt Flow Rate (MFR) of from 0.5 to 50g/10min as measured at 190℃under a load of 2.16kg (DIN ISO 1133).

The olefinic copolymers B can be prepared by generally known polymerization techniques, such as free radical polymerization, for example by emulsion, solution or bulk polymerization. The polyolefin graft copolymer may be prepared by graft copolymerizing a polyolefin with an unsaturated carboxylic acid, an ester or an anhydride thereof using various conventionally known methods. The manufacturing method may for example be carried out by solid phase synthesis, as described for example in WO 2002/093157. In addition, other known methods are also possible, such as melt, solvent or suspension methods. For example, the melt method includes melting a polyolefin using an extruder or the like, and then adding a monomer to be grafted to the melted polyolefin to copolymerize the polyolefin therewith.

Particulate heterophasic graft copolymer C

The polymer composition according to the invention comprises 5.0 to 40.0 wt.%, preferably 10.0 to 36.0 wt.%, more preferably 18.0 to 35.0 wt.%, based on the total polymer composition, of at least one particulate heterophasic graft copolymer C comprising a core and at least one shell comprising at least one alkyl (meth) acrylate. Typically, the particulate heterophasic graft copolymer C comprises an elastomeric core or at least one elastomeric intermediate layer.

For the purposes of the present invention, an elastomeric core or elastomeric layer refers to a core or layer composed of a polymer or polymer composition having a glass transition temperature Tg <20 ℃, preferably Tg <0 ℃.

"particulate heterophasic graft copolymer" refers herein to a crosslinked graft copolymer, which may have a core-shell structure comprising at least one core and one or more shells.

The term alkyl (meth) acrylate "as used in relation to the graft copolymer C; "monovinylaromatic vinyl monomer"; and "vinyl cyanide monomer" has the same meaning as described above for polymers a and D.

Preferably, the particulate heterophasic graft copolymer C is dispersed in a polymer matrix formed by the acrylic polymer a and optionally the additional polymer component D. In some embodiments, the graft copolymer C may be dispersed almost uniformly in the polymer matrix in the form of non-aggregated single particles. However, in other embodiments, the particulate graft copolymer C may form aggregates, wherein the aggregates are nearly uniformly dispersed in the polymer matrix.

Preferably, the particulate heterophasic graft copolymer C has a core-shell structure or a core-shell structure.

In a preferred embodiment, the particulate heterophasic graft copolymer C has a volume average particle diameter of 20 to 1000nm, preferably 50 to 500nm, more preferably 100nm to 400nm, as determined by photon correlation spectroscopy in water at 23 ℃ according to DIN ISO 13321 (2017). For example, commercially available instruments such as a laser diffraction particle size analyzer from Beckman Coulter inc (e.g., LS13 320 particle size analyzer from Beckman Coulter) may be used for this purpose.

The particulate heterophasic graft copolymer C may be selected from known particulate impact modifiers, such as impact modifiers based on polybutadiene cores or impact modifiers based on crosslinked poly (meth) acrylate cores. The particulate heterophasic graft copolymer C exhibits a heterophasic structure comprising a core and at least one, preferably one or two shells. Typically, the particulate heterophasic graft copolymer C exhibits a rigid shell comprising (preferably consisting of) at least one alkyl (meth) acrylate and optionally other comonomers, such as monovinylaromatic monomers (e.g. styrene) and/or vinyl cyanide monomers (e.g. acrylonitrile). Preferably, the rigid shell exhibits the same or similar refractive index as the polymer matrix formed by acrylic polymer a and optional additional polymer component D (e.g., D1 described below).

Preferably, the heterophasic graft copolymer C comprises an elastomeric core or one or more elastomeric inner shells, which represent the rubber phase. Typically, the elastomeric or rubber phase exhibits a glass transition temperature Tg <20 ℃, preferably Tg <0 ℃, and is based on a crosslinked polymer, for example comprising a conjugated diene or a crosslinked alkyl (meth) acrylate, preferably a crosslinked C1-C10 alkyl (meth) acrylate.

In particular, the conjugated diene in the core of C contains at least two, preferably exactly two conjugated carbon-carbon double bonds, and preferably a total of 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms. For example, suitable conjugated dienes may be selected from the group consisting of 1, 3-butadiene, 2-methyl-1, 3-butadiene, 2-ethyl-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 3-butyl-1, 3-octadiene, and mixtures thereof. Preferably, the conjugated diene monomer is 1, 3-butadiene or isoprene, more preferably 1, 3-butadiene.

In a preferred embodiment, the particulate heterophasic graft copolymer C has a butadiene-based elastomer core, wherein butadiene may be copolymerized with styrene and/or butyl acrylate. Preferably, the graft copolymer C is a particulate core-shell graft copolymer comprising (preferably consisting of) a butadiene-based core as the rubber phase and a rigid shell of a polymer comprising at least one alkyl (meth) acrylate, optionally at least one monovinylaromatic monomer (e.g. styrene) and optionally at least one vinylcyanide monomer (e.g. acrylonitrile). Preferably, the butadiene-based core comprises at least 65.0 wt%, preferably at least 75.0 wt%, more preferably at least 80.0 wt% polybutadiene, and optionally 0 to 20 wt% of one or more additional monomers preferably selected from styrene and/or butyl acrylate, based on the weight of the butadiene-based core.

In a particularly preferred embodiment, the particulate heterophasic graft copolymer C is substantially free of vinyl cyanide monomers.

Generally, the vinyl cyanide monomer as defined above is present in the particulate core-shell graft copolymer C in an amount of not more than 5.0 wt%, preferably not more than 2.0 wt%, more preferably not more than 0.5 wt%, based on the weight of the graft copolymer C.

In a preferred embodiment, the graft copolymer C comprises a butadiene-based elastomer core as the rubber phase and a copolymer comprising alkyl (meth) acrylate and optionally aromatic vinyl monomers as the hard shell. Preferably, the particulate heterophasic graft copolymer C comprises (preferably consists of) the following:

a butadiene-based core comprising

At least 65.0 wt%, preferably at least 75.0 wt%, more preferably at least 80.0 wt%, polybutadiene based on the weight of the butadiene-based core; and

a housing, which comprises

50.0 to 100.0 wt%, preferably 60.0 to 100.0 wt%, more preferably 65.0 to 100.0 wt%, based on the weight of the housing, of at least one alkyl (meth) acrylate, such as methyl methacrylate, and

from 0.0% to 50.0% by weight, preferably from 0.0% to 40.0% by weight, more preferably from 0.0% to 35.0% by weight, based on the weight of the shell, of at least one aromatic vinyl monomer, for example styrene.

In a preferred embodiment of the invention, the particulate heterophasic graft copolymer C comprises a polybutadiene core, optionally comprising further copolymerizable monomers, such as up to 2 wt.% of butyl acrylate, based on the total weight of the particulate heterophasic graft copolymer; grafted with 17 to 22 parts by weight of MMA, 0 to 7 parts by weight of styrene and 0 to 3 parts by weight of ethyl acrylate and/or butyl acrylate. Typically, the weight ratio of polybutadiene to other monomers is about 1:1 to about 4:1, respectively. Such graft copolymers are described, for example, in U.S. Pat. No. 4,085,166A. The corresponding materials can be prepared by essentially any known polymerization method, for example by free radical polymerization using initiators and molecular weight regulators customary in the art.

According to another preferred embodiment, the particulate heterophasic graft copolymer C is selected from the group of graft copolymers based on an elastomer crosslinked alkyl (meth) acrylate core (hereinafter also referred to as heterophasic alkyl (meth) acrylate graft copolymer).

Preferably, such heterophasic alkyl (meth) acrylate graft copolymers are obtained by emulsion polymerization of alkyl (meth) acrylate monomers and optionally other copolymerizable monomers, preferably by sequential emulsion polymerization, wherein the resulting emulsion polymer (graft copolymer C) has a heterophasic structure comprising at least one core and at least one, preferably one or two shells.

For example, the heterophasic alkyl (meth) acrylate graft polymer C may be formed from crosslinked particles having a core-shell structure or a core-shell structure, having a volume average particle diameter of 20nm to 500nm, preferably 50nm to 450nm, more preferably 100nm to 400nm, most preferably 150nm to 350nm, as determined by photon correlation spectroscopy in water at 23 ℃ according to DIN ISO 13321 (2017).

In a preferred embodiment, the heterophasic alkyl (meth) acrylate graft copolymer comprises a soft elastomeric core and a hard non-elastomeric outer phase (core-shell graft copolymer) which is typically made via graft emulsion polymerization in the presence of the core.

In another preferred embodiment, the heterophasic alkyl (meth) acrylate graft copolymer comprises a hard non-elastomeric core; a soft elastomeric intermediate shell, typically made via graft emulsion polymerization in the presence of a core, and a hard non-elastomeric shell (core-shell graft copolymer), typically made via graft emulsion polymerization in the presence of intermediate core-shell particles. Preferably, the particulate heterophasic graft copolymer C consists of a hard core (which consists for example of crosslinked methyl methacrylate), a soft intermediate shell (which consists for example of crosslinked C1-C10 alkyl acrylate, preferably n-butyl acrylate); and a hard shell (which is composed of, for example, non-crosslinked methyl methacrylate). Typically, the core-shell graft copolymers are prepared as described in EP 1,331166 B1, WO 02/20634 or EP 0 522 351.

Preferably, the shell of the particulate heterophasic graft copolymer C is a hard phase comprising at least 80% by weight, based on the shell, of at least one C1-C6 alkyl methacrylate, preferably at least 80% by weight, based on the shell, of methyl methacrylate.

Preferably, at least 50 wt%, more preferably at least 55 wt%, more preferably at least 80 wt%, of the outer layer is covalently bonded to the soft phase, i.e. the soft core of the core-shell graft copolymer or the intermediate shell of the core-shell graft copolymer, based on the total weight of the particulate heterophasic graft copolymer C. In general, the amount of covalently bonded outer layer (graft polymer) (or also referred to as the degree of grafting) is measured as the amount insoluble in acetone.

Preferably, the particulate heterophasic graft copolymer C comprises at least 60 wt%, preferably at least 75 wt%, based on the graft copolymer C, of at least one C1-C20 alkyl (meth) acrylate, more preferably methyl methacrylate and/or n-butyl acrylate.

Typically, the (meth) acrylic acid esters include C1-C10 alkyl (meth) acrylates, C2-C20 alkenyl (meth) acrylates, C6-C20 aryl (meth) acrylates, C6-C20 aralkyl (meth) acrylates, C1-C10 hydroxyalkyl (meth) acrylates, glycol di (meth) acrylates, and multifunctional (meth) acrylates.

Preferably, the particulate heterophasic graft copolymer C comprises at least one C1-C10 alkyl methacrylate, preferably selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, isooctyl methacrylate and ethylhexyl methacrylate, and cycloalkyl methacrylates, such as cyclohexyl methacrylate.

Preferably, the particulate heterophasic graft copolymer C comprises at least one C1-C10 alkyl acrylate, preferably selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate and ethylhexyl acrylate, and cycloalkyl acrylates, such as cyclohexyl acrylate.

In a preferred embodiment, the particulate heterophasic graft copolymer C is selected from graft copolymers based on an elastomer crosslinked alkyl (meth) acrylate core and comprises (preferably consists of):

At least 40% by weight, preferably 40 to 70% by weight, of at least one C1-C10-preferably C1-C6-alkyl methacrylate, preferably methyl methacrylate;

from 5 to 45% by weight, preferably from 20 to 45% by weight, preferably from 25 to 42% by weight, of at least one C1-C10-alkyl acrylate, preferably C1-C6-alkyl acrylate, preferably selected from ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate and butyl methacrylate, more preferably C1-C10-alkyl acrylate comprises n-butyl acrylate;

0 to 2 wt%, preferably 0.1 to 2 wt%, more preferably 0.5 to 1 wt% of at least one crosslinking monomer, preferably a multifunctional (meth) acrylate and/or allyl (meth) acrylate; and

from 0 to 15% by weight, preferably from 0 to 10% by weight, more preferably from 0.5 to 5% by weight, of optional additional monomers, preferably different from the monomers mentioned above, for example vinylaromatic monomers, such as styrene, benzyl methacrylate.

These amounts are given based on the total mass of the monomers.

Preferably, the particulate heterophasic graft copolymer C comprises vinylaromatic monomers, for example styrene and/or C7-C20 aralkyl (meth) acrylates, such as benzyl methacrylate, to adjust the difference in the reflection index (reflection index) of the hard and soft phases. Vinyl aromatic monomers which can be used are styrene, substituted styrenes having an alkyl substituent in the side chain, for example, α -methylstyrene and α -ethylstyrene, substituted styrenes having an alkyl substituent on the ring, for example, vinyltoluene and p-methylstyrene, and halogenated styrenes, for example, monochlorostyrene, dichlorostyrene, tribromostyrene and tetrabromostyrene.

Typically, the crosslinking monomer has two or more polymerizable double bonds in the molecule. The crosslinking monomer may be selected from difunctional (meth) acrylates, trifunctional or multifunctional (meth) acrylates and other known crosslinking agents such as allyl methacrylate, allyl acrylate and divinylbenzene.

For example, difunctional (meth) acrylates are diesters of (meth) acrylic acid and polyfunctional alcohols, such as, for example, the di (meth) acrylates of propylene glycol, butylene glycol, hexylene glycol, octylene glycol, nonylene glycol, decylene glycol, eicosane glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, decadiethylene glycol, tetradecylene glycol, propylene glycol, dipropylene glycol, tetradecylene glycol. For example, trifunctional or multifunctional (meth) acrylates are triesters or polyesters of (meth) acrylic acid and polyfunctional alcohols, such as trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. Suitable crosslinking monomers are described, for example, in WO 02/20634 and EP 0 522 351.

Preferably, the particulate heterophasic graft copolymer C comprises at least one crosslinking monomer selected from ethylene glycol methacrylate, 1, 4-butanediol dimethacrylate, divinylbenzene and allyl (meth) acrylate. More preferably, the crosslinking monomer is allyl methacrylate.

In a preferred embodiment, the particulate heterophasic graft copolymer C is a core-shell graft copolymer comprising (preferably consisting of) the following:

C-A2) from 5 to 40% by weight, based on the total graft copolymer, of a hard, non-elastomeric core C-A2 having a glass transition temperature Tg of above 50℃which consists of:

C-A2.1) from 80 to 100% by weight, based on CA2, of at least one C1-C6-alkyl methacrylate, preferably methyl methacrylate;

c-a 2.2) 0 to 20% by weight, based on C-A2, of at least one other ethylenically unsaturated free-radically polymerizable monomer; and

c-a 2.3) 0 to 5% by weight, based on C-A2, of at least one crosslinking monomer having two or more ethylenically unsaturated groups;

C-B2) 20 to 75% by weight, based on the total graft copolymer, of a soft elastomeric intermediate shell C-B2 having a glass transition temperature Tg below 0 ℃, consisting of:

C-B2.1) 45 to 99.5% by weight, based on B2, of at least one C1-C10-alkyl acrylate, preferably n-butyl acrylate;

C-B2.2) 0.5 to 5% by weight, based on B2, of at least one crosslinking monomer having two or more ethylenically unsaturated groups; and

C-B2.3) 0 to 50% by weight, based on B2, of at least one other ethylenically unsaturated free-radically polymerizable monomer, preferably a monomer having an aromatic group; and

C-C2) 15 to 60% by weight, based on the total graft copolymer, of a hard shell C-C2 having a glass transition temperature Tg of above 50 ℃, consisting of:

from 80 to 100% by weight, preferably from 90 to 100% by weight, based on C-C2, of at least one C1-C6-alkyl methacrylate, preferably methyl methacrylate; and

C-C2.2) from 0 to 20% by weight, preferably from 0 to 10% by weight, based on C-C2, of at least one other ethylenically unsaturated free-radically polymerizable monomer.

Preferably, at least 15 wt.%, more preferably at least 25 wt.% of the hard outer shell C-C2 is covalently bonded to the soft elastomeric intermediate shell C-B2.

Preferred graft copolymers C are polymer particles which can have a multilayer core-shell structure and are obtained by emulsion polymerization, as described, for example, in EP 0 113 924 A2, EP 0 522 351 A1, EP 0 465 049 A2 and EP 0 683 028 A1.

Optional Polymer component D

The polymer composition of the invention may comprise one or more optional polymer components D, which are different from the acrylic polymer a, the olefinic copolymer B and the particulate heterophasic graft copolymer C. In general, the optional polymer component D may be present in an amount of from 0.0 to 50.0 wt%, preferably from 1.0 to 30.0 wt%, more preferably from 2.0 to 20.0 wt%, also preferably from 4.0 to 15.0 wt%, also preferably from 4.0 to 10 wt%, based on the total polymer composition. Preferably, the optional polymer component D is selected from polymers which can be homogeneously mixed with the acrylic polymer a and which can form a polymer matrix together with the acrylic polymer a.

According to a preferred embodiment, the polymer composition of the invention comprises at most 50.0 wt.%, preferably from 1.0 to 50.0 wt.%, more preferably from 2.0 to 20.0 wt.%, based on the total polymer composition, of at least one additional polymer component D selected from the group consisting of:

In a preferred embodiment, the polymer composition according to the invention comprises, as polymer component D, from 0 to 20% by weight, preferably from 2.0 to 20.0% by weight, more preferably from 4.0 to 15.0% by weight, based on the total polymer composition, of a copolymer D1 comprising at least one monovinylaromatic monomer and at least one carboxylic anhydride monomer.

Preferably, the optional copolymer D1 is a copolymer of:

65.0 to 90.0% by weight, preferably 70.0 to 90.0% by weight, more preferably 72.0 to 85.0% by weight, still more preferably 75.0 to 80.0% by weight, based on the weight of the copolymer D1, of at least one monovinylaromatic monomer, preferably styrene; and

From 10.0% to 35.0% by weight, preferably from 10.0% to 30.0% by weight, more preferably from 15.0% to 28.0% by weight, still more preferably from 20.0% to 25.0% by weight, based on the weight of the copolymer D1, of at least one carboxylic anhydride monomer, preferably maleic anhydride.

Such copolymers D1 are commonly referred to as styrene-maleic anhydride (SMAH) resins and are commercially available from a number of manufacturers, such as Polyscope from Geleen, the NetherlandsTypes.

In another preferred embodiment, the polymer composition according to the invention comprises as component D at least one copolymer (copolymer D2) comprising at least one monovinylaromatic monomer and at least one vinylcyanide monomer. According to a preferred embodiment, the polymer composition of the invention comprises, as additional polymer component D, from 0 to 20% by weight, preferably from 2.0 to 20.0% by weight, more preferably from 4.0 to 13.0% by weight, most preferably from 4.0 to 10.0% by weight, based on the total polymer composition, of a copolymer D2 comprising at least one monovinylaromatic monomer and at least one vinylcyanide monomer.

Preferably, the optional copolymer D2 is a copolymer of:

68.0 to 85.0% by weight, 72.0 to 80.0% by weight, based on the weight of the copolymer D2, of at least one monovinylaromatic monomer, preferably styrene; and

15.0 to 32.0% by weight, preferably 20.0 to 28.0% by weight, based on the weight of the copolymer D2, of at least one vinyl cyanide monomer, preferably acrylonitrile.

Such copolymers D2 are commonly referred to as styrene-acrylonitrile (SAN) resins and are available from a number of manufacturers, such as from INEOS Styrolution Group GmbH (Frankfurt Germany)Type or +.f. from Trinseo S.A. (Luxembourg)>Types.

The preparation of copolymer D2 may be carried out by essentially any known polymerization process described for preparing SAN resins, such as bulk, solution, emulsion or bead polymerization.

Although copolymers D1 and/or D2 of essentially any molecular weight can be used, the use of copolymers D1 and/or D2 having a weight average molecular weight Mw of from 60 g/mol to 300 g/mol, preferably from 100 g/mol to 250 g/mol, has proven to be particularly advantageous in terms of the mechanical properties of the composition. The average molecular weight Mw of the copolymer D1 can be determined by GPC using PMMA standard.

In general, the monovinylaromatic monomer in the copolymers D1 and D2 is the same as one of the monovinylaromatic monomers mentioned above in relation to the acrylic polymer A. Suitable monovinylaromatic monomers for the optional copolymer D1 are styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-n-propylstyrene, tert-butylstyrene, 2, 4-dimethylstyrene, vinyltoluene and mixtures thereof. In a preferred embodiment, the monovinylaromatic monomer is styrene and/or alpha-methylstyrene, more preferably the monovinylaromatic monomer is styrene.

Examples of suitable vinyl cyanide monomers for use in the present invention, in particular for copolymer D2, include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, fumaric acid nitrile, and the like. These may be used alone or as a mixture thereof. For example, the vinyl cyanide monomer may include acrylonitrile and/or methacrylonitrile. More preferably, the vinyl cyanide monomer is acrylonitrile.

Optional additional component E

The polymer composition according to the invention may optionally comprise one or more additional components E, preferably selected from the non-polymeric components, such as additives, adjuvants and/or fillers generally known. Typically, the additional component E may be present in an amount of 0.0 to 15.0 wt%, preferably 0.0 to 10.0 wt%, more preferably 0.0001 to 5.0 wt%, also preferably 0.001 to 2.0 wt%, based on the total polymer composition.

The polymer compositions of the invention may optionally contain conventional additives, adjuvants and/or fillers, such as heat stabilizers, processing stabilizers, uv absorbers, gamma ray stabilizers, antioxidants, in particular soluble or insoluble dyes or colorants, and plasticizers, provided that these additives do not adversely affect the properties of the compositions according to the invention.

Suitable UV absorbers may be, for example, derivatives of benzophenone with substituents such as hydroxy and/or alkoxy groups usually present in the 2-and/or 4-position. These include 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone, 2' -dihydroxy-4-methoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone.

Particularly suitable UV absorbers include, for example, benzotriazoles of the general formula (III)

Wherein R4, R5 and R6 are independently selected from hydrogen or C1-C12-alkyl.

Examples of compounds (III) which are particularly suitable for the present invention are 2- (2 '-hydroxy-5' -methyl-phenyl) benzotriazole (which is available under the trade nameP is commercially available from BASF SE; ludwigshafen, germany) or 2- (2' -hydroxy)Phenyl-3 '-dodecyl-5' -methyl-decyl) benzotriazole.

Particularly preferred ultraviolet absorbers further include the following hydroxyphenyl benzotriazole derivatives:

in addition, substituted benzotriazoles suitable for use as external ultraviolet light absorbers include, inter alia, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [ 2-hydroxy-3, 5-bis (α, α -dimethylbenzyl) phenyl ] benzotriazole, 2- (2-hydroxy-3, 5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-t-pentylphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) benzotriazole, and 2- (2-hydroxy-5-t-octylphenyl) benzotriazole.

Also useful ultraviolet absorbers are ethyl-2-cyano-3, 3-diphenylacrylate, 2-ethoxy-2 '-ethyloxanilide (oxalic acid bisanilide), 2-ethoxy-5-tert-butyl-2' -ethyloxanilide and benzoic acid substituted phenyl esters.

The ultraviolet light absorber may be present in the polymer composition as a low molecular weight compound. However, the UV absorbing groups in the matrix polymer molecules may also be covalently bonded after copolymerization with a polymerizable UV absorbing compound, such as an acrylic, methacrylic or allyl derivative of a benzophenone derivative or benzotriazole derivative.

As one skilled in the art will readily recognize, mixtures of chemically different uv absorbers may also be used.

The total content of uv absorbers in the polymer composition is generally from 0.01 to 1.0% by weight, in particular from 0.01 to 0.5% by weight, especially from 0.02 to 0.2% by weight, based on the total weight of the polymer composition according to the invention.

Examples of suitable radical scavengers/UV stabilizers include, inter alia, HALS @ under the nameHindered Amine Light Stabiliser) is a known sterically hindered amine. They areCan be used to inhibit the ageing process in finishes and plastics, in particular in polyolefin plastics (Kunststoffe [ plastics ] ]74 (1984) 10, pages 620 to 623; farbe+Lack [ color paint and varnish ]],96 ^th Annual, 9/1990, pages 689 to 693). The presence of tetramethylpiperidine groups in HALS compounds renders them stable. Such compounds may be unsubstituted or substituted on the piperidine nitrogen with alkyl or acyl groups. Sterically hindered amines do not absorb in the UV region. They trap the free radicals formed, which again cannot be done by uv absorbers.

Examples of HALS compounds which have a stabilizing effect and which can also be used as mixtures are: bis (2, 6-tetramethyl-4-piperidinyl) sebacate, 8-acetyl-3-dodecyl-7, 9-tetramethyl-1, 3, 8-triazaspiro (4, 5) -decane-2, 5-dione bis (2, 6-tetramethyl-4-piperidinyl) succinate poly (N-beta-hydroxyethyl-2, 6-tetramethyl-4-hydroxypiperidine succinate) and bis (N-methyl-2, 6-tetramethyl-4-piperidinyl) sebacate.

The radical scavenger/uv stabilizer is used in the composition according to the invention in an amount of 0.01% to 1.5% by weight, in particular in an amount of 0.02% to 1.0% by weight, in particular in an amount of 0.02% to 0.5% by weight, based on the total amount of all ingredients.

Lubricants and release agents that reduce or completely prevent possible sticking of the molding material to the injection mold are important to the injection molding process and may also be used.

For example, a lubricant selected from saturated fatty acids having less than C20, preferably from C16 to C18 carbon atoms or saturated fatty alcohols having less than C20, preferably from C16 to C18 carbon atoms may be present as optional additional auxiliary E. For example, stearic acid, stearyl alcohol, palmitic acid, palmitol, lauric acid, lactic acid, glycerol monostearate, pentaerythritol, and technical mixtures of stearic and palmitic acid. Also suitable are n-cetyl alcohol, n-stearyl alcohol and technical mixtures of n-cetyl alcohol and n-stearyl alcohol. A particularly preferred lubricant or mold release agent is stearyl alcohol.

The lubricant is typically used in an amount of no greater than 0.35 wt%, such as 0.05 wt% to 0.25 wt%, based on the weight of the polymer composition.

Furthermore, if the composition comprises at least one plasticizer as optional additional component E, the crack resistance and chemical resistance of the molding composition can be additionally improved. Plasticizers are known per se to the person skilled in the art and are described, for example, in Ullmann's Encyclopaedia of Industrial Chemistry (wullmann's university of industrial chemistry), 2012, plasticizers, d.f. cadogan et al. For the purposes of the present invention, plasticizers generally have a molecular weight of from 100g/mol to 200 g/mol and a melting temperature of not more than 40 ℃. If polymeric compounds are used as plasticizers in the molding compositions of the present invention, such polymeric compounds should desirably have a glass transition temperature Tg of not more than 40℃as measured according to the standard ISO 11357-2:2013. Furthermore, in order to ensure that the presence of the plasticizer does not adversely affect the optical properties of the polymer composition, the plasticizer should be miscible with the molding composition.

Examples of particularly suitable plasticizers include in particular polyethylene glycol having a molecular weight of 500 to 15 g/mol, tributyl citrate, diisononyl 1, 2-cyclohexanedicarboxylate (for example as a mixture of isomers under the trade nameDINCH is available from BASF SE, ludwigshafen, germany) and adipic acid polyesters (for example as a mixture of isomers under the trade name +.>IV was purchased from Lanxess, leverkusen, germany). Typically, the diisononyl 1, 2-cyclohexanedicarboxylate is a mixture of isomers and typically comprises 10% by weight n-nonanol, 35-40% by weight methyl octyl alcohol, 40-45% by weight dimethyl heptyl alcohol and 5-10% by weight methyl ethylhexyl alcohol, based on the total weight of isononyl alcohol residues. Some of the additives, such as ultraviolet absorbers, ultraviolet stabilizers, antioxidants, and plasticizers, such as adipic acid polyesters, may also improve color stability upon and after gamma-ray exposure.

The plasticizer is generally used in an amount of 0.01 to 5.0 wt%, preferably 0.05 to 3.0 wt%, based on the weight of the polymer composition.

In the present invention, component c as described below ₁ )、c ₂ )、c ₃ ) And/or c ₄ ) The addition of (c) has also proven to be particularly useful.

Component c ₁ ) Refers to triaryl phosphites of the general formula (I)

Wherein R is ¹ And R is ² Represents a C1-C12-alkyl group, such as methyl, ethyl, propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1-dimethylpropyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 3-dimethylbutyl, 1, 1-dimethylbutyl, 2-dimethylbutyl, 3-dimethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, decyl, undecyl and dodecyl, C3-C12-alkyl which is preferably branched in the 1-position (. Alpha.) and in particular C3-C7-alkyl, such as 1-methylethyl, 1-methylpropyl, 1-dimethylethyl, 1-methylbutyl, 1, 2-dimethylpropyl, 1-dimethylpropyl, 1-ethylpropyl, 1-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, 1-methylhexyl, 1-ethylpentyl and 1-propylbutyl and 1, 3-tetramethylbutyl, 1,1,2,2,5,5-hexamethylhexyl,

C5-C8 cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctaneRadicals, preferably cyclohexyl, C6-C10-aryl and C6-C100-aryl-C1-C4-alkyl, the aryl radical of which may be up to trisubstituted by C1-C4-alkyl, such as phenyl, naphthyl or 2, 2-dimethylbenzyl, and R ³ Refers to hydrogen and C1-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably hydrogen and methyl.

Examples of compounds (I) are the commercially available tris (2, 4-di-tert-butylphenyl) phosphites [ ]168, commercially available from BASF SE, ludwigshafen, germany) and tris (nonylphenyl) phosphite, preferably tris (2, 4-di-tert-butylphenyl) phosphite.

Component c ₂ ) Refers to phenols of the general formula (IV)

AB _k (IV)

Wherein k is 1, 2 or 4, and if k is 1, A represents-COOR ⁷ 、-CONHR ⁷

R ⁷ Refers to C1-C21-alkyl, and

if k is 2, A represents-CONH- (CH) ₂ ) _n -CONH-，

Wherein p and m refer to integers from 1 to 10, and if k is 4, A represents

Wherein q is an integer of 1 to 4, and

b represents

Wherein R is ⁸ And R is ⁹ Represents hydrogen, methyl or tert-butyl.

Component c ₃ ) The addition of (3) may lead to further improvements in stress crack resistance.

Compounds c of particular importance for the invention ₃ ) Examples of (A) are octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (which may be used as 1076 from BASF SE; ludwigshafen, germany) and +.>

Furthermore, the use of the following stabilizers as compounds c 4) has been shown to be particularly advantageous:

sulfides or organic disulfides and sulfides, such as di-tert-dodecyl disulfide, di-tert-butyl disulfide, di-tert-dodecyl disulfide, can also be used advantageously for this purpose.

Component c ₁ )、c ₂ )、c ₃ ) And c ₄ ) Preferably as a mixture to achieve a synergistic effect with respect to the improvement of stress cracking resistance after weathering.

Component c ₁ ) To c ₃ ) In each case based on polymer components A, B and C and optionally D and +.Or F from 0.01 to 1.0 wt%, preferably from 0.01 to 0.1 wt%, based on the total weight of F. The preferred amount of component C4) is generally in the range of from 0.01 to 2.0 wt%, preferably from 0.05 to 1.0 wt%, based on the total weight of the polymer components A, B and C and optionally D and/or F.

Optional additional impact modifier F

Optionally, the polymer composition according to the invention may comprise, in addition to the particulate heterophasic graft copolymer C as described above, one or more additional impact modifiers as component F. For example, the optional additional impact modifier may be selected from so-called thermoplastic impact modifiers, in particular thermoplastic impact modifiers that establish individual domains within the polymer composition of the invention, in particular within the polymer matrix formed by the acrylic polymer a. In general, the additional impact modifier F may be present in an amount of from 0.0 to 40.0 wt.%, preferably from 0.0 to 35.0 wt.%, more preferably from 5.0 to 40.0 wt.%, and also preferably from 10.0 to 35.0 wt.%, of at least one or more additional impact modifiers F based on the total polymer composition.

Generally, thermoplastic impact modifiers have a different mechanism of action than particulate impact modifiers. They are typically mixed with a matrix material. In the case of the formation of micro-domains, which occurs for example in the case of the use of block copolymers, the preferred dimensions of these micro-domains, which can be determined for example by electron microscopy, correspond to the preferred dimensions of the core-shell particles.

There are various classes of thermoplastic impact modifiers. For example, aliphatic Thermoplastic Polyurethanes (TPU) such as those available from Covestro AG may be usedAnd (5) a product. For example, TPU->WDP 85784A, WDP 85092A, WDP 89085A and WDP 89051D (both of which have refractive indices between 1.490 and 1.500) are particularly suitable as impact modifiers.

As an additional impact modifier FAnother class of thermoplastic polymers of (a) is methacrylate-acrylate block copolymers, especially acrylic TPEs, which contain PMMA-poly-n-butyl acrylate-PMMA triblock copolymers and can be given the product name by KurarayAre provided commercially. The poly (n-butyl acrylate) blocks form nano-domains in the polymer matrix with a size between 10nm and 20 nm.

Another class of polymers used as additional impact modifiers F is based on styrene-butadiene block copolymers (SBC) optionally included in a polymer matrix, such as acrylic-styrene copolymers (e.g., from Ineos Styrolution) ) And ethylene-propylene-diene rubbers (EPDM) or grafted EPDM, such as EPDM grafted with an acrylic polymer matrix.

According to a preferred embodiment, the polymer composition of the invention comprises 5.0 to 40.0 wt.%, preferably 10.0 to 35.0 wt.%, based on the total polymer composition, of at least one additional impact modifier F, preferably selected from thermoplastic impact modifiers such as aliphatic Thermoplastic Polyurethanes (TPU), methacrylate-acrylate block copolymers, styrene-butadiene block copolymers (SBC) and ethylene-propylene-diene rubbers (EPDM).

Properties of the Polymer composition

As already mentioned above, the polymer compositions of the invention have excellent stress crack resistance in the presence of common disinfectants (in particular alcohols or water/alcohol mixtures), oils and fats. In particular, the polymer composition exhibits improved stress crack resistance in the presence of oils and fats, including emulsions comprising soybean oil, glycerol and/or water, and an emulsifier, such as a phospholipid. For example, the oil and fat test liquids may be those available from Fresenius Kabi Austria GmbHAn emulsion.

In addition, the polymer compositions of the present invention have excellent clarity and an attractive appearance that is substantially haze-free. In a preferred embodiment, the polymer composition has a haze of equal to or less than 70%, preferably equal to or less than 60%, also preferably equal to or less than 50%, more preferably equal to or less than 40%, measured at 23 ℃ on an injection molded specimen having a thickness of 3mm according to standard ASTM D1003 (2013).

Furthermore, the polymer composition maintains its excellent transparency even in the presence of common disinfectants, oils and fats and has a particularly low haze increase under these conditions. Typically, a sample of 3mm thickness is exposed to an isopropanol/water mixture (63.0 wt% isopropanol, 37.0 wt% water) at 23 ℃ for at least 48 hours, preferably 72 hours at 23 ℃, more preferably 96 hours at 23 ℃ resulting in a haze increase of at most 40%, preferably at most 25%, even more preferably at most 20%.

Furthermore, the polymer composition preferably exhibits a light transmission TD65 according to DIN 5033-7 (2014) in the range from 40 to 93%, in particular in the range from 65 to 92%, measured at 23℃on injection-molded test specimens having a thickness of 3 mm.

According to DIN 6167 (1980) (light source D) ₆₅ 10 ° at a layer thickness of 3 mm) should preferably be less than 15, preferably less than 8 (typically the value of the uncolored polymer), measured on injection molded specimens of 3mm thickness at 23 ℃.

The vicat softening temperature of the polymer composition according to ISO 306-B50 (2014) is advantageously at least 60 ℃, preferably at least 70 ℃, more preferably at least 75 ℃.

The nominal elongation at break of the polymer composition according to ISO 527 (2012) should preferably be at least 3.0%, particularly preferably at least 5.0%.

The elastic modulus of the polymer composition according to ISO 527 (2012) is advantageously greater than 1500MPa, preferably greater than 1700MPa.

The polymer composition according to the invention is very suitable for the manufacture of medical grade articles by means of injection moulding, due to its advantageous rheological properties. The compositions of the present invention typically have a length of greater than 0.3cm ³ Preferably greater than 0.5cm for a period of time of 10min ³ Preferably greater than 0.7cm for a period of time of 10min ³ 10min, most preferably 1.0 to 12.0cm ³ Melt volume flow rate MVR measured according to ISO 1133 (2012) at 230 ℃ and 5.0kg in the range of/10 min.

Preferably, the polymer composition of the present invention has one or more of the following properties (i) - (iv):

(i) A vicat softening temperature according to ISO 306-B50 (2014) of at least 60 ℃, preferably at least 70 ℃, more preferably at least 75 ℃;

(ii) A nominal elongation at break according to ISO 527 (2012) of at least 3.0%, particularly preferably at least 5.0%;

(iii) An elastic modulus according to ISO 527 (2012) of greater than 1500MPa, preferably greater than 1700 MPa;

(iv) At least 40%, preferably at least 60%, more preferably at least 65% of the light transmittance (TD 65) according to DIN 5033-7 (2014) measured on injection molded test pieces having a thickness of 3mm at 23 ℃.

Preparation of compositions and molded articles

Furthermore, the present invention relates to a process for the manufacture of the polymer composition of the invention as described above, wherein the process comprises mixing component A, B, C and optionally D, E and/or F, preferably melt mixing component A, B, C and optionally D, E and/or F.

The compositions of the present invention may be prepared by dry blending the above components which may be present as powders, granules or preferably pellets.

The compositions according to the invention can also be prepared by mixing components B and C simultaneously or successively into a melt of polymer A and optionally D and/or F. The composition may also be prepared by melting and mixing the components in the molten state or by melting a dry premix of the components to obtain a ready-to-use molding material. This can be done, for example, in a single-screw or twin-screw extruder. The extrudate obtained may then be granulated. Conventional additives, adjuvants and/or fillers can be incorporated directly or subsequently added as desired by the end user.

The composition according to the invention is suitable as a raw material for producing molded articles, such as medical molded articles, which have improved chemical and stress crack resistance and are transparent. The shaping of the composition can be carried out by methods known per se, for example by processing via the elastomehc state, i.e. by kneading, rolling, calendaring, extrusion or injection molding, extrusion and injection molding, in particular injection molding being particularly preferred here.

Injection molding of the composition can be carried out in a manner known per se at temperatures of 220℃to 280℃and preferably at mold temperatures of 60℃to 90 ℃.

The extrusion is preferably carried out at a temperature of 220℃to 280 ℃.

A further aspect of the invention relates to molded articles comprising the polymer composition as described above, in particular for applications requiring high chemical resistance and chemical stress cracking resistance.

In a particularly preferred embodiment, the molded article is a medical device, preferably a disposable medical device, selected from the group consisting of medical diagnostic devices, venous and catheter attachments, blood processing devices, chest drainage devices, respiratory ventilation devices, medical filter housings, permanent device housings, tubes, connectors, fittings and cuvettes, for example. Such devices include, but are not limited to, luer locks, Y-points (sites), tips, fittings, nozzles, protective caps and shields, plasma separators, collection and sample containers, needle interfaces and adapters, catheter attachments, chest drainage devices, valve assemblies, meter housings, flow controllers, filter housings, drip chambers, intravenous adapters, yang Keshi aspiration tubing (yankauer), rigid tubing, diagnostic cuvettes, diagnostic test packs, diagnostic rotors, optical sensor windows, microfluidic devices, brachytherapy (brachytherapy) needle interfaces, suction nozzles (mouthpiecs), and spacers.

In a particularly preferred embodiment, the molded article is selected from the group of articles for: parts of a household appliance; a component of a communication device; an electronic component; a component of a hobby device; a component of an exercise apparatus; a component of a gardening device; external and internal components of an automobile, a ship or an aircraft; a component for constructing a body component of an automobile, a ship or an aircraft; components in bathroom facilities.

Drawings

FIG. 1 illustrates the setup of a chemical stress cracking resistance test as described in the experimental examples. A test specimen (2) having a thickness h is fixed on a bending model (3) having a bending surface with a radius r, wherein the test specimen (2) is fixed by means of two clamps (1). Epsilon _x Is the nominal strain of the surface.

Fig. 2 shows the shape of a test specimen (2) fixed on a bending model (3) with two clamps (1).

The following examples explain the invention in more detail but are not intended to limit the concept of the invention.

Detailed Description

Examples

I. Preparation of Polymer compositions

The polymer compositions of examples 1-12 were prepared from dry blends of the components with the aid of a tumble mixer. The dry mixture was compounded on a Leistritz LSM 30 twin screw extruder at a barrel temperature of 240℃and an output of 12kg/h at a screw speed of 150 rp. The compositions of examples 1 to 10 are summarized in table 1. Component A, B, C, optional D and optional F are described below.

Components of Polymer compositions

Acrylic polymers A1 and A2, PE-MAH graft copolymers B1 and B2, particulate heterophasic graft copolymers (impact modifiers) C1 and C2, optionally SAN copolymer D2 and optionally additives F as described below are used.

A1 acrylic Polymer A1, a copolymer (prepared as described below) comprising about 75.0 wt% MMA, 15.0 wt% styrene and 10.0 wt% maleic anhydride;

a2 acrylic Polymer A2 having a molecular weight average M of about 110.000g/mol composed of 97% by weight of methyl methacrylate and 3% by weight of methyl acrylate _w Polymethyl methacrylate resin (polymethyl methacrylate without impact modifier);

a3 acrylic Polymer A3, (meth) acrylic Polymer comprising a particulate core-shell impact modifier (prepared as described below), i.e., component A3 comprises component A (acrylic Polymer) and C (particulate heterophasic graft copolymer);

b1-polyolefin graft copolymer B, modic 814E (Mitsubishi Chemical/Japan), LLDPE polyethylene grafted with Maleic Anhydride (MAH) in an amount > 1.0% by weight (PE-g-MAH);

b2 polyolefin graft copolymer B, scona TPPE 5002GALL (BYK/Germany), LLDPE polyethylene grafted with maleic anhydride, MAH in an amount > 1.0% by weight (PE-g-MAH);

C1 impact modifier C, kaneM731 (Kaneka/united states), a core-shell copolymer comprising a polybutadiene core grafted with a polymethyl methacrylate shell;

c2 impact modifier C, kaneM711 (available from Kaneka corp., takasago, japan) comprising a core-shell copolymer of a polybutadiene core grafted with a polymethyl methacrylate shell;

d2. optional copolymer D2, styrene acrylonitrile copolymer (SAN) comprising 76.0 wt.% styrene and 24.0 wt.% acrylonitrile;

e1-optional additive E, polyethylene glycol PEG3350 (Dow Chemical/U.S.) having a molecular weight of about 3350.

TABLE 1 Polymer compositions (all amounts given in wt% based on the total Polymer composition)

Examples	A1	A2	A3**	B1	B2	C1	C2	D2	E1
										1	63.0		5.0			30.0		2.0
2	59.0			5.0			30.0	4.0	2.0
										3	60.8		5.0		30.0		4.2
4	59.0				5.0	30.0		4.0	2.0
										5*	61.0					30.0	7.0	2.0
6*	61.0					30.0		7.0	2.0
										7		96.0	4.0
8*	96.0			4.0
										9*	87.0			4.0			9.0
10*		96.0		4.0
										11		94.0	4.0					2.0
12*			100.0

* Comparative example

* A3=blend of PMMA (component a) and impact modifier (component B)

III preparation of the Components

a. Preparation of acrylic Polymer A1

Copolymer A1 comprising 75.0 wt.% MMA, 15.0 wt.% styrene and 10.0 wt.% maleic anhydride was prepared according to the procedure described in DE 44 40 219 A1.

The raw materials used for this preparation are as follows:

74.638 g of methyl methacrylate

15.00 g of styrene

10.00 g of maleic anhydride

0.33 g of n-dodecyl mercaptan

0.034 g of tert-butyl peroxyneodecanoate

0.01 g of t-butyl peroxyisononanoate

Placing the raw material inIn a polyester bag, polymerization was carried out in a water bath (12 hours at 52 ℃ C., then 16 hours at 44 ℃ C.), followed by tempering in a tempering furnace (6 hours at 110 ℃ C.). Finally, the copolymer a obtained is ground and degassed using an extruder.

The resulting copolymer A1 had a molecular weight Mw (described below) of about 150000g/mol, measured using GPC with PMMA as a standard, and had a solution viscosity in chloroform at 25℃of about 72ml/g (ISO 1628-part 6).

b. Preparation of acrylic Polymer A3 (impact modified PMMA)

The particulate core-shell impact modifier of A3 was prepared as follows:

in a polymerization vessel equipped with a stirrer, a feed vessel and external cooling, an aqueous phase containing acetic acid, iron (II) sulfate (FeSO 4) and seed crystals (containing 10 wt.% PMMA) was placed. Emulsion I, described below, was added over a period of 1 hour at a temperature of 52℃ (the outside temperature of the vessel). 0.69 grams of sodium metabisulfite in 20 grams of water (over the course of the first 10 minutes) was added in parallel. After 15 minutes, 1.94 grams of sodium metabisulfite in 100 grams of water was added over 10 minutes, in parallel with the beginning of the addition of emulsion II as described below. Emulsion II was added over 2 hours and then discontinued for 50 minutes. Emulsion III, described below, was added simultaneously with 0.62 grams of sodium metabisulfite in 50 grams of water. The addition of sodium metabisulfite was completed within 10 minutes and emulsion III was completed after 1 hour. The reaction mixture was thereafter stirred for 30 minutes, cooled to 35℃and filtered through VA-steel (mesh size 100 μm).

Emulsions I, II and III were each obtained by emulsifying the monomers and components (given in parts by weight) as follows:

aqueous phase

Emulsion I

Emulsion II

Emulsion III

The resulting latex is coagulated by freeze coagulation, dewatered and dried.

The resulting impact modifier polymer powder was melt compounded with a polymethyl methacrylate resin composed of 97 weight percent methyl methacrylate and 3 weight percent methyl acrylate having a molecular weight average Mw of about 150.000g/mol, wherein the amount of impact modifier was about 19 weight percent based on the total polymer blend. The polymer blend was mixed at a temperature of 220-230℃at 30 rpm. The resulting melt was removed from the chamber and crushed with pliers.

Results IV

Test specimens (details described below) were prepared by injection molding from the polymer compositions according to examples 1-12. The melt volume flow rate (MVR), vicat softening temperature (B50), optical properties (haze, transmittance (TD 65)), tensile properties (elongation at break (Elong@break), tensile modulus (E), tensile strength maximum (TS) _max ) Chemical resistance (stress crack resistance) to alcohols and fats. Unless otherwise indicated, all test specimens were stored at 23 ℃/50% relative humidity for at least 24 hours prior to testing. Unless otherwise indicated, the tests were carried out at 23 ℃/50% relative humidity.

The results are summarized in tables 2 and 3 below.

TABLE 2 test results examples 1-12

* Comparative example

Examples 1-4 of the present invention, which included polybutadiene core-shell impact modifier (C1 or C2) and polyethylene maleic anhydride graft copolymer PE-MAH (B1 or B2), exhibited high transmittance (TD 65) and low haze. Furthermore, all examples 1-4 were high in stress cracking resistance, and all tensile bars exhibited ductile fracture in tensile test (at 0.5% strain and 0.75% strain). Comparative examples 5 and 6 (without polyethylene maleic anhydride graft copolymer C1 or C2) also exhibited high transparency and low haze. However, providing sufficient stress crack resistance at only 0.5% strain, all tensile bars showed brittle fracture and lower elongation at break and tensile strength at break in tensile testing under more severe conditions (0.75% strain). Thus, the stress crack resistance (see 0.75% strain) to alcohols according to examples 1-4 of the present invention is higher than that of comparative examples 5-6 (without component B, PE-MAH). Furthermore, it has been found that this advantageous higher resistance to chemical stress cracking becomes clearly visible using the specific chemical resistance test as described, which involves adjustable more severe conditions.

Test specimens according to comparative examples 8 and 9, which have a polymer matrix similar to that of examples 1 to 4 (A1 or A1+D1) and comprise PE-MAH (B1 or B2) but no impact modifier (C1 or C2), are not transparent (white). Comparing inventive example 7 with comparative example 10, similar results are shown. Both examples are based on PMMA matrix polymer (A2 or A3) and comprise 4% by weight of PE-MAH (B1). However, the polymer composition of example 7 included an impact modified particulate core-shell (component A3 is impact modified PMMA). The polymer composition of example 7 of the present invention is transparent (having high transmittance TD 65), whereas the polymer composition of comparative example 10 is not transparent (white). Thus, it has surprisingly been found that transparent polymer compositions can be obtained when an acrylic polymer is mixed in combination with PE-MAH and a particulate impact modifier (e.g. C1 or C2).

Furthermore, it was demonstrated that by adding PE-MAH component B, improved stress crack resistance was obtained in the impact modified polymer composition based on PMMA polymer A3. The stress crack resistance (see 0.5% strain) to alcohol of example 11 (impact modified PMMA A3+PE-MAH21+PEG E1) according to the invention is higher than that of comparative example 12 (100% impact modified PMMA A3). In comparative example 12, all five test bars failed after IPA/H2O exposure at 0.5% strain.

V. test method

GPC measurement conditions:

eluent THF (HPLC-grade) +0.2 vol% TFA

Flow rate 1ml/min

Injection volume 100. Mu.l

Detection of RI HPS

Concentration of

Sample solution 2g/l

Standard sample PMMA

b. Optical and mechanical Properties and other Properties

The haze of the polymer composition was measured at 23℃on injection molded test specimens having a thickness of 3mm according to standard ASTM D1003.

The light transmittance (TD 65) of the polymer composition was measured at 23℃on injection-molded test specimens having a thickness of 3mm in accordance with DIN 5033-7 (2014).

Melt volume flow rate MVR was measured according to ISO 1133 (2012) at 230 ℃ and a load of 5.0 kg.

The Vicat softening temperature of the polymer composition is determined according to ISO 306-B50 (2014).

Tensile properties of the polymer compositions were determined according to ISO 527-1:2012 using test specimens (tensile bars) prepared by injection molding according to ISO 294-1:2016. Elongation at break, tensile modulus and tensile strength (ultimate tensile strength or tensile strength at break) are summarized in tables 2 and 3 above. The nominal elongation at break of the polymer composition according to ISO 527 (2012) should preferably be at least 4.0%, particularly preferably at least 5.0%. The modulus of elasticity of the polymer composition according to ISO 527 (2012) is advantageously greater than 1500MPa, preferably greater than 1700MPa.

c. Determination of chemical stress cracking resistance

Stress crack resistance to alcohols was determined by the bending tape procedure ISO 22088-3 as follows:

five tensile bars according to ISO 294-1:2016 were prepared from each polymer composition by injection molding at 250 ℃. The tensile bars were thereafter annealed at about 70-80 ℃ for 2 hours (20K below Vicat B50 softening temperature, depending on the polymer).

The test specimen (160 mm×20mm×thickness h=4mm) is laid flat on the bending model. A specific experimental setup is schematically illustrated by fig. 1 and 2. As shown in fig. 1, each tensile bar (test specimen (2)) was fixed on a bending model (3) having a bending surface with radius r by means of two clamps (1), wherein a strain of 0.5% or 0.75% was applied.

Strain as nominal strain epsilon on an externally stretched surface _x Given and calculated as in ISO 22088-3 (2006):

where r is the radius of the bending model and h is the thickness of the test specimen (see FIG. 1).

The spline fixed on the bending model was exposed to a mixture of 63.0 wt.% isopropyl alcohol (IPA) and 37.0 wt.% water. For this purpose, cotton cloth (50 mm x 8 mm) saturated with the mixture (63.0 wt% isopropyl alcohol (IPA) and 37.0 wt% water) was placed in the middle of the top of the bars, and then a curved model with a fixed bar covered with cotton cloth was placed in a closed polyethylene bag of approximately 4 liters volume along with an open 100 ml glass cup containing a mixture of 63.0 wt% isopropyl alcohol (IPA) and 37.0 wt% water. The arrangement was kept in a closed polyethylene bag for 5 hours at 23 ℃.

The bending mould was removed from the polyethylene bag, the cotton was removed, and the tensile bars were removed from the bending mould. Tensile properties of the tensile bars were measured 2 hours after removal according to ISO 527-1:2012. The result is the average of five bars. The results are summarized in table 3 above.

High chemical resistance is given when the surface of the tensile spline shows no defects after a 5 hour procedure as described above and the tensile spline shows ductile fracture under tensile stress.

Stress crack resistance to fat was determined as follows:

as test liquid, use was made of20% emulsion (available from Fresenius Kabi Austria GmbH). />20% is a sterile fat emulsion having a pH of 8, an osmolality of about 350mosmol/kg and comprising 20% soybean oil, 1.2% egg yolk phospholipids, 2.25% glycerol and water. Five tensile bars were prepared and annealed as described above.

According to the procedure described above, each tensile bar was fixed on a bending model having a bending surface, in which a strain of 1.0% was applied (see fig. 1). Exposing a test spline secured to a bending model to a test liquid20%. For this purpose, it will be soaked->20% cotton cloth (50 mm. Times.8 mm) was placed in the middle of the top of the bars. The arrangement was maintained at 23 ℃ for 24 hours. The cotton was removed and the tensile bars were removed from the bending model. Tensile properties of the tensile bars were measured 2 hours after removal according to ISO 527-1:2012. The results are summarized in table 3 above.

d. Impregnation test with aqueous isopropanol mixture

Samples of examples 1-4 were tested using a mixture comprising 63.0 wt% isopropyl alcohol (IPA) and 37.0 wt% water. The duration of the immersion test was 72 hours at 23 ℃. Visual evaluation of the samples was then performed. The results are summarized in table 4. All samples of the polymer compositions of the present invention exhibited a transparent appearance.

TABLE 4 test results impregnation test

Examples	Test medium	Appearance after 72 hours
			1	Isopropanol/water	Transparent and transparent
2	Isopropanol/water	Transparent and transparent
			3	Isopropanol/water	Transparent and transparent
4	Isopropanol/water	Transparent and transparent

Claims

1. A polymer composition comprising the following components A, B and C, based on the weight of the polymer composition:

from 0.5 to 12.0% by weight, preferably from 1.0 to 10.0% by weight, of at least one olefinic copolymer B comprising at least one olefinic monomer and at least one polar monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids,

c.5.0 to 40.0 wt%, preferably 10.0 to 36.0 wt%, of at least one particulate heterophasic graft copolymer comprising a core and at least one shell comprising at least one alkyl (meth) acrylate.

2. The polymer composition according to claim 1, wherein the polymer composition has a haze of equal to or less than 70% measured according to standard ASTM D1003 on injection molded test specimens having a thickness of 3mm at 23 ℃.

3. The polymer composition according to claim 1 or 2, wherein the polymer composition comprises at most 50.0 wt.%, based on the total polymer composition, of at least one additional polymer component D selected from the group consisting of

A copolymer D1 comprising at least one monovinylaromatic monomer and at least one carboxylic anhydride monomer; and

copolymer D2 comprising at least one monovinylaromatic monomer and at least one vinyl cyanide monomer.

4. A polymer composition according to any one of claims 1 to 3, wherein the acrylic polymer a comprises 40.0 to 100.0 wt%, preferably 45.0 to 100.0 wt%, more preferably 55.0 to 99.5 wt%, based on the total weight of acrylic polymer a, of at least one alkyl methacrylate monomer having 1 to 20, preferably 1 to 12, more preferably 1 to 8, most preferably 1 to 4 carbon atoms in the alkyl group.

5. The polymer composition according to any one of claims 1 to 4, wherein the acrylic polymer a is a thermoplastic (meth) acrylate polymer comprising:

0.0 to 20.0 wt%, preferably 0.1 to 4 wt% of at least one alkyl (meth) acrylate other than methyl methacrylate, preferably selected from C1-C10 alkyl acrylates;

from 0.0 to 20% by weight, preferably from 5.0 to 20.0% by weight, of one or more other copolymerizable monomers, preferably selected from anhydrides of unsaturated carboxylic acids,

wherein all amounts are given based on the total weight of acrylic polymer a.

6. The polymer composition according to any one of claims 1 to 5, wherein the acrylic polymer a is a copolymer of:

48.0 to 90.0 wt%, preferably 63.0 to 81.0 wt% of at least one alkyl (meth) acrylate, preferably methyl methacrylate;

Wherein all amounts are based on the total weight of acrylic polymer a.

7. The polymer composition according to any one of claims 1 to 6, wherein the at least one olefinic copolymer B is a polyolefin graft copolymer comprising at least one polyolefin base polymer grafted with at least one polar monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids.

8. The polymer composition according to any one of claims 1 to 7, wherein the at least one olefinic copolymer B is a polyolefin graft copolymer comprising at least one polyolefin base polymer grafted with 0.5 to 3.0 wt%, preferably 0.7 to 2.5 wt%, based on the weight of the graft copolymer B, of the at least one polar monomer selected from the group consisting of anhydrides of unsaturated carboxylic acids, preferably maleic anhydride.

9. The polymer composition according to any one of claims 1 to 8, wherein the particulate heterophasic graft copolymer C comprises:

a butadiene-based core comprising at least 65.0 wt%, preferably at least 75.0 wt% polybutadiene, based on the weight of the butadiene-based core; and

a shell comprising 60.0 to 100.0 wt%, preferably 65.0 to 100.0 wt%, based on the weight of the shell, of at least one alkyl (meth) acrylate, and 0.0 to 40.0 wt%, preferably 0.0 to 35.0 wt%, based on the weight of the shell, of at least one aromatic vinyl monomer.

10. The polymer composition according to any one of claims 1 to 8, wherein the particulate heterophasic graft copolymer C is selected from the group of graft copolymers based on an elastomer crosslinked alkyl (meth) acrylate core and comprises:

at least 40% by weight, preferably 40 to 70% by weight, of at least one C1-C10-alkyl methacrylate, preferably methyl methacrylate;

from 5 to 45% by weight, preferably from 20 to 45% by weight, preferably from 25 to 42% by weight, of at least one C1-C10-alkyl acrylate;

0 to 2 wt%, preferably 0.1 to 2 wt%, more preferably 0.5 to 1 wt% of at least one crosslinking monomer; and

from 0 to 15% by weight, preferably from 0 to 10% by weight, more preferably from 0.5 to 5% by weight, of optional additional monomers.

11. The polymer composition according to any one of claims 1 to 10, wherein the polymer composition comprises 5.0 to 40.0 wt%, preferably 10.0 to 35.0 wt%, based on the total polymer composition, of at least one additional impact modifier F selected from thermoplastic impact modifiers such as aliphatic thermoplastic polyurethanes, methacrylate-acrylate block copolymers, styrene-butadiene block copolymers and ethylene-propylene-diene rubbers.

12. The polymer composition according to any one of claims 1 to 11, wherein the polymer composition has one or more of the following properties (i) - (iv):

13. A process for the manufacture of a polymer composition according to any one of claims 1 to 12, wherein the process comprises mixing component A, B, C and optionally D, E and/or F, preferably melt mixing component A, B, C and optionally D, E and/or F.

14. A method of manufacturing a molded article from a polymer composition according to any one of claims 1 to 12, wherein the method comprises an injection molding step of the composition.

15. Molded article comprising a polymer composition according to any one of claims 1 to 12.

16. The molded article according to claim 15, wherein the molded article is a medical device, preferably a disposable medical device, for example selected from the group consisting of medical diagnostic devices, venous and catheter attachments, blood treatment devices, chest drainage devices, respiratory ventilation devices, medical filter housings, permanent device housings, tubes, connectors, fittings and cuvettes; or the molded article is selected from the group consisting of parts of household appliances; a component of a communication device; an electronic component; a component of a hobby device; a component of an exercise apparatus; a component of a gardening device; external and internal components of an automobile, a ship or an aircraft; a component for constructing a body component of an automobile, a ship or an aircraft; components in bathroom facilities.

17. Use of a polymer composition according to any of claims 1 to 12 in medical devices, preferably disposable medical devices, for example selected from medical diagnostic devices, venous and catheter attachments, blood treatment devices, chest drainage devices, respiratory ventilation devices, medical filter housings, permanent device housings, tubes, connectors, fittings and cuvettes.