Thermoplastic composition with improved resistance to ultraviolet light

文档序号：816756 发布日期：2021-03-26 浏览：8次中文

阅读说明：本技术 具有改善的抗紫外线性的热塑性组合物 (Thermoplastic composition with improved resistance to ultraviolet light ) 是由 T·舒尔茨 C·鲁萨德于 2019-06-11 设计创作，主要内容包括：本发明涉及一种改善乙烯基芳族模塑材料的抗紫外线性的方法,其包括配混热塑性聚合物组合物,其包括至少一种接枝共聚物,一种有机聚硅氧烷化合物以及任选的其他组分。(The present invention relates to a process for improving the UV resistance of vinylaromatic molding materials which comprises compounding a thermoplastic polymer composition comprising at least one graft copolymer, an organopolysiloxane compound and optionally further components.)

1. A method for improving the resistance of a moulding material (P) to uv light, comprising the step of compounding:

(A)80 to 99.5 wt% of at least one thermoplastic polymer composition (A) comprising:

(A-1) at least one graft copolymer (A-1), and

(A-2) at least one thermoplastic matrix (A-2) based on one or more vinylaromatic copolymers;

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D) from 0 to 5% by weight of one or more further additives (D), where components (A) to (D) add up to 100% by weight of the molding material (P).

2. The process according to claim 1, wherein the molding material (P) obtained with the process has at least one of the following characteristics:

(a) after 2400 hours of artificial weathering according to PV3929, the color shift of the molding materials (P) is less than 70% of the color shift of comparable molding materials (P) which have been likewise artificially weathered and have not used an organopolysiloxane compound (B);

(b) the color shift of the molding material (P) after 3200 hours of artificial weathering according to PV3929 is 65% lower than that of a comparable molding material (P) which has been likewise artificially weathered and which does not use an organopolysiloxane compound (B);

(c) after 2400 hours of artificial weathering according to PV3930, the color shift of the molding materials (P) is less than 80% of that of comparable molding materials (P) which have been likewise artificially weathered and which have not used an organopolysiloxane compound (B);

(d) after 3200 hours of artificial weathering according to PV3930, the colour shift of the molding materials (P) is less than 25% of that of comparable molding materials (P) which have been subjected to the same artificial weathering without the use of organopolysiloxane compounds (B); and/or

(d) Compared with a comparable molding material (P) which has been likewise artificially weathered and which does not use an organopolysiloxane compound (B), the gray scale of the molding material (P) is at least 1 unit higher after 3200 hours of weathering according to PV 3930.

3. The process according to any one of claims 1 or 2, wherein the at least one graft copolymer (A-1) is or comprises an Acrylonitrile Styrene Acrylate (ASA) wherein the average particle size d of the rubber particles in the ASA copolymer₅₀From 50 to 1000nm, wherein the average particle size is measured by scattered light.

4. The process according to any one of claims 1 to 3, wherein the at least one thermoplastic matrix (A-2) comprises a copolymer containing at least one vinyl cyanide and at least one vinyl aromatic compound.

5. The process according to any one of claims 1 to 4, wherein the at least one thermoplastic polymer composition (A) comprises at least one copolymer (A-2) comprising:

18 to 45 weight percent of at least one vinyl cyanide; and

from 55 to 82% by weight of at least one vinylaromatic compound.

6. The process according to any one of claims 1 to 5, wherein the at least one thermoplastic polymer composition (A) comprises

(A-1) 5 to 50% by weight, relative to the thermoplastic polymer composition (A), of at least one graft copolymer (A-1) comprising, or consisting of, an Acrylonitrile Styrene Acrylate (ASA), wherein the mean particle diameter d of the rubber particles in the ASA copolymer₅₀From 50 to 1000nm, wherein the average particle size is measured by scattered light; and

(A-2) 20 to 95% by weight, relative to the thermoplastic polymer composition (A), of at least one thermoplastic matrix (A-2) comprising 18 to 45% by weight of at least one vinyl cyanide and 55 to 82% by weight of at least one vinyl aromatic compound, and

(A-3) 0 to 75% by weight, relative to the thermoplastic polymer composition (A), of one or more additional thermoplastic polymers (A-3).

7. The process according to any one of claims 1 to 6, wherein the graft copolymer (A-1) comprises a binary or ternary size distribution comprising

(A-1a) at least one graft copolymer (A-1a) in which the mean particle diameter d of the rubber particles in the ASA copolymer₅₀From 50 to 150 nm; and

(A-1b) at least one graft copolymer (A-1b) in which the mean particle diameter d of the rubber particles in the ASA copolymer₅₀From 200 to 750 nm.

8. The method according to any one of claims 1 to 7, wherein the at least one organopolysiloxane compound (B) comprises repeating units having the following formula (I):

wherein each R¹Independently selected from linear or branched, saturated or unsaturated hydrocarbon groups having 1 to 10.

9. The method according to any one of claims 1 to 8, wherein the process of compounding the ingredients comprises at least the steps of:

(i) providing predetermined amounts of components (a) to (D) to an optionally heated mixing device; and

(ii) blending components (A) to (D) in the optionally heated mixing device at a temperature above the glass transition points of components (A) to (D) to obtain molding material (P).

10. The method according to any one of claims 1 to 9, wherein the molding material (P) comprises:

(A)85 to 99.3% by weight of at least one thermoplastic polymer composition (A) comprising at least one graft copolymer (A-1) and at least one thermoplastic matrix (A-2);

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D)0.1 to 5% by weight of one or more further additives (D),

wherein components (A) to (D) add up to 100% by weight of the molding material (P).

11. A molding material (P) obtainable from the process according to any one of claims 1 to 10.

12. A molding material (P) comprising:

(A)80 to 99.5 wt% of at least one thermoplastic polymer composition (A) comprising:

(A-3) 0 to 75 wt.%, relative to the thermoplastic polymer composition (A), of one or more additional thermoplastic polymers (A-3);

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D)0 to 5% by weight of one or more further additives (D),

wherein the sum of components (A) to (D) is 100% by weight of the molding composition (P),

and wherein the molding compound (P) has at least one of the following characteristics:

13. An article prepared from a molding material (P) as claimed in claim 11 or 12.

14. Use of an organopolysiloxane compound for improving the UV resistance of moulding materials.

15. Use according to claim 14, wherein the moulding compound is characterised as defined in any one of claims 1 to 10.

Description of the invention

The present invention relates to a process for improving the UV resistance of vinylaromatic molding materials by compounding a thermoplastic polymer composition comprising at least one graft copolymer with an organopolysiloxane compound and optionally further components.

Impact-modified molding materials, such as acrylonitrile-styrene acrylate (ASA) and its blends with other thermoplastic polymers, are widely used in many applications, for example in the automotive industry, the electronics industry or in household articles. The popularity of these thermoplastic polymer compositions may be due to their combination of good impact strength and melt flow characteristics.

Good surface properties, for example good scratch resistance, are often of interest for impact-modified molding materials. Therefore, a component for improving scratch resistance is sometimes added to the molding material. For example, it has been reported that silicon-containing compounds such as siloxanes can improve scratch resistance in some cases. EP-A3219755 relates to impact-modified thermoplastic molding materials having high scratch resistance, comprising siloxane-acrylate-based copolymers which use siloxane-polyester copolymers to improve scratch resistance. WO 2015/132190 teaches the use of silicones to improve scratch resistance and focuses on polypropylene molding materials.

EP-B1983018 relates to crosslinkable silicone compositions for coatings, which preferably comprise colloidal silica. Similarly, EP-A2436736 relates to compositions comprising organopolysiloxanes and colloidal silica, which are used for laminating films, but does not teach blends of organopolysiloxanes with vinyl aromatic molding materials (e.g.ASA). EP-A0369203 relates to graft copolymers comprising siloxanes and styrene which are grafted as graft shells onto rubber cores. Similarly, EP-A0369204 relates to graft copolymers based on polysiloxane/polyethylene. EP-A0653447 teaches graft polymers comprising polysiloxanes in the graft base. However, the preparation of these graft copolymers changes the chemical and mechanical properties of the graft copolymers and is rather complicated.

EP-A1529810 relates to polyester compositions comprising polysiloxane/polycarbonate copolymers, but does neither teach nor suggest stabilized thermoplastic polymer compositions based on graft polymers and vinyl aromatic copolymers (such as ASA). EP-A1153950 teaches crosslinked silyl-terminated vinyl polymers of star structure.

For certain applications, the impact-modified molding materials have good weathering stability, in particular UV resistance. ASA generally has better weathering stability and UV resistance than many other impact-modified compositions, such as Acrylonitrile Butadiene Styrene (ABS). However, its ultraviolet resistance is insufficient for other various uses. In particular, undesirable greying and color shifts often occur when the article is exposed to UV light and to weathering. For many applications, there is still a need to use uv stabilizers, such as Hindered Amine Light Stabilizer (HALS) compounds or uv absorbers. Some documents, such as US 4,692,486, US 9,701,813, EP-B2593510 and DE-A10316198, teach HALS stabilizers and combinations thereof as UV absorbers and light stabilizers. Even with the addition of such stabilizers, undesirable color shifts and graying still occur.

Thus, there is still a need for more stable compounds for improving the uv resistance of vinyl aromatic molding materials, and it is further desirable that such compounds can be readily used without altering the chemical structure of the thermoplastic polymer matrix.

It has surprisingly been found that organopolysiloxane compounds are effective stabilizers for improving the UV resistance of vinylaromatic molding materials. In particular, molding materials comprising ASA are further stabilized (in terms of resistance to UV light). For this purpose, this advantageous effect can be easily obtained by adding an organopolysiloxane compound. The prior art mentioned above neither teaches nor suggests that organopolysiloxanes have such surprising effects.

Accordingly, a first aspect of the present invention relates to a process for improving the resistance of a moulding material (P) to ultraviolet light, wherein the process comprises one (or only one) step of compounding:

(A)80 to 99.5 wt. -% of at least one thermoplastic polymer composition (a) comprising (or consisting of):

(A-1) at least one graft copolymer (A-1), and

(A-2) at least one thermoplastic matrix (A-2) based on one or more vinylaromatic copolymers;

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D)0 to 5% by weight of one or more further additives (D),

wherein components (A) to (D) add up to 100% by weight of the molding material (P).

Here, the organopolysiloxane compound (B) refers to a compound, i.e., a chemical entity. The organopolysiloxane compound (B) is generally not part of the graft copolymer (A-1), i.e.is not the core or graft shell of the graft copolymer (A-1).

Thermoplastic Polymer composition (A) (component A)

As mentioned above, the molding composition (P) comprises at least one thermoplastic polymer composition (A). The thermoplastic polymer composition (A) comprises at least one graft copolymer (A-1).

Graft copolymer (component A-1)

In a preferred embodiment, the graft copolymer (A-1) is a rubber-modified copolymer of acrylonitrile and styrene. In a preferred embodiment, the rubber particles are obtained by polymerizing at least one conjugated diene monomer or at least one acrylate monomer, and the copolymer of acrylonitrile and styrene used is graft-polymerized onto the rubber particles.

In a preferred embodiment, the at least one graft copolymer (A-1) used consists of:

a-1.1: from 20 to 90% by weight, preferably from 40 to 90% by weight, particularly preferably from 45 to 85% by weight, very particularly preferably from 50 to 80% by weight, based on the total amount of graft copolymer (A-1), of a graft base composed of one or more of the following monomers:

a-1.11: 65 to 100% by weight or 65 to 99.99% by weight, preferably 75 to 99.99% by weight, particularly preferably 80 to 99.98% by weight, based on the total weight of the graft base (A-1.1), of at least one (meth) acrylic acid C₁-C₈Alkyl esters, in particular n-butyl acrylate and/or 2-ethylhexyl acrylate,

a-1.12: from 0 to 35% by weight, preferably from 0 to 25% by weight, particularly preferably from 0 to 20% by weight, based on the total weight of the graft base (A-1.1), of at least one further comonomer selected from: styrene, alpha-methylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and N-phenylmaleimide, preferably styrene and alpha-methylstyrene, particularly preferably styrene;

a-1.13: from 0 to 10% by weight or from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight, particularly preferably from 0.02 to 2% by weight, based on the total weight of the grafting base (A-1.1), of one or more polyfunctional crosslinking monomers from the group consisting of allyl (meth) acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and dihydrodicyclopentadienyl acrylate (DCPA), which are present in an amount of at least 0.1% by weight, when component A11 is an acrylate;

a-1.2: from 10 to 80% by weight, preferably from 10 to 60% by weight, more preferably from 15 to 55% by weight, very particularly preferably from 20 to 50% by weight, based on the total amount of graft copolymer (A-1), of at least one graft layer consisting of one or more of the following monomers:

a-1.21: from 65 to 95% by weight, preferably from 70 to 90% by weight, particularly preferably from 75 to 85% by weight, based on the total weight of the graft layer (A-1.2), of at least one vinylaromatic monomer, preferably styrene and/or a-methylstyrene, in particular styrene;

a-1.22: 5 to 35 wt.%, preferably 10 to 30 wt.%, particularly preferably 15 to 25 wt.%, based on the total weight of the graft layer (A-1.2), of acrylonitrile and/or methacrylonitrile, preferably acrylonitrile; or and

a-1.3: from 0 to 30% by weight, preferably from 0 to 20% by weight, particularly preferably from 0 to 15% by weight, based on the total weight of the graft copolymer (A-1), of another component selected from:

at least one monoethylenically unsaturated monomer selected from methyl methacrylate, maleic anhydride and N-phenylmaleimide, preferably methyl methacrylate, and/or

At least one molecular weight regulator, in particular a mercaptan-based molecular weight regulator, such as tert-dodecyl mercaptan.

Preferred polyfunctional crosslinking monomers are allyl (meth) acrylate and/or dihydrodicyclopentadienyl acrylate (DCPA), more preferably DCPA.

Preferably, the graft copolymer (A-1) is prepared in an emulsion polymerization method or a suspension polymerization method. The graft base A-1.1, comprising (or consisting of) the monomers A-1.11, A-1.12 and optionally A-1.13, and processes for their preparation are known and described in the literature, for example, DE-A2826925, DE-A3149358 and DE-A3414118.

The graft polymerization for the synthesis of the graft shell A-1.2 can be carried out conveniently in the same vessel as the emulsion polymerization for the synthesis of the graft base A-1.1. During the reaction, additives such as emulsifiers, pH buffers and initiators may be added. The monomers of the graft shell, in particular monomers A-1.21 and A-1.22, can be added to the reaction mixture in one portion or in several portions (preferably stepwise in succession) during the polymerization. When the monomers A-1.21 and/or A-1.22 are added stepwise, a multilayer graft shell A-1.2 is generally obtained.

Suitable emulsifiers, buffers and initiators are described in WO 2015/150223 and WO 2015/078751.

In a preferred embodiment, the styrene-based graft copolymer (A-1) is acrylonitrile-styrene acrylate (ASA) and mixtures thereof.

In a preferred embodiment, the graft copolymer (A-1) according to the invention is particularly preferably an ASA copolymer having the following characteristics:

a-1.1: 40 to 90% by weight, based on the total weight of the styrene-based graft copolymer (A-1), of a graft base comprising:

a-1.11: 65 to 99.9 wt.%, preferably 90 to 99.5 wt.%, based on the total weight of the graft base (A-1.1), of at least one (meth) acrylic acid C₁-C₈Alkyl esters, preferably n-butyl acrylate and/or 2-ethylhexyl acrylate, particularly preferably n-butyl acrylate,

a-1.12: from 0 to 35% by weight, preferably from 1 to 10% by weight, of styrene, based on the total weight of the graft base (A-1.1),

a-1.13: from 0.1 to 5% by weight, preferably from 0.5 to 5% by weight, particularly preferably from 0.5 to 3% by weight, most preferably from 1 to 2.5% by weight, based on the total weight of the grafting base (A-1.1), of at least one polyfunctional crosslinking monomer from the group consisting of allyl (meth) acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and dihydrodicyclopentadienyl acrylate (DCPA), preferably from the group consisting of allyl (meth) acrylate and DCPA, particularly preferably DCPA, and

a-1.2: 10 to 60% by weight, based on the total weight of the styrene-based graft copolymer (a-1), of a graft comprising (or consisting of):

a-1.21: from 65 to 95% by weight, based on the total weight of the graft layer (A-1.2), of styrene;

a-1.22: 5 to 35 wt.%, based on the total weight of the graft layer (A-1.2), of acrylonitrile and

a-1.3: 0 to 30% by weight of MMA, based on the total weight of the styrene-based graft copolymer (A-1).

In a preferred embodiment, the at least one graft copolymer (A-1) is or comprises Acrylonitrile Styrene Acrylate (ASA) in which the rubber particles have an average particle diameter d₅₀From 50 to 1000nm, preferably from 60 to 600nm, where the average particle size is determined by scattered light measurements.

In general, the average particle size can be determined by scattered light measurements, i.e.by turbidimetry (Lange, J. colloids and polymers (Kolloid-Zeitschrift und Zeitschrift fur Polymer), 1968, 223 (1): 24-30), or by ultracentrifugation (for example Scholtan and Lange, J. colloids and polymers (Kolloid-Zeitschrift und Zeitschrift fur Polymer), 1972, 250 (8): 782-796), or by using a hydrochromatographic HDC (for example W.Wohlleben, H.Schuch, "measurement of the particle size distribution of a polymer latex", 2010, eds: L.Gugliotta, J.Vega, pp.129-153).

In a preferred embodiment, the graft copolymer (A-1) comprises a binary or ternary size distribution comprising (or consisting of)

(A-1a) at least one graft copolymer (A-1a) having an average particle diameter d of rubber particles in the ASA copolymer₅₀From 50 to 150 nm; and

(A-1b) at least one graft copolymer (A-1b) having an average particle diameter d of rubber particles in the ASA copolymer₅₀From 200 to 750 nm.

In a preferred embodiment, the graft copolymer (A-1) comprises a binary or ternary size distribution comprising (or consisting of)

(A-1a) at least one graft copolymer (A-1a) having an average particle diameter d of rubber particles in the ASA copolymer₅₀From 50 to 150nm or from 70 to 100 nm; and

(A-1b) at least one graft copolymer (A-1b) having an average particle diameter d of rubber particles in the ASA copolymer₅₀From 200 to 750nm or from 400 to 600 nm.

In a preferred embodiment, the first matrix rubber latex (L1) may be obtained from the (co) polymerization of butyl acrylate and one or more crosslinkers (e.g., tricyclodecenyl acrylate) in an aqueous solution, which may contain other ingredients, such as one or more salts (e.g., C)₁₂-C₁₈Paraffin sulfonic acid and/or sodium bicarbonate). The reaction temperature may be in the range of 55 to 70 ℃. In a preferred embodiment, the ratio of butyl acrylate: the mass ratio of tricyclodecenyl acrylate is from 10: 1 to 100: 1, preferably from 40: 1 to 80: 1, and the mass ratio and definition of the components used for the polymerization are preferably as described herein, more specific examples of which are provided below in the experimental section.

In a preferred embodiment, the first graft rubber latex (component A-1a) can be obtained by (co) polymerizing a base rubber latex (the first base rubber latex L1 obtainable as described above) with styrene and acrylonitrile in an aqueous solution. The aqueous solution may contain other ingredients, such as one or more salts (e.g., sodium persulfate). The reaction temperature may be in the range of 50 to 80 ℃. Optionally, the graft latex obtained may be coagulated (coagulation), the coagulation may be carried out in a salt solution (for example a magnesium sulphate solution) at a temperature of 50 to 80 ℃. The setting may optionally be followed by sintering (sintering, e.g., at a temperature in the range of 80 to 150 ℃). The mass ratios and definitions of the components are preferably as described herein, more specific examples of which are provided below in the experimental section.

In a preferred embodiment, the second matrix rubber latex (L2) may be obtained by (co) polymerizing butyl acrylate and one or more crosslinking agents (e.g., tricyclodecenyl acrylate) in an aqueous solution in the presence of the first matrix rubber latex (e.g., L1 described above). The aqueous solution may contain other ingredients, for example, one or more salts (e.g., sodium bicarbonate, sodium persulfate, and/or C)₁₂-C₁₈Paraffin sulfonic acid). The reaction temperature may be in the range of 55 to 70 ℃. In a preferred embodiment, the ratio of butyl acrylate: the mass ratio of tricyclodecenyl acrylate is from 10: 1 to 100: 1, preferably from 40: 1 to 80: 1. The mass ratios and definitions of the components are preferably as described herein, more specific examples of which are provided below in the experimental section.

In a preferred embodiment, the second graft rubber latex (component A-1b) can be obtained by (co) polymerizing a base rubber latex (e.g., the above-mentioned second base rubber latex L2) with styrene and acrylonitrile in an aqueous solution. The aqueous solution may contain other ingredients, such as one or more salts (e.g., sodium persulfate). The reaction temperature may be in the range of 50 to 80 ℃. Optionally, the graft latex obtained may be coagulated, the coagulation may be carried out in a salt solution (for example, a magnesium sulfate solution) at a temperature of 70 to 99 ℃. The setting may optionally be followed by sintering (e.g., at a temperature in the range of 80 to 150 ℃). The mass ratios and definitions of the components are preferably as described herein, more specific examples of which are provided below in the experimental section.

Thermoplastic matrix (component A-2)

In a preferred embodiment, the at least one thermoplastic matrix (A-2) comprises a copolymer comprising at least one vinyl cyanide and at least one vinyl aromatic compound. In a preferred embodiment, vinyl cyanide in the present invention refers to acrylonitrile. In a preferred embodiment, the vinyl aromatic compound in the present invention refers to styrene, alpha-methylstyrene or a combination thereof.

In a preferred embodiment, the at least one thermoplastic matrix (a-2) comprises a copolymer comprising acrylonitrile and at least one vinyl aromatic compound selected from styrene, alpha-methylstyrene and combinations thereof, with styrene being particularly preferred. Copolymers comprising or consisting of acrylonitrile and styrene are also known as poly (styrene-acrylonitrile) (SAN). Copolymers comprising or consisting of acrylonitrile and alpha-methylstyrene are also known as poly (alpha-methylstyrene/acrylonitrile) (AMSAN).

Poly (styrene-acrylonitrile) (SAN) and/or poly (alpha-methylstyrene/acrylonitrile) (AMSAN) can be used as thermoplastic polymer (a). Generally, any SAN and/or AMSAN copolymer known in the art may be used in the present invention.

In a preferred embodiment, the at least one thermoplastic polymer composition (a) comprises at least one copolymer (a-2) comprising (or consisting of):

18 to 45% by weight of at least one vinyl cyanide, in particular acrylonitrile; and from 55 to 82% by weight of at least one vinylaromatic compound, in particular a vinylaromatic compound selected from styrene and alpha-methylstyrene.

In a preferred embodiment, the SAN and AMSAN copolymers of the present invention comprise:

50 to 99 wt% of at least one selected from the group consisting of styrene and alpha-methylstyrene, based on the total weight of the SAN and/or AMSAN copolymer; and

1 to 50 wt% acrylonitrile based on the total weight of the SAN and/or AMSAN copolymer.

The weight average molecular weight of the SAN or AMSAN copolymer, determined by gel permeation chromatography on polystyrene standards, may be in the range from 15,000 to 200,000g/mol, preferably in the range from 30,000 to 150.000 g/mol.

In a preferred embodiment, the proportion of styrene and/or alpha-methyl groups is from 60 to 95% by weight and the proportion of acrylonitrile is from 40 to 5% by weight, based on the total weight of the SAN and/or AMSAN copolymer.

In a preferred embodiment, SAN or AMSAN is used, which incorporates acrylonitrile monomer units in an amount of < 36% by weight, based on the total weight of the SAN and/or AMSAN copolymer.

In a preferred embodiment, copolymers of styrene and acrylonitrile of the SAN or AMSAN type are used, which incorporate less acrylonitrile, not more than 35% by weight, based on the total weight of the SAN and/or AMSAN copolymer).

Among the most preferred SAN or AMSAN copolymers mentioned above, those having a viscosity number VN (determined in accordance with DIN 53726 at 25 ℃ in 0.5% by weight of dimethylformamide) of from 50 to 120ml/g are particularly preferred.

Herein, unless otherwise defined, all measurement specifications (e.g. DIN and PV specifications) preferably refer to the latest version of 3 months in 2018.

Copolymers of SAN or AMSAN components are known and their preparation, for example by free-radical polymerization, more particularly emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization, is also well documented in the literature.

Thermoplastic Polymer composition (A)

In a preferred embodiment, the at least one thermoplastic polymer composition (a) comprises (or consists of)

(A-1) 5 to 50% by weight, based on the amount of thermoplastic polymer composition (A), of at least one graft copolymer (A-1) comprising or consisting of Acrylonitrile Styrene Acrylate (ASA) wherein the rubber particles in the ASA copolymer have a d₅₀From 50 to 1000nm, wherein the average particle diameter is determined by scattered light, and

(A-2) 20 to 95% by weight, based on the amount of thermoplastic polymer composition (A), of at least one thermoplastic matrix (A-2) comprising 18 to 45% by weight of at least one vinyl cyanide (especially acrylonitrile) and 55 to 82% by weight of at least one vinyl aromatic compound (especially selected from styrene and alpha-methylstyrene), and

(A-3) from 0 to 75% by weight, based on the amount of thermoplastic polymer composition (A), of one or more further thermoplastic polymers (A-3), in particular one or more thermoplastic polymers (A-3) selected from the group consisting of Polycarbonates (PC), Polyamides (PA) and mixtures thereof.

In another preferred embodiment, the thermoplastic polymer composition (a) comprises 5 to 50% by weight, preferably 7 to 50% by weight, in particular 10 to 45% by weight, of at least one styrene-based graft copolymer (a-1), and 0 to 95% by weight, preferably 20 to 93% by weight, in particular 45 to 90% by weight, of at least one thermoplastic matrix (a-2) selected from the group consisting of poly (styrene-acrylonitrile) (SAN), poly (alpha-methylstyrene-acrylonitrile) (AMSAN) and mixtures thereof, based on the total weight of the thermoplastic polymer composition (a).

In another preferred embodiment, the thermoplastic polymer composition (a) comprises from 20 to 50% by weight, preferably from 30 to 40% by weight, based on the total weight of the thermoplastic polymer composition (a), of at least one styrene-based graft copolymer (a-1), and from 40 to 80% by weight, preferably from 60 to 70% by weight, of at least one thermoplastic matrix (a-2) selected from the group consisting of poly (styrene-acrylonitrile) (SAN), poly (alpha-methylstyrene-acrylonitrile) (AMSAN) and mixtures thereof.

In another preferred embodiment, the thermoplastic polymer composition (a) comprises 5 to 50% by weight, preferably 20 to 40% by weight, based on the total weight of the thermoplastic polymer composition (a), of at least one styrene-based graft copolymer (a-1), and 40 to 80% by weight, preferably 60 to 70% by weight, based on the total weight of the thermoplastic matrix (a-2), of a thermoplastic matrix (a-2) comprising 40 to 60% by weight of SAN and 60 to 40% of AMSAN, preferably 45 to 55% of SAN and 55% to 45% of AMSAN, based on the total weight of the thermoplastic matrix (a-2).

In another preferred embodiment, the thermoplastic polymer composition (a) comprises 5 to 50 wt. -%, based on the total weight of the thermoplastic polymer composition (a), of at least one component a-1; 5 to 80% by weight of at least one component A-2 selected from poly (styrene-acrylonitrile) (SAN), poly (alpha-methylstyrene-acrylonitrile) (AMSAN) and mixtures thereof; and from 0 to 75% by weight (in particular from 40 to 55% by weight) of a further polymer component (A-3) selected from the group consisting of Polycarbonate (PC), Polyamide (PA) and mixtures thereof. In particular, component (A-3) is one or more Polycarbonates (PC).

In a preferred embodiment, the thermoplastic polymer composition (a) comprises from 0 to 75 wt%, from 10 to 70 wt%, from 20 to 65 wt%, from 30 to 60 wt%, or from 40 to 55 wt% of the polymer component (a-3).

In a preferred embodiment, the thermoplastic polymer composition (a) comprises from 0 to 75 wt%, from 10 to 70 wt%, from 20 to 65 wt%, from 30 to 60 wt%, or from 40 to 55 wt% of a polymer component (a-3) selected from the group consisting of Polycarbonate (PC), Polyamide (PA) and mixtures thereof, in particular wherein a-3 is one or more Polycarbonates (PC).

In another preferred embodiment, the thermoplastic polymer composition (A) comprises (or consists of)

(A-1) 5 to 50 weight percent (or 20 to 40 weight percent) of at least one graft copolymer (A-1), based on the total weight of the thermoplastic polymer composition (A); and

(A-2) from 20 to 65% by weight (or from 25 to 40% by weight), based on the total weight of the thermoplastic polymer composition (A), of at least one thermoplastic matrix (A-2) comprising at least one vinyl cyanide and at least one vinyl aromatic compound, and,

(A-3) from 30 to 75% by weight (or from 40 to 55% by weight), based on the total weight of the thermoplastic polymer composition (A), of one or more other thermoplastic polymers (A-3), in particular one or more polycarbonate polymers.

In another preferred embodiment, the thermoplastic polymer composition (A) comprises (or consists of)

(A-1) 5 to 50 wt.% (or 20 to 40 wt.%) based on the thermoplastic polymer composition (A), of at least one graft copolymer (A-1) comprising or consisting of styrene acrylic acrylate (ASA), wherein the mean particle diameter d of the rubber particles in the ASA copolymer₅₀From 50 to 1000nm, the average particle diameter being determined by scattered light, and

(A-2) from 20 to 65% by weight (or from 25 to 40% by weight), based on the thermoplastic polymer composition (A), of at least one thermoplastic matrix (A-2) comprising from 18 to 45% by weight of at least one vinyl cyanide compound and from 55 to 82% by weight of at least one vinyl aromatic compound, and

(A-3) 30 to 75 wt.% (or 40 to 55 wt.%) based on the thermoplastic polymer composition (A), of one or more other thermoplastic polymers (A-3), in particular one or more polycarbonate polymers.

Polycarbonate component the polycarbonate may be any polycarbonate. The polycarbonate includes one or more, preferably one or two, more preferably one aromatic polycarbonate. Aromatic polycarbonates include, for example, polycondensation products, such as aromatic polycarbonates, aromatic polyester carbonates.

Suitable aromatic polycarbonates and/or aromatic polyester carbonates according to the invention are known in the literature or can be prepared by processes known in the literature (for the preparation of aromatic polycarbonates see, for example, DE-B1495626, DE-A2232877, DE-A2703376, DE-A2714544, DE-A3610 and DE-A3832396). The preparation of aromatic polycarbonates can be carried out by reacting diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface process. Chain terminators, for example monophenols, may optionally be used and branching agents which are trifunctional or more than trifunctional, for example triphenols or tetraphenols, may optionally be used.

Or by melt polymerization by reacting a dihydric phenol with diphenyl carbonate.

The diphenols used for the preparation of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably compounds of the formula (Ia).

Wherein A is a single bond, C₁To C₅Alkylene radical, C₂To C₅Alkylene radical, C₅To C₆Cycloalkylene, -O-, -SO-, -CO-, -S-, -SO2-, C₆To C₁₂Arylene (onto which an aryl group optionally containing a heteroatom may be fused), a group of formula (IIa) or (IIIa),

b is C₁-C₁₂Alkyl, preferably methyl, or halogen, preferably chlorine and/or bromine,

x is each independently of the others 0, 1 or 2

p is 1 or 0, and

for each X¹，R⁵And R⁶Independently of one another, hydrogen or C₁-C₆Alkyl, preferably hydrogen, methyl or ethyl,

X¹which represents carbon, is a carbon atom,

m represents an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one X¹，R⁵And R⁶And is an alkyl group.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenol, bis- (hydroxyphenyl) -C₁-C₅Alkanes, bis- (hydroxyphenyl) -C₅-C₆Cycloalkanes, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl) sulfoxides, bis- (hydroxyphenyl) ketones, bis- (hydroxyphenyl) sulfones and α, α -bis- (hydroxyphenyl) -diisopropylbenzenes, and their nuclear brominated and/or nuclear chlorinated derivatives. Particularly preferred diphenols are 4,4 '-dihydroxydiphenyl, bisphenol A, 2, 4-bis- (4-hydroxyphenyl) -2-methylbutane, 1, 1-bis- (4-hydroxyphenyl) -cyclohexane, 1, 1-bis- (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 4,4' -dihydroxydiphenylsulfone, and their dibromo and tetrabromo or chlorinated derivatives, for example 2, 2-bis- (3-chloro-4-hydroxyphenyl) propane, 2, 2-bis- (3, 5-dichloro-4-hydroxyphenyl) propane or 2, 2-bis- (3, 5-dibromo-4-hydroxyphenyl) -propane. 2, 2-bis- (4-hydroxyphenyl) -propane (bisphenol A) is particularly preferred. The diphenols may be used individually or as mixtures, as desired. The diphenols are known from the literature or are obtainable by processes known from the literature.

Suitable chain terminators for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4, 6-tribromophenol, and long-chain alkylphenols, such as 4- [2- (2,4, 4-trimethylpentyl) ] -phenol, 4- (1, 3-tetramethylbutyl) -phenol or 4- (1, 3-tetramethylbutyl) -phenol according to DE-A2842005

Monoalkylphenols or dialkylphenols having a total of from 8 to 20 carbon atoms in the alkyl substituents, for example 3, 5-di-tert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3, 5-dimethylheptyl) -phenol and 4- (3, 5-dimethylheptyl) -phenol. The amount of chain terminators to be used can generally be between 0.5 mol% and 10 mol%, based on the molar sum of the particular diphenols used.

In a preferred embodiment, the polycarbonates are, for the purposes of the present invention, thermoplastic, aromatic polycarbonates having an average weight-average molecular weight (MW, determined by ultracentrifuge or by scattered light measurement) of from 10,000 to 200,000g/mol, preferably from 15,000 to 80,000g/mol, particularly preferably from 24,000 to 32,000 g/mol.

The thermoplastic, aromatic polycarbonates may be branched in a known manner, particularly preferably by incorporation of 0.05 to 2.0 mol%, based on the total amount of diphenols used, of trifunctional or more than trifunctional compounds, for example compounds having more than three phenolic groups. Both homopolycarbonates and copolycarbonates are suitable.

The aromatic polyester carbonates may be in the linear or branched known form (cf. DE-A2940024 and DE-A3007934). Branching agents which may be used are, for example, trifunctional or more than trifunctional carboxylic acid chlorides, such as trimellitic trichloride, cyanuric acid trichloride, 3,3',4,4' -benzophenone-tetracarboxylic acid tetrachloride, 1,4,5, 8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride. In amounts of from 0.01 to 1.0 mol%, based on the dicarboxylic acid dichloride used. Or using trifunctional or more than trifunctional phenols, for example phloroglucinol, 4, 6-dimethyl-2, 4, 6-tri- (4-hydroxyphenyl) hept-2-ene, 4, 6-dimethyl-2, 4, 6-tri- (4-hydroxyphenyl) heptane, 1,3, 5-tri- (4-hydroxyphenyl) -benzene, 1,1, 1-tri- (4-hydroxyphenyl) -ethane, tri (4-hydroxyphenyl) -phenylmethane, 2, 2-bis- [4, 4-bis- (4-hydroxyphenyl) -cyclohexyl ] -propane, 2, 4-bis- (4-hydroxyphenyl-isopropyl) -phenol, tetra (4-hydroxyphenyl) methane, 2, 6-bis- (2-hydroxy-5-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2, 4-dihydroxyphenyl) -propane, tetrakis- (4- [ 4-hydroxyphenyl-isopropyl ] -phenoxy) -methane and 1, 4-bis- [4,4' -dihydroxytriphenyl) -methyl ] -benzene. The amount used is from 0.01 to 1.0 mol%, based on the diphenols used. Phenolic branching agents may be introduced into the reaction vessel first together with the diphenols, acid chloride branching agents may be introduced together with the acid dichlorides.

The content of carbonate structural units in the thermoplastic, aromatic polyester carbonates may be varied as desired. Preferably, the content of carbonate groups is at most 100 mol%, in particular at most 80 mol%, particularly preferably at most 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and the carbonate content of the aromatic polyester carbonates may be present in the polycondensate in the form of blocks or in random distribution.

The relative solution viscosity (. eta.rel) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.20 to 1.32 (measured at 25 ℃ in a solution of 0.5g of polycarbonate or polyester carbonate in 100ml of methylene chloride).

The thermoplastic aromatic polycarbonates and polyester carbonates may be used individually or in the form of any desired mixtures of one or more, preferably one to three or one or two. Most preferably, only one type of polycarbonate is used. Preferably, the aromatic polycarbonate is a polycarbonate based on bisphenol a and phosgene, which includes polycarbonates prepared from the corresponding precursors or synthetic building blocks of bisphenol a and phosgene. These preferred aromatic polycarbonates may be linear or branched due to the presence of branch points.

Polyamide component

The polyamide may be any polyamide. Examples of suitable polyamides are the known homopolyamides, copolyamides and mixtures of these polyamides. They may be semi-crystalline and/or amorphous polyamides. Suitable semi-crystalline polyamides are polyamide-6, 6, and mixtures and corresponding copolymers thereof. Also included are semi-crystalline polyamides whose acid component consists wholly or partly of terephthalic acid and/or isophthalic acid and/or suberic acid and/or sebacic acid and/or azelaic acid and/or adipic acid and/or cyclohexanedicarboxylic acid and whose diamine component consists wholly or partly of isophthalylene and/or terephthalylene diamine and/or hexamethylenediamine and/or 2,2, 4-trimethylhexamethylenediamine and/or isophoronediamine, the composition of which is known per se. Mention may furthermore be made of polyamides prepared wholly or partly from lactams having 7 to 12 carbon atoms in the ring, optionally together with one or more of the abovementioned starting components.

Particularly preferred semi-crystalline polyamides are polyamide-6 and polyamide-6, 6 and mixtures thereof. Polyamides which can be used as amorphous are known products. They are prepared by polycondensation of diamines, such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2, 4-and/or 2,4, 4-trimethylhexamethylenediamine, m-and/or p-xylylenediamine, bis- (4-aminocyclohexyl) -methane, bis- (4-aminocyclohexyl) -propane, 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane, 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine, 2, 5-and/or 2, 6-bis- (aminomethyl) -norbornane and/or 1, 4-diaminomethylcyclohexane, with dicarboxylic acids, such as oxalic acid, adipic acid, azelaic acid, sebacic acid, heptanedioic acid, 2,2, 4-and/or 2,4, 4-trimethyladipic acid, isophthalic acid and terephthalic acid.

Also suitable are copolymers obtained by polycondensation of various monomers, and copolymers prepared by addition of aminocarboxylic acids such as epsilon-aminocaproic acid, omega-aminoundecanoic acid or omega-aminolauric acid or lactams thereof. Particularly suitable amorphous polyamides are those prepared from isophthalic acid, hexamethylenediamine and other diamines such as 4,4' -diaminodicyclohexylmethane, isophoronediamine, 2,2, 4-and/or 2,4, 4-trimethylhexamethylenediamine, 2, 5-and/or 2, 6-bis- (aminomethyl) -norbornene; or from isophthalic acid, 4,4' -diamino-dicyclohexylmethane and epsilon-caprolactam; or from isophthalic acid, 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and isomer mixtures of 2,2, 4-and/or 2,4, 4-trimethylhexamethylenediamine. Instead of pure 4,4 '-diaminodicyclohexylmethane, it is also possible to use mixtures of positionally isomeric diaminodicyclohexylmethanes which consist of 70 to 99 mol% of the 4,4' -diamino isomer, from 1 to 30 mol% of the 2,4 '-diamino isomer, from 0 to 2 mol% of the 2, 2' -diamino isomer and optionally correspond to the more highly condensed diamines obtained by hydrogenation of technical-grade diaminodiphenylmethane. Terephthalic acid can replace up to 30% of isophthalic acid.

The relative viscosity of the polyamide (measured at 25 ℃ in a 1% by weight solution in m-cresol or in a 1% (w/v) solution in sulfuric acid (96% by weight)) is preferably from 2.0 to 5.0, particularly preferably from 2.5 to 4.0.

In a preferred embodiment, the at least one thermoplastic polymer composition (a) comprises (or consists of):

(A-1), based on the thermoplastic polymer composition (A), from 5 to 50% by weight (or from 20 to 40% by weight) of at least one graft copolymer (A-1) comprising or consisting of styrene acrylic acrylate (ASA), wherein the mean particle diameter d of the rubber particles in the ASA copolymer₅₀From 50 to 1000nm, the average particle diameter being determined by scattered light, and

(A-2) from 20 to 95% by weight (or from 25 to 40% by weight), based on the thermoplastic polymer composition (A), of at least one thermoplastic matrix (A-2) comprising from 18 to 45% by weight of at least one vinyl cyanide, in particular acrylonitrile, and from 55 to 82% by weight of at least one vinyl aromatic compound, in particular a vinyl aromatic compound selected from styrene and alpha-methylstyrene, and

(A-3), based on the thermoplastic polymer composition (A), from 0 to 75% by weight, from 30 to 75% (or from 40 to 55% by weight) of one or more further thermoplastic polymers (A-3), in particular selected from Polycarbonates (PC), Polyamides (PA) and mixtures thereof.

Organopolysiloxane compound (component B)

The organopolysiloxane compound (B) can be any organopolysiloxane. It has surprisingly been found that the addition of small amounts of at least one organopolysiloxane compound (B) is sufficient to improve the UV resistance of the molding materials (P) according to the invention.

In a preferred embodiment, the at least one organopolysiloxane compound (B) has a weight-average molecular weight Mw of from 20,000g/mol to 100,000g/mol, preferably from 30,000g/mol to 80,000g/mol, determined by Gel Permeation Chromatography (GPC), based on polystyrene and Tetrahydrofuran (THF) as solvent.

In a preferred embodiment, the organopolysiloxane compound (B) has a viscosity of from 500 to 5000mPas at 25 ℃, determined by falling ball viscometer or capillary viscometer. In a preferred embodiment, the at least one organopolysiloxane compound (B) comprises repeating units having the following formula (I):

wherein each R¹Independently selected from linear or branched, saturated or unsaturated hydrocarbon radicals having from 1 to 10, preferably from 1 to 6, carbon atoms.

In a preferred embodiment, each R is¹Independently selected from linear or branched or cyclic saturated or unsaturated hydrocarbon radicals having from 1 to 6 carbon atoms.

As used herein, hydrocarbyl groups are to be understood in the broadest sense. For example, the hydrocarbyl group can be an aliphatic group, an aromatic group, an alkylaromatic group, an alkenylaromatic group, an alkynylaromatic group, an alkylated aryl group, an alkenylated aryl group, an alkylated (and/or alkenylated and/or alkynylated) alkylaromatic group, and the like. The hydrocarbon group may be selected from linear, branched or cyclic alkyl, linear, branched or cyclic alkynyl and linear, branched or cyclic alkenyl. For example, the hydrocarbon group may be selected from methyl, ethyl, n-propyl, isopropyl, linear, branched or cyclic butyl, linear, branched or cyclic pentyl, or linear, branched or cyclic hexyl. For example, the hydrocarbyl group may be selected from aryl groups, in particular phenyl groups, which may optionally be alkylated; and alkylaryl groups, particularly alkylphenyl groups, which may optionally be alkylated.

In a preferred embodiment, the organosiloxane portion of organopolysiloxane compound (B) is selected from the group consisting of poly (dimethylsiloxane), poly (diethylsiloxane), poly (dipropylsiloxane), poly (dibutylsiloxane), and mixtures thereof.

In a preferred embodiment, the organopolysiloxane compound (B) is not poly [ methylpropyl-3-oxy-4- (2,2,6, 6-tetramethyl-4-piperidyl) ] siloxane. In a preferred embodiment, the organopolysiloxane compound (B) does not form part of the graft copolymer.

In an alternative preferred embodiment, the at least one organopolysiloxane compound (B) comprises polysiloxane moieties derived from recurring units having the above formula (I) and from recurring units having the following formula (Ib):

wherein R is¹As defined above, R⁴Represents a polyolefin moiety, preferably derived from repeating units selected from ethylene, propylene and mixtures thereof. The recurring units of the formula (Ib) are statistically distributed in the polysiloxane part in amounts of from 1 to 50% by weight, preferably from 2 to 30% by weight, in particular from 3 to 15% by weight, based on the total weight of the polysiloxane part. Accordingly, an alternative embodiment relates to block copolymers having a brush structure.

In a preferred embodiment, the at least one organopolysiloxane compound (B) is a block copolymer comprising blocks of polysiloxane moieties and blocks of polyester and/or polyolefin moieties having repeating units of formula (I).

The organopolysiloxane compound (B) can further comprise at least one further repeating unit, in particular a repeating unit derived from a polymerizable ester and/or olefin. In another preferred embodiment, the organopolysiloxane compound (B) is a block copolymer comprising at least one block of polysiloxane moieties having repeating units of formula (I) and at least one block of polyester moieties and/or at least one block of polyolefin moieties. Furthermore, a functional group may be present, preferably a functional group as a terminal group. Particularly preferred functional groups are selected from vinyl and/or alkoxy groups, in particular alkoxy groups having a linear or branched alkyl group comprising 1 to 6 carbon atoms.

In a preferred embodiment, the organopolysiloxane compound (B) comprises more than 70% by weight, preferably more than 80% by weight, particularly preferably more than 90% by weight, of recurring units of the following formula (I): in particular wherein each R is¹represents-CH₃or-CH₂CH₃。

In another preferred embodiment, the polyester portion of the organopolysiloxane compound (B), if present, is derived from a repeat unit having the following formula (II):

wherein R is²Independently selected from hydrogen atoms and linear or branched, saturated or unsaturated hydrocarbon radicals having from 1 to 10, preferably from 1 to 6, carbon atoms, and m is an integer from 1 to 10, preferably from 1 to 5. In another preferred embodiment, R²Represents a hydrogen atom.

In another preferred embodiment, the polyolefin portion of the organopolysiloxane compound (B), if present, is derived from repeating units selected from ethylene, propylene, and mixtures thereof.

In one embodiment of the present invention, at least one organopolysiloxane compound is a polyester-polysiloxane-block copolymer. Wherein the polysiloxane blocks are preferably derived from repeating units having formula (I) above.

In another preferred embodiment of the present invention, at least one organopolysiloxane compound is a polyolefin-polysiloxane-block copolymer. Wherein the polysiloxane blocks are preferably derived from repeating units having formula (I) above.

In another preferred embodiment, at least one organopolysiloxane compound (B) is a [ polyolefin-B-polysiloxane-B-polyester ] triblock copolymer. Wherein the polysiloxane blocks are preferably derived from repeating units having formula (I) above.

As previously mentioned, the at least one organopolysiloxane compound (B) may be present in an amount of 0.5 to 5 wt.%, based on the entire molding material (P). It has been found that even very small amounts of said one organopolysiloxane compound, in particular in amounts in the range of 0.55 to 4% by weight or 0.6 to 3% by weight, are sufficient to achieve beneficial technical effects.

Colorants, dyes and pigments (optional component C)

As mentioned above, the molding materials (P) may further comprise from 0 to 10% by weight, generally from 0.1 to 5% by weight, of dyes, pigments or colorants, which may be added in the form of a dye-, pigment-containing masterbatch or as colorants to the polymer matrix. In a preferred embodiment, the dye, pigment or colorant is added in the form of a masterbatch comprising from 20 to 70% by weight, preferably from 40 to 60% by weight, based on the total amount of the masterbatch, of a dye, pigment, colorant or mixture thereof and from 30 to 80% by weight, preferably from 40 to 60% by weight, based on the total amount of the masterbatch, of a copolymer of a vinyl aromatic olefin and acrylonitrile as matrix polymer. Preferably, the matrix polymer is selected from poly (styrene-acrylonitrile) (SAN), poly (alpha-methylstyrene/acrylonitrile) (AMSAN) and/or poly (styrene-methyl methacrylate) (SMMA).

Examples of suitable pigments include titanium dioxide, phthalocyanines, ultramarine blue, iron oxides and carbon black, and all organic pigments. Examples of suitable colorants include all transparent, translucent or opaque dyes which can be used for coloring polymers, in particular those dyes which are suitable for the coloring of styrene copolymers.

In a preferred embodiment, the molding material (P) comprises carbon black as component (C).

Other additives (optional component D)

As used herein, the one or more further additives (D) are any additives that may be used in the moulding compound (P). For example, the further additive (D) may be selected from plasticizers, aliphatic amide waxes, aliphatic fatty acid esters and UV stabilizers.

Optionally, various additives may be added to the molding compounds in amounts of from 0 to 5% by weight, usually from 0.1 to 5% by weight, as auxiliaries and processing additives. Suitable additional additives (D) include all substances which are customarily used for processing or working up polymers. In general, the presence of the organopolysiloxane compound (B) does not exclude the presence of organopolysiloxane compounds also in the additive (D), which are different from the organopolysiloxane compound (B).

The additive (D) may be added in the form of a masterbatch, wherein the additive (D) is contained in a polymer matrix. In a preferred embodiment, the additive (D) is added in the form of a masterbatch comprising from 20 to 70% by weight, preferably from 40 to 60% by weight, based on the total amount of masterbatch, of the additive (D) or a mixture thereof and from 30 to 80% by weight, preferably from 40 to 60% by weight, based on the total amount of masterbatch, of a copolymer of a vinylaromatic olefin and acrylonitrile as matrix polymer. Preferably, the matrix polymer is selected from poly (styrene-acrylonitrile) (SAN), poly (alpha-methylstyrene/acrylonitrile) (AMSAN) and/or poly (styrene-methyl methacrylate) (SMMA).

Examples of additives (D) include, for example, antistatic agents, antioxidants, flame retardants, stabilizers for improving thermal stability, stabilizers for improving light stability, stabilizers for enhancing hydrolysis resistance and chemical resistance, agents against thermal decomposition, especially lubricants, which can be used for producing shaped bodies/articles. These other added substances may be mixed at any stage of the manufacturing operation, but are preferably mixed at an early stage in order to benefit as early as possible from the stabilizing effect (or other specific effect) of the added substances.

Examples of suitable antistatic agents include amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or-alkyleneamines, polyethylene glycol esters, copolymers of ethylene oxide glycol and propylene oxide glycol (especially di-or tri-block copolymers of ethylene oxide blocks and propylene oxide blocks), and glycerol monostearate and stearate and mixtures thereof.

Examples of suitable antioxidants include sterically hindered mono-or polycyclic phenolic antioxidants, which may contain various substitutions and may also be bridged by substituents. They include not only monomers but also oligomeric compounds which may be built up from a plurality of phenol units. Hydroquinone and hydroquinone analogues are also suitable, and antioxidants based on tocopherol and derivatives or substituted compounds thereof are also suitable. Can also makeMixtures of different antioxidants were used. In principle, any compounds customary in the art or suitable for styrene copolymers, for example fromA series of antioxidants. In addition to the phenolic antioxidants listed above as examples, co-stabilisers (co-stabilisers), in particular phosphorus-or sulphur-containing co-stabilisers, may also be used. These phosphorus-or sulfur-containing costabilizers are known to the person skilled in the art.

Examples of suitable flame retardants that may be used include halogen-or phosphorus-containing compounds known to those skilled in the art, magnesium hydroxide, and other common compounds, or mixtures thereof.

Examples of suitable light stabilizers include various substituted resorcinols, salicylates, benzotriazoles and benzophenones.

Suitable matting agents include not only inorganic substances, for example talc, glass beads or metal carbonates (e.g. MgCO)₃，CaCO₃) And also polymer particles, in particular based on methyl methacrylate, styrene compounds, acrylonitrile or mixtures thereof, with a diameter D₅₀Spherical particles larger than 1 μm. Polymers comprising copolymerized acidic and/or basic monomers may also be used.

Examples of suitable anti-dripping agents (antidrip agents) include polytetrafluoroethylene (Teflon) polymers and ultra high molecular weight polystyrene (weight average molar mass Mw higher than 2,000,000).

Examples of fibrous/pulverulent fillers include glass fibers, glass mats or filament glass rovings, chopped glass, glass beads and carbon or glass fibers in the form of wollastonite, glass fibers being particularly preferred. When glass fibers are used, they may be finished with sizing and coupling agents to improve their compatibility with the blend components. The incorporated glass fibers may take the form of short glass fibers or continuous filaments (rovings).

Examples of suitable particulate fillers include carbon black, amorphous silica, magnesium carbonate, powdered quartz, mica, bentonite, talc, feldspar or especially calcium silicates, such as wollastonite and kaolin.

Examples of suitable stabilizers include hindered phenols, but also include vitamin E/compounds of similar structure, and butylated condensation products of cresols and dicyclopentadiene. HALS stabilizers (hindered amine light stabilizers), benzophenones, resorcinols, salicylates, benzotriazoles are also suitable. Other suitable compounds include thiocarboxylates. C of thiopropionic acid may also be used₆-C₂₀Alkyl esters, in particular stearates and laurates thereof.

Dilauryl thiodipropionate (dilauryl thiodipropionate), distearyl thiodipropionate (distearyl thiodipropionate) or mixtures thereof may also be used. Examples of further additives include HALS absorbers, such as bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate or UV absorbers, such as 2H-benzotriazol-2-yl- (4-methylphenol). Additional UV stabilizers, in particular HALS, may optionally be used to support the stabilizing action of the organopolysiloxane compound (B).

Suitable lubricants and mold release agents include stearic acid, stearyl alcohol, stearates, polyolefin waxes and/or generally higher fatty acids, derivatives thereof and corresponding fatty acid mixtures containing from 1 to 45 carbon atoms. In another preferred embodiment, the composition comprises a compound having the formula R¹-CONH-R²Wherein R is¹And R²Each independently selected from aliphatic, saturated or unsaturated hydrocarbon radicals having from 1 to 30 carbon atoms, preferably from 12 to 24 carbon atoms, particularly preferably from 16 to 20 carbon atoms. In another preferred embodiment of the present invention, the composition may additionally comprise a compound having the formula R³-CO-OR⁴The fatty acid ester compound of (1), wherein R³And R⁴Each independently selected from aliphatic, saturated or unsaturated hydrocarbon radicals having from 1 to 45 carbon atoms, preferably from 15 to 40 carbon atoms, particularly preferably from 25 to 35 carbon atoms. In addition, ethylene-bis (stearamide) is also particularly suitable.

In another preferred embodiment, the thermoplastic polymerThe composition (P) may comprise organic, inorganic or mixed phosphates, in particular of alkali or alkaline earth metals, e.g. Ca₃(PO₄)₂And/or an organophosphate having an alkyl or aryl group having 1 to 12 carbon atoms. These phosphates may conveniently be added in the form of a masterbatch, for example in combination with a polyolefin wax and/or an olefin/styrene copolymer.

In another preferred embodiment, the thermoplastic polymer composition (P) may further comprise a polyester-modified polysiloxane, in particular a polyester-polysiloxane-block copolymer, preferably a [ polyester-b-polysiloxane-b-polyester ] triblock copolymer. The polysiloxane moiety contained in the polyester-polysiloxane-block copolymer is preferably derived from poly (dimethylsiloxane), poly (diethylsiloxane), poly (dipropylsiloxane), poly (dibutylsiloxane) and mixtures thereof.

Molding material (P)

Since the molding material (P) of the present invention comprises at least one vinylaromatic component (since component (A-2) is based on one or more vinylaromatic copolymers), it may also be referred to as "vinylaromatic molding material".

In a preferred embodiment, the molding material (P) comprises (or consists of):

(A)85 to 99.3 wt. -% of at least one thermoplastic polymer composition (a) comprising (or consisting of) at least one graft copolymer (a-1) and at least one thermoplastic matrix (a-2);

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D)0.1 to 5% by weight of one or more further additives (D),

wherein components (A) to (D) add up to 100% by weight of the molding material (P).

In a preferred embodiment, the molding material (P) comprises (or consists of):

(A)85 to 99.3 wt. -% of at least one thermoplastic polymer composition (a) comprising (or consisting of):

(A-1), based on the thermoplastic polymer composition (A), from 5 to 50% by weight (or from 20 to 40% by weight) of at least one graft copolymer (A-1) comprising (or consisting of) an Acrylonitrile Styrene Acrylate (ASA), wherein the mean particle diameter d of the rubber particles in the ASA copolymer₅₀From 50 to 1000nm, the average particle diameter being determined by scattered light, and

(A-3), based on the thermoplastic polymer composition (A), from 0 to 75% by weight (or from 40 to 55% by weight) of one or more further thermoplastic polymers (A-3), in particular one or more further thermoplastic polymers selected from the group consisting of Polycarbonates (PC), Polyamides (PA) and mixtures thereof.

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D)0.1 to 5% by weight of one or more further additives (D),

wherein components (A) to (D) add up to 100% by weight of the molding material (P).

In a preferred embodiment, the molding material (P) does not contain colloidal silica.

In a preferred embodiment, the molding material (P) obtained by the process of the invention has at least one of the following characteristics:

(a) after 2400 hours of artificial ageing according to PV3929, the color shift of the molding material (P) is less than 70%, preferably 60%, of the color shift of a comparable molding material (P) without organopolysiloxane compound (B) after 2400 hours of the same artificial weathering according to PV 3929;

(b) after 3200 hours of artificial ageing according to PV3929, the colour shift of the molding material (P) is less than 65%, preferably 60%, of the colour shift of a comparable molding material (P) without organopolysiloxane compound (B) after 3200 hours of the same artificial weathering according to PV 3929;

(c) after 2400 hours of artificial ageing according to PV3929, the color shift of the molding material (P) is less than 80%, preferably 75%, of the color shift of a comparable molding material (P) without organopolysiloxane compound (B) after 2400 hours of the same artificial weathering according to PV 3929;

(d) after 3200 hours of artificial ageing according to PV3929, the colour shift of the molding material (P) is less than 25%, preferably 20%, of the colour shift of a comparable molding material (P) without organopolysiloxane compound (B) after 3200 hours of the same artificial weathering according to PV 3929; and/or

(d) Compared with comparable molding materials (P) which have likewise been artificially weathered and do not use organopolysiloxane compounds (B), the inventive molding materials (P) have a gray scale which is at least 1 unit higher, preferably at least 2 units higher, after 3200 hours of weathering according to PV 3930.

In a preferred embodiment, the molding materials (P) obtained by the process of the invention have, after 3200 hours of weathering according to PV3930, up to 1 unit, preferably at least 2 units, higher than comparable molding materials (P) which have also been artificially weathered without the use of organopolysiloxane compounds (B). Furthermore, the molding materials (P) obtained by the process according to the invention have a colour shift after 2400 hours of weathering according to PV3930 of less than 70%, preferably less than 60%, of the latter colour shift compared with comparable molding materials (P) likewise artificially weathered without the use of organopolysiloxane compounds (B).

In a preferred embodiment, the molding material (P) comprises (or consists of):

(A)80 to 99.5 wt. -% of at least one thermoplastic polymer composition (a) comprising (or consisting of):

(A-1) 5 to 50 wt% (or 20 to 40 wt%) of at least one graft copolymerization based on the thermoplastic polymer composition (A)The substance (A-1) comprising (or consisting of) an Acrylonitrile Styrene Acrylate (ASA) wherein the mean particle size d of the rubber particles in the ASA copolymer₅₀From 50 to 1000nm, the average particle diameter being determined by scattered light,

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D)0 to 5% by weight of one or more further additives (D),

wherein the sum of components (A) to (D) is 100% by weight of the molding material (P),

and wherein the molding material (P) obtained by the process of the invention has at least one of the following characteristics:

In a preferred embodiment, the molding material (P) comprises (or consists of):

(A)85 to 99.3 wt. -% of at least one thermoplastic polymer composition (a) comprising (or consisting of):

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D)0.1 to 5% by weight of one or more further additives (D),

wherein the sum of components (A) to (D) is 100% by weight of the molding material (P),

and wherein the moulding material (P) obtained by the process of the invention has a greyscale after 3200 hours of weathering according to PV3930 which is at least 1 unit higher, preferably at least 2 units higher, than the greyscale of an equivalent product which has been subjected to the same artificial weathering, of a moulding material (P) which does not contain an organopolysiloxane compound (B), and optionally has one of the following properties:

(d) after 3200 hours of artificial ageing according to PV3929, the colour shift of the molding materials (P) is less than 25%, preferably 20%, of the colour shift of comparable molding materials (P) without organopolysiloxane compound (B) after 3200 hours of the same artificial weathering according to PV 3929.

Preparation of the Molding materials (P)

The method of the invention may comprise any steps suitable for the claimed method.

In a preferred embodiment, the procedure for compounding the components comprises at least the following steps:

(i) providing predetermined amounts of components (a) to (D) to an optionally heated mixing device; and

(ii) blending components (A) to (D) in the optionally heatable mixing apparatus at a temperature above the glass transition points of components (A) to (D) to obtain molding material (P).

Optionally, components (a) to (D) may be prepared as a homogeneous mixture of particulate materials prior to step (ii). However, when the optionally heatable mixing device is used for this reason without prior mixing, homogeneous mixing can generally also be achieved in the optionally heatable mixing device.

Each of components (a) to (D) (in terms of solids) may be provided in the form of particulate materials (e.g., as pellets, granules and/or powders) having different particle sizes and particle size distributions.

The particulate materials (a) to (D) may be provided to the mixing apparatus in the required amounts and proportions described above, and optionally mixed prior to the blending step (ii) to obtain a homogeneous mixture of particulate materials. In a preferred embodiment, this may take from 1 to 60 minutes, preferably from 1 to 20 minutes, particularly preferably from 2 to 10 minutes, depending on the amount of particulate material to be mixed.

The homogeneous mixture of particulate material thus obtained is then transferred to and mixed in an optionally heatable mixing device, thereby producing a polymer mixture which is essentially a liquid melt.

By "substantially liquid melt" is meant that the polymer mixture and the major liquid melt (softened) portion may also contain proportions of solid components, such as unmelted fillers and reinforcing materials, such as glass fibers, metal flakes, or other unmelted pigments, colorants, and the like. By "liquid melt" is meant that the polymer mixture has at least low flowability, i.e. at least softens to the extent that it is plastic.

The mixing devices used are those known to the person skilled in the art. Components (A) and (B), and, if included, (C) and/or (D), may be mixed by co-extrusion, kneading or roller compaction, it being understood that the above-mentioned components must have been separated from the aqueous dispersion or extracted from the aqueous polymerization solution.

Examples of mixing devices for carrying out the process according to the invention include discontinuously operating heated internal kneading devices with or without RAM, continuously operating kneaders, such as continuously operating internal kneaders, screw kneaders with axially oscillating screws, Banbury kneaders, and furthermore extruders and roll mills, mixing roll mills with heated rolls and calenders.

Optionally, the process may comprise a further step (iii) of cooling the blend obtained from step (ii) to a temperature below the glass transition point of components (a) to (D) to obtain a molding material (P).

The mixing devices preferably used are extruders or kneaders. Particularly suitable for melt extrusion are single-screw or twin-screw extruders. A twin screw extruder is preferred. In some cases, the mechanical energy introduced by the mixing device during mixing is sufficient to melt the mixture, which means that it is not necessary to heat the mixing device. Otherwise, the mixing device is typically heated.

The temperature employed depends on the chemical and physical properties of the styrene-based polymer composition (a) and the organopolysiloxane compound (B), and, if present, of the colorant or colorant masterbatch (C) and/or other additives (D). The temperature should be selected to result in a substantially liquid melt of the polymer mixture. On the other hand, the temperature is not unnecessarily high in order to prevent thermal damage to the polymer mixture. However, the mixing device may even require cooling if the mechanical energy introduced may generate too high a temperature. The mixing apparatus is generally operated at from 150 to 400 c, preferably from 170 to 300 c.

In a preferred embodiment, a heatable twin-screw extruder is used, the speed of which is from 50 to 150rpm, preferably from 60 to 100 rpm. In a preferred embodiment extrusion temperatures of 170 ℃ and 270 ℃, preferably 210 ℃ and 250 ℃ are used to obtain the molding material (P). The molding material (P) can be used directly in the molding process, preferably in the injection molding process, or can be processed into granules and then subjected to the molding process. The molding process is preferably carried out at a temperature of from 170 to 270 ℃, particularly preferably from 210 to 250 ℃, to give a molded article.

The moulding process can be carried out using known methods for thermoplastic processing and can in particular be produced by thermoforming, extrusion, injection moulding, calendering, blow moulding, compression moulding, pressure sintering, deep drawing or sintering, preferably by injection moulding.

As mentioned above, the molding materials (P) of the invention have particular UV resistance and good mechanical properties. Accordingly, a further aspect of the present invention relates to the molding materials (P) obtainable from the process of the present invention.

Furthermore, a further aspect of the invention relates to a molding material (P) comprising (or consisting of):

(A)80 to 99.5 wt. -% of at least one thermoplastic polymer composition (a) comprising (or consisting of):

(B)0.5 to 5% by weight of at least one organopolysiloxane compound (B);

(D)0 to 5% by weight of one or more further additives (D),

wherein the sum of components (A) to (D) is 100% by weight of the molding material (P),

and wherein the molding material (P) obtained by the process of the invention has at least one of the following characteristics:

It should be understood that the definitions and preferred embodiments described above in the context of the process according to the invention apply equally to the moulding mass (P) mutatis mutandis.

Furthermore, since the molding compounds (P) have advantageous properties, the articles obtained, in particular shaped articles, will also have these advantageous properties, for example resistance to UV light and retention of mechanical properties. A further aspect of the present invention therefore relates to articles, in particular moldings, prepared from the molding compositions (P) of the invention.

It should be understood that the definitions and preferred embodiments described in the context of the process and molding composition (P) according to the invention apply equally, mutatis mutandis, to the articles, in particular molded articles, according to the invention described.

The invention also relates to articles, in particular molded articles, prepared from the molding compounds (P) or polymer compositions, comprising the molding compounds (P) in combination with a further thermoplastic polymer as described above. The articles, particularly molded articles, may be prepared by any known thermoplastic processing method. In particular, it can be prepared by thermoforming, extrusion, injection molding, calendering, blow molding, compression molding, press sintering, deep drawing or sintering, preferably by injection molding.

The molding compositions (P) and the articles, in particular the moldings, can be used advantageously for producing components or articles for electronic devices, household articles and exterior and/or interior parts of automobiles, in particular for producing visible components or articles. Preferably to be applied to a/B/C pillars in automobiles.

As mentioned above, the present invention relates to the improvement of the UV resistance of moulding compositions by organopolysiloxane compounds (B). Accordingly, a further aspect of the present invention relates to the use of organopolysiloxane compounds for improving the UV resistance of moulding compositions.

It is to be understood that the definitions and preferred embodiments listed above in the context of the process and the molding composition (P) apply equally, mutatis mutandis, to the use according to the invention.

In a preferred embodiment, the organopolysiloxane compound is as defined above. In a preferred embodiment, the molding composition comprises the thermoplastic polymer composition (A) as defined above. In a preferred embodiment, the organopolysiloxane compound is as defined above and the molding compound comprises the thermoplastic polymer composition (A) as defined above. In a preferred embodiment, the molding compound is a molding compound (P) as defined above.

The invention will be further illustrated by the claims and examples.

Examples

Components

And (2) component A: the thermoplastic polymer composition (A) is Acrylonitrile Styrene Acrylate (ASA), i.e.SAN impact modified poly (styrene-acrylonitrile) grafted onto a core of Butyl Acrylate (BA) (BA-g-SAN)

(SAN) with the following specified attributes.

Component B1: the polysiloxane component (B1) was provided in the form of a Masterbatch (MB) comprising 50 wt% of an ultra-high molecular weight siloxane polymer dispersed in a poly (styrene-acrylonitrile) (SAN) carrier. Master Batches (MB) are commercially available (MB50-008 masterbatch). MB50-008 may be used as Polydimethylsiloxane (PDMS) dispersed in SAN.

Ingredient B2: the silicone component (B2) is provided in the form of a liquid component having a viscosity (at 25 ℃) of 950-. It can be derived from Evonik Nutrition&Care Corp. (Antisscratch L) were obtained commercially. The molecular weight (mass mean, Mw) determined by GPC (solvent: THF) was 39.311kDa (relative to polystyrene standards).The antisscratch L is an organomodified polysiloxane (polydimethylsiloxane, PDMS) containing vinyl and methoxy groups.

Component C1: di (2-propylheptyl) phthalate (DPHP) is a plasticizer.

Component C2: polyethylene waxes are useful as lubricants.

Component C3: bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate is a UV stabilizer of the Hindered Amine Light Stabilizer (HALS) class available from basf, germany.

Component C4:the UV-3853 series is a Hindered Amine Light Stabilizer (HALS) available from the Cytec Solvay Group.

Component C5: has a melting point of 42-50 deg.C and a viscosity of 0.92g/cm³Aliphatic fatty acid ester compositions of density (e.g., available from Croda International, uk)100。

Component D1: carbon black is used as the black pigment.

Matrix rubber latex L1:

to the reaction vessel were added 90.2 parts of demineralized water, 0.61 part of the sodium salt of a C12-to C18-paraffinsulfonic acid and 0.23 part of sodium bicarbonate. When the temperature in the reaction vessel reached 59 deg.C, 0.16 parts of sodium persulfate dissolved in 5 parts of demineralized water was added. A mixture of 59.51 parts of butyl acrylate and 1.21 parts of tricyclodecenyl acrylate is added over 210 minutes. Thereafter, the reaction was continued for 60 minutes. Finally, the total solids content of the polymer dispersion was 39.6% and the particle size of the latex particles was 75nm (determined by turbidity).

Graft rubber latex (component A-1 a):

151.9 parts of the above-described substrate latex was charged into a reaction vessel together with 92.2 parts of demineralized water and 0.14 part of sodium persulfate dissolved in 3.22 parts of demineralized water. A mixture of 31.18 parts of styrene and 9.31 parts of acrylonitrile was added at a temperature of 61 ℃ over 190 minutes and then left to stand at 65 ℃ for 60 minutes to obtain a polymer dispersion having a total solids content of 35.5%. The latex particles had a diameter of 87nm (determined by turbidity). After synthesis, the latex was coagulated with magnesium sulfate solution at a temperature of about 60 ℃ and then sintered at a temperature of about 90 ℃. The resulting slurry was centrifuged to give wet rubber crumb which was further processed.

Matrix rubber latex L2:

the reaction vessel was charged with 70.66 parts of demineralized water, 0.3 parts of latex L1 and 0.23 parts of sodium bicarbonate. After heating the reaction vessel to 60 ℃, 0.16 parts of sodium persulfate dissolved in 5 parts of demineralized water was added to the reaction mixture. A mixture of 59.51 parts of butyl acrylate and 1.21 parts of tricyclodecenyl acrylate is added over 210 minutes. Simultaneously with the first feed, 0.36 part of C12-C18 sodium salt of paraffin wax sulfonic acid (dissolved in 16.6 parts of demineralized water) was added over 210 minutes. After 200 minutes from the start of the feed, the temperature rose to 65 ℃.

Thereafter, the reaction was continued at 65 ℃ for 60 minutes. Finally, the total solids content of the polymer dispersion was 39.4% and the particle size of the latex particles was 440nm (determined by turbidity).

Graft rubber latex (component A-1 b):

154 parts of the matrix latex are added to a reaction vessel together with 88.29 parts of demineralized water, 0.11 part of the sodium salt of a C12-C18-paraffinsulfonic acid and 0.14 part of sodium persulfate dissolved in 5.61 parts of demineralized water. The reaction mixture was heated to 61 ℃. 13.16 parts are added at a temperature of 61 ℃ over 60 minutes, followed by waiting for 90 minutes during which the temperature is increased from 61 ℃ to 65 ℃. A mixture of 20.5 parts of styrene and 6.83 parts of acrylonitrile is then added to the reaction over 150 minutes. The reaction was continued at 65 ℃ for 60 minutes to give a polymer dispersion having a total solids content of 35.2%. The latex particles had a diameter of 500nm (determined by turbidity). After synthesis, the latex was coagulated with magnesium sulfate solution at a temperature of about 88 ℃ and then sintered at a temperature of about 130 ℃. The resulting slurry was centrifuged to give wet rubber crumb which was further processed.

Experimental procedures

TABLE 1 blending formulation

Here, each BA-g-SAN (i.e.components A-1a and A-1b) contains about 60 parts of n-Butyl Acrylate (BA) containing a crosslinking agent, about 40 parts of SAN (styrene to acrylonitrile mass ratio of 1:3 to 1:4), and about 1 part of other monomers, for example dihydrodicyclopentadienyl acrylate (DCPA) or tricyclodecenyl acrylate.

Sample preparation

The sample of example 1 was prepared using a twin-screw extruder (model ZSK26MC, Coperion GmbH, length: 1035mm) and components A and B were mixed at a Tm of 240 ℃ in the specific proportions given in Table 1. DIN A5 samples (approx.14.8X 21.0cm) were injection molded (Tm: 242 ℃ C.).

Aging conditions

PV3929 (simulated dry hot climate):

black standard 90. + -.2 ℃ (dry phase: 50. + -.2 ℃), relative humidity: 20 +/-10%;

radiation: at a wavelength of 340nm, 0.6W/m²；

The instrument comprises the following steps: Weather-O-meter Ci35A

Evaluation: the grey scale according to EN 20105AO2 is used; color measurements were carried out according to DIN 6174; the yellowing index according to DIN 6167 is used;

PV3930 (simulating a humid and warm climate):

black standard 65. + -. 2 ℃ (dry phase: 35-45 ℃), relative humidity: 70 +/-10%;

radiation: at a wavelength of 340nm, 0.51W/m²(or 60W/m at a wavelength of 300-400nm²) (ii) a According to ISO 4892-2 standard;

the device comprises the following steps: Weather-O-meter Ci 5000;

evaluation: the grey scale according to EN 20105AO2 is used; color measurements were carried out according to DIN 6174; the yellowing index according to DIN 6167 is used;

and (3) evaluating the gray level unit: 1: strong ash; 2: gray; 3: some ash; 4: slightly gray 5: substantially free of ash

Results

It has surprisingly been found that the addition of organopolysiloxane component (B) to thermoplastic resin compositions (e.g.ASA) can significantly improve the weathering resistance. According to the results in Table 2, the colour shift (dE) of the inventive samples after artificial ageing for 3200h according to PV3929 is significantly lower than that of the inventive samples without component (B). The results for PV3930 are similar to the significantly reduced color shift of the inventive sample compared to the non-inventive sample lacking component (B). In addition to color shift, the aged gray scale is an interesting attribute. The results in table 3 show that the grey scale of the inventive samples is at least 2 units higher after artificial ageing for 3200 hours according to PV3930 compared to the non-inventive samples lacking component (B).

TABLE 2 color shift upon artificial aging/weathering according to PV3929 and PV3930

TABLE 3 grayscales for artificial aging according to PV3930 standard

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