COLOR MASTER BATCH ON THE BASIS OF VINYL CHLORIDE GRAFT COPOLYMERS

Abstract

The present invention relates to the use of vinyl chloride graft copolymers for producing a color masterbatch and a color masterbatch based on vinyl chloride graft copolymers.

Claims

1-12. (canceled)

13. A method for production of a color masterbatch, comprising: using a vinyl chloride graft copolymer comprising: A) 35 to 60 wt.-%, based on the total weight of the vinyl chloride graft copolymer, of a grafted, crosslinked copolymer which can be prepared by copolymerizing: 80 to 99.95 wt.-%, vinyl chloride, 0.05 to 3.0 wt.-% polyethylenically unsaturated comonomers and 0 to 19.95 wt.-% copolymerizable, ethylenically unsaturated comonomers, or 35 to 60 wt.-%, based on the total weight of the vinyl chloride graft copolymer, of a grafted (co)polymer, obtainable by (co) polymerization of 80 to 100 wt.-% vinyl chloride and 0 to 20 wt.-% of further copolymerizable, ethylenically unsaturated comonomers, at a polymerization temperature of 0 to 45 C., and B) 40 to 65 wt.-%, based on the total weight of the vinyl chloride graft copolymer of a crosslinked graft base containing a crosslinked acrylate copolymer with 0.01 to 5 wt.-% polyethylenically unsaturated comonomer units and, if appropriate, further comonomer units copolymerizable with acrylic acid esters.

14. The method of claim 13 wherein the polyethylenically unsaturated comonomers do not contain conjugated double bonds like divinyl esters of dicarboxylic acids such as divinyl adipate; diallyl esters of polycarboxylic acids such as diallyl phthalate, diallyl fumarate; divinyl ethers of polyhydric alcohols such as ethylene glycol divinyl ether; divinyl aromates such as divinyl benzene; allyl and methallyl esters of ethylenically unsaturated monocarboxylic acids such as allyl methacrylate; di- and triacrylates of polyhydric alcohols such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate (DEGDA), diethylene glycol dimethacrylate (DEGDMA), trimethylene glycol diacrylate, butylene glycol diacrylate, pentamethylene glycol diacrylate, glyceryl triacrylate, trimethylol propane triacrylate (TMPTA), trimethyol propane trimethacrylate (TMPTMA); tetraacrylate of polyhydric alcohols such as pentaerythritol tetraacrylate; triallyl cyanurate.

15. The method of claim 13 wherein the polyethylenically unsaturated comonomers are selected from diallyl phthalate, divinyl adipate, triallyl cyanurate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate and trimethyol propane triacrylate or mixtures thereof.

16. The method of claim 13 wherein the further copolymerizable, ethylenically unsaturated comonomers are selected from: vinyl esters of saturated carboxylic acids having 2 to 12 carbon atoms such as vinyl acetate, vinyl propionate, vinyl laurate or vinyl versatic acid esters; (meth) acrylic acid esters of alcohols having 1 to 8 carbon atoms, such as methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, 2-ethylhexyl acrylate; ethylenically unsaturated mono and dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid; mono- and diesters of ethylenically unsaturated dicarboxylic acids such as diisopropyl fumarate; vinyl aromatics such as styrene; and olefins such as ethylene.

17. The method of claim 13 wherein the crosslinked acrylate copolymer is prepared from one or more acrylic acid esters of alcohols having 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate.

18. The method of claim 13 wherein the vinyl chloride graft copolymer comprises: A) 40 to 55 wt.-%, based on the total weight of the graft copolymer, of a grafted crosslinked copolymer of 98.5 to 99.9 wt.-% vinyl chloride and 0.1 to 1.5 wt.-% of one or more polyethylenically unsaturated comonomers selected from the group consisting of diallyl phthalate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, trimethyol propane triacrylate, or 40 to 55 wt.-%, based on the total weight of the vinyl chloride graft copolymer, of a grafted VC polymer, obtainable by graft polymerization of vinyl chloride at a polymerization temperature of 0 to 45 C., and B) 45 to 60 wt.-%, based on the total weight of the graft copolymer, of a crosslinked graft base consisting of a crosslinked copolymer of n-butyl acrylate and/or 2-ethylhexyl acrylate, or of a crosslinked acrylic acid ester-ethylene-vinyl acetate copolymer having an acrylate content of 35 to 70 wt.-% or mixtures of said copolymers, whereby the copolymers are crosslinked with 0.05 to 0.5 wt.-% of one or more copolymerized, polyethylenically unsaturated comonomers selected from the group consisting of diallyl phthalate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, trimethyol propane triacrylate, for the production of a color masterbatch.

19. The method of claim 13 wherein the vinyl chloride graft copolymer is admixed with at least one pigment.

20. A color masterbatch comprising a vinyl chloride graft copolymer comprising: A) 35 to 60 wt.-%, based on the total weight of the vinyl chloride graft copolymer, of a grafted, crosslinked copolymer obtainable by copolymerization of: 80 to 99.95 wt.-% vinyl chloride, 0.05 to 3.0 wt.-% polyethylenically unsaturated comonomers and 0 to 19.95 wt.-% of further copolymerizable, ethylenically unsaturated comonomers, or 35 to 60 wt.-%, based on the total weight of the vinyl chloride graft copolymer, of a grafted (co) polymer which can be prepared by (co) polymerizing 80 to 100 wt.-% vinyl chloride and 0 to 20 wt.-% of further copolymerizable, ethylenically unsaturated comonomers, at a polymerization temperature of 0 to 45 C., and B) 40 to 65 wt.-%, based on the total weight of the vinyl chloride graft copolymer of a crosslinked graft base containing a crosslinked acrylic acid ester copolymer containing 0.01 to 5 wt.-% of polyethylenically unsaturated comonomer units and, if appropriate, further comonomers which can be copolymerized with acrylic acid esters, and at least one pigment.

21. A color masterbatch according to claim 20 comprising: a vinyl chloride graft copolymer comprising: A) 40 to 55 wt.-%, based on the total weight of the graft copolymer, of a grafted crosslinked copolymer of 98.5 to 99.9 wt.-% of vinyl chloride and 0.1 to 1.5 wt.-% of one or more polyethylenically unsaturated comonomers selected from the group consisting of diallyl phthalate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, trimethyol propane triacrylate, or 40 to 55 wt.-%, based on the total weight of the vinyl chloride graft copolymer, of a grafted VC polymer obtainable by graft polymerization of vinyl chloride at a polymerion temperature from 0 to 45 C., and B) 45 to 60 wt.-% based on the total weight of the graft copolymer, of a crosslinked graft base consisting of a crosslinked copolymer of n-butyl acrylate and/or 2-ethylhexyl acrylate, or of a crosslinked acrylic acid ester-ethylene-vinyl acetate copolymer with an acrylate content of 35 to 70 wt.-% or mixtures of the copolymers mentioned, wherein the copolymers are crosslinked with 0.05 to 0.5 wt.-% of one or more copolymerized, polyethylenically unsaturated comonomers selected from the group consisting of diallyl phthalate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, trimethyol propane triacrylate, and at least one pigment.

22. The method of claim 13 wherein the vinyl chloride graft copolymer and at least one pigment are admixed in weight ratio of 80:20 to 20:80.

23. The method of claim 13 wherein the vinyl chloride graft copolymer and at least one pigment are admixed at a weight ratio of 75:25 to 25:75.

24. The method of claim 13 wherein a color masterbatch produced that comprises the vinyl chloride graft copolymer and at least one pigment in weight ratio of 80:20 to 20:80.

25. The method of claim 13 wherein a color masterbatch is produced that comprises the vinyl chloride graft copolymer and at least one pigment at a weight ratio of 75:25 to 25:75.

26. A color masterbatch according to claim 20 wherein the vinyl chloride graft copolymer and the pigment are contained in a weight ratio of 80:20 to 20:80.

27. A color masterbatch according to claim 20 wherein the vinyl chloride graft copolymer and the pigment are contained in a weight ratio of 75:25 to 25:75.

Description

EXAMPLES

[0049] The following color master batches were prepared:

Extruder: Weber DS 85 16 D, S-Screw

[0050]

TABLE-US-00001 Temperatures: cylinder zone 1 150 C., Cylinder zone 2 160 C. Cylinder zone 3 170 C. Cylinder zone 4 170 C. Cylinder zone 5 175 C. Cylinder zone 6 175 C.

[0051] Screw speed 30 rpm; Dosing screw speed 4 rpm

[0052] A pelletizing head was used as the tool.

TABLE-US-00002 TABLE 1 Ingredient example 1 example 2 Trade name - trade type HA 3350/6 HA 3350/7 K 707 E (Vinnolit) 30.0000 70.0000 Heucodur Brown 869 70.0000 Heucodur Yellow 3975 30.0000 Mark CZ 2001/1 (Ca/Zn stabilizer) 1.2500 1.2500 Edenol D 81 (epoxidized soybean oil) 1.5000 1.5000 Paraloid K 120 N (acrylic processing aid) 1.0000 1.0000 Loxiol G 70 (lubricant) 0.2500 0.2500

[0053] Carrier according to the invention: K 707 E; Pigments: Heucodur Brown 869 and Heucodur Yellow 3975; Stabilizers: Mark CZ 2001/1 and Edenol D 81; Processing aid: Paraloid K 120 N; lubricating agent: Loxiol G 70.

[0054] Window profiles were manufactured with these color masterbatches according to the invention. The compositions are shown in Table 2:

Extruder: Cincinnati CMT-45, Screw Konical Counter Rotating

[0055]

TABLE-US-00003 Temperatures: screw 155-160 C. Cylinder zone 1 165 C. Cylinder zone 2 170 C. Cylinder zone 3 180 C. Cylinder zone 4 195 C. Tool 206 C.
Screw speed 22 rpm
Window profile-tool

TABLE-US-00004 TABLE 2 Reference Ex (without Comp.- Comp.- Comp.- Comp.- pigment) Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ingredient Vinnolit S 3268 95 95 95 95 95 95 95 95 95 S-PVC Vinnolit K 707 10 10 10 10 10 10 10 10 10 E Graft copolymer Bropan R 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 90901 stabilizer Kronos 2220 4 without without without without without without without without Titanium dioxide Hydrocarb 95T 8 8 8 8 8 8 8 8 8 chalk Yellow -HA 4 6 3350/7 Brown-HA 4 6 3350/6 Heucobatch 4 6 Yellow 190 07 99 Heucobatch 4 6 Brown 890 103 Test method Impact strength 24.38 100.79 102.04 23.8 101.81 18.33 17.28 24.03 18.33 (DIN ISO 179- 1, 23 C.) Gloss 50.9 47.4 50.6 49.3 50.8 35.2 35.2 34.7 34.2 (DIN ISO 67530, 60 C.) Impact strength 53.0 54.0 55.2 52.0 52.7 36.8 25.1 48.9 48.9 (RAL716-1, 23 C.) Vicat A 89.0 89.1 88.6 88.5 88.6 88.0 87.5 86.5 87.5 (DIN EN ISO 306) Mean C.

[0056] By using the color masterbatches produced in accordance with the invention (examples 3, 4, 5, 6), the impact strength remains at a high level or is further improved. In contrast to the comparative examples (see comp. Ex. 1, 2, 3, 4), the high gloss of the extrudates desired in many cases is retained.

[0057] A particularly high Vicat softening temperature is sought, especially for pigmented articles for outdoor use. The use of the color masterbatches produced according to the invention proved to be advantageous here.