AN ABRASION RESISTANT MULTI-LAYERED COMPOSITE

Abstract

Described herein is a multi-layered composite including a substrate, an adhesive layer and a top coat layer, the top coat layer being formed by a silicone coating composition including: (A) at least one organopolysiloxane polymer having at least two alkene functions; (B) at least one cross-linking organohydrogensiloxane having at least two Si—H groups; and (C) a catalyst capable of promoting the reaction between component (A) and component (B); wherein the component (B) contains at least 25%, preferably at least 30%, more preferably at least 45% by weight of component (B) of a three-dimensional net-like organohydrogensiloxane resin (B′) containing at least two different units selected from a group including: units M of formula R′.sub.3SiO.sub.1/2; units D of formula R′.sub.2SiO.sub.2/2; units T of formula R′SiO.sub.3/2; and units Q of formula SiO.sub.4/2, wherein R′ represents hydrogen atom or a monovalent hydrocarbonyl group having from 1 to 20 carbon atoms, and with the proviso that at least one of these units is the unit T or Q, preferably Q, and at least one of the units M, D and T comprises a hydrogen atom. Also described, are embodiments where the multi-layered composite has a surface with excellent abrasive resistance and good mechanical properties.

Claims

1. A multi-layered composite comprising a substrate, an adhesive layer and a top coat layer, the top coat layer being formed by a silicone coating composition comprising the following components: (A) at least one organopolysiloxane polymer having at least two alkene functions comprising: (i) at least two units of formula (I-1)
R.sup.1.sub.aZ.sub.bSiO.sub.[4-(a+b)]/2  (I-1) in which R.sup.1 represents a monovalent radical containing from 2 to 12 carbon atoms, having at least one alkene function, Z which can be the same or different and represents a monovalent radical comprising from 1 to 20 carbon atoms and does not comprise an alkene function, a is an integer of 1, 2 or 3, b is an integer of 0, 1 or 2 and the sum of a+b is 1, 2 or 3, (ii) and optionally other units of formula (I-2):
Z.sub.cSiO.sub.(4-c)/2  (I-2) in which Z has the same meaning as above, and cis an integer of 0, 1, 2 or 3; (B) at least one cross-linking organohydrogensiloxane having at least two Si—H groups; and (C) a catalyst that promotes a reaction between component (A) and component (B); wherein the component (B) comprises at least about 25 wt weight of component (B) of a three-dimensional net-like organohydrogensiloxane resin (B′) comprising at least two different units selected from the group consisting of: units M of formula R′.sub.3SiO.sub.1/2, units D of formula R′.sub.2SiO.sub.2/2, units T of formula R′SiO.sub.3/2 and units Q of formula SiO.sub.4/2, wherein R′ represents a hydrogen atom or a monovalent hydrocarbonyl group having from 1 to 20 carbon atoms, and with the proviso that at least one of these units is the unit T or Q, and at least one of the units M, D and T comprises a hydrogen atom.

2. The multi-layered composite according to claim 1, wherein the component (A) comprises from about 8 wt % to about 80 wt %, by total weight of the component (A) of alkenyl organopolysiloxane resin (A′) comprising: at least two different units selected from the group consisting of units M of formula R.sub.3SiO.sub.1/2, units D of formula R.sub.2SiO.sub.2/2, units T of formula RSiO.sub.3/2 and units Q of formula SiO.sub.4/2, wherein R have the meanings given for groups R.sup.1 or Z in claim 1, with the proviso that at least one of these units is the siloxane unit T or Q and at least two of the units M, D and T comprises an alkene function.

3. The multi-layered composite according to claim 1, wherein the component (B) comprises about 100 wt % of the three-dimensional net-like organohydrogensiloxane resin (B′).

4. The multi-layered composite according to claim 1, wherein the mole molar ratio of the M unit to the Q unit in said organohydrogensiloxane resin (B′) is from about 0.5 mol/mol to about 8 mol/mol.

5. The multi-layered composite according to claim 1, wherein the molar ratio of silicon-bonded hydrogen atoms to the sum of the silicon-bonded vinyl groups in the whole composition is from about 0.8 mol/mol to about 10 mol/mol.

6. The multi-layered composite according to claim 1, wherein the composition comprises component (D) which is composed of spherical particle fillers with a particle size D50 from about 0.2 μm to about 60 μm.

7. The multi-layered composite according to claim 6, wherein the amount of component (D) is from about 1 wt % to about 30 wt %, by total weight of whole silicone coating composition.

8. The multi-layered composite according to claim 6, wherein component (D) is selected from the group consisting of: precipitated silica particles, spherical silicone resin particles, polyamide particles and mixtures thereof.

9. The multi-layered composite according to claim 8, said wherein the spherical silicone resin particles are particles of silicone resin material formed by polysiloxanes of the general formula of
R.sup.6.sub.mSiX.sub.nP.sub.(4-m-n)/2, where R.sup.6 is an alkyl, aryl, aralkyl or alkylaryl group having two or more carbon atoms, X is a functional group selected from the group consisting of an epoxy group, an alkoxyl group, a vinyl group, a hydrogen group, an acryloxy group, a methacryloxy group, a polyethylene glycol group, a hydroxy group, and an amino group, m is an integer of 0 to 2, n is an integer of 0 to 1, and m+n is 0 to 3.

10. The multi-layered composite according to claim 9, said wherein the silicone resin material is formed by polysiloxane comprising siloxane units selected from the group consisting of: unit M of R.sup.7.sub.3SiO.sub.0.5, unit D of R.sup.7.sub.2SiO, unit T of R.sup.7SiO.sub.3/2 and unit Q of SiO.sub.4/2, wherein R.sup.7 is selected from the group consisting of: a methyl, an ethyl, a phenyl, a phenylethyl a 3 phenylpropyl groups, a hydroxyl, acryloxy, a methacryloxy, a hydrogen, an epoxy, and an amino group, with the proviso that the amount of unit T or unit D is higher than about 50 mol %.

11. The multi-layered composite according to claim 8, wherein spherical silicone resin particles are added into the silicone coating composition in the form of a dispersion with the content of about 10 wt % to about 30 wt % based on the total weight of the dispersion.

12. The multi-layered composite according to claim 1, wherein the silicone coating composition comprises a crosslinking inhibitor.

13. The multi-layered composite according to claim 1, wherein the coat weight of the top coat layer is from about 5 gsm to about 250 gsm.

14. The multi-layered composite according claim 1, wherein the abrasion resistance of the top coat layer is ranked according to ASTM D4157 at Ranking 5 after at least about 100,000 scrubbing.

15. The multi-layered composite according to claim 1, wherein the adhesive layer is formed by a silicone adhesive composition.

16. The multi-layered composite according to claim 1, wherein the adhesive layer contains no three-dimensional net-like organohydrogensiloxane resin (B′) and/or no component (D), which is a component selected from the group consisting of: precipitated silica particles, spherical silicone resin particles, polyamide particles and mixtures thereof.

17. The multi-layered composite according claim 1, wherein the adhesive layer comprises an adhesive promotor in an amount from about 0.2 wt % to about 10 wt % by total weight of the adhesive layer.

18. The multi-layered composite according to claim 17, wherein the adhesive promotor is one or more selected from the group consisting of epoxy silane, alkoxy silane, acyloxy silane, aryloxy silane, oligomers thereof and combinations thereof.

19. The multi-layered composite according to claim 1, wherein the substrate is a fabric or film or sheet based on the polymers selected from the group consisting of polypropylene, polyethylene, fiberglass, polyamides, polyurethane and polyvinyl chloride, poly(ethylene) terephthalate and other polymers and mixtures thereof.

20. A product comprising the multi-layered composite according to claim 1.

21. The product according to claim 20, wherein the product is an artificial leather, an airbag or apparel.

22. A silicone coating composition comprising following components: (A) at least one organopolysiloxane polymer having at least two alkene functions comprising: (i) at least two units of formula (I-1)
R.sup.1.sub.aZ.sub.bSiO.sub.[4-(a+b)]/2  (I-1) in which R.sup.1 represents a monovalent radical containing from 2 to 12 carbon atoms, having at least one alkene function, Z is the same or different and represents a monovalent radical comprising from 1 to 20 carbon atoms and does not comprise an alkene function, a is an integer of 1, 2 or 3, b is an integer of 0, 1 or 2 and the sum of a+b is 1, 2 or 3, (ii) and optionally other units of formula (I-2):
Z.sub.cSiO.sub.(4-c)/2  (1-2) in which Z has the same meaning as above, and cis an integer of 0, 1, 2 or 3; (B) at least one cross-linking organohydrogensiloxane having at least two Si—H groups; (C) a catalyst that promotes a reaction between component (A) and component (B); (D) spherical particle fillers with a particle size D50 from about 0.2 μm to about 60 μm, in an amount of from about 2 wt % to about 50 wt by total weight of component (A); wherein the component (B) comprises at least about 25 wt % by weight of a three-dimensional net-like organohydrogensiloxane resin (B′) comprising at least two different units selected from the group consisting of units M of formula R′.sub.3SiO.sub.1/2, units D of formula R′.sub.2SiO.sub.2/2, units T of formula R′SiO.sub.3/2 and units Q of formula SiO.sub.4/2, wherein R′ represents hydrogen atom or a monovalent hydrocarbon group having from 1 to 20 carbon atoms, and with the proviso that at least one of these units is the unit T or Q and at least one of the units M, D and T comprises a hydrogen atom.

23. The silicone coating composition according to claim 22, wherein component (D) is selected from the group consisting of: precipitated silica particles, spherical silicone resin particles, polyamide particles, silicone elastomer particles and mixtures thereof.

24. The silicone coating composition according to claim 22, wherein the composition further comprises a crosslinking inhibitor and/or a fumed silica.

25. The silicone coating composition according to claim 22, wherein the component (A) comprises from about 8 wt % to about 80 wt % by total weight of the component (A) of alkenyl polysiloxane resin (A′) comprising: at least two different units selected from the group consisting of units M of formula R.sub.3SiO.sub.1/2, units D of formula R.sub.2SiO.sub.2/2, units T of formula RSiO.sub.3/2 and units Q of formula SiO.sub.4/2, wherein R have the meanings given for groups R.sup.1 or Z in claim 1, with the proviso that at least one of these units is the siloxane unit T or Q and at least two of the units M, D and T comprises an alkenyl group.

26. A method of making a silicone coated textile, the method comprising using the silicone coating composition according to claim 22 to surface modify the silicone coated textile in an application selected from the group consisting of heat shielding, durable water repellent (DWR) coating, silicone inks in textile screen printing, airbags and injection molding of parts, and for applying directly to textile for apparel printing.

27. The multi-layered composite according to claim 1, wherein the at least one cross-linking organohydrogensiloxane (B) comprises at least three Si—H groups.

28. The multi-layered composite according to claim 1, wherein the component (B) comprises at least about 30% by weight of the three-dimensional net-like organohydrogensiloxane resin (B′).

29. The multi-layered composite according to claim 1, wherein the component (B) comprises at least about 45% by weight of the three-dimensional net-like organohydrogensiloxane resin (B′).

30. The multi-layered composite according to claim 1, wherein at least one of the units M, D, T and Q of the three-dimensional net-like organohydrogensiloxane resin (B′) is Q.

31. The multi-layered composite according to claim 1, wherein at least two of the units M, D and T comprises a hydrogen atom.

32. The multi-layered composite according to claim 2, wherein the component (A′) comprises from about 10 wt % to about 60 wt % of the alkenyl organopolysiloxane resin (A′).

33. The multi-layered composite according to claim 2, wherein the component (A′) comprises from about 15 wt % to about 50 wt % of the alkenyl organopolysiloxane resin (A′).

34. The multi-layered composite according to claim 2, wherein the at least two of the units M, D and T comprises an alkenyl group as the alkene function.

35. The multi-layered composite according to claim 4, wherein the molar ratio of the M unit to the Q unit is from about 0.5 mol/mol to about 6 mol/mol.

36. The multi-layered composite according to claim 4, wherein the molar ratio of the M unit to the Q unit is from about 0.8 mol/mol to about 5 mol/mol.

37. The multi-layered composite according to claim 5, wherein the molar ratio of silicon-bonded hydrogen atoms to the sum of the silicon-bonded vinyl groups in whole composition is from about 1.1 mol/mol to about 6 mol/mol.

38. The multi-layered composite according to claim 5, wherein the molar ratio of silicon-bonded hydrogen atoms to the sum of the silicon-bonded vinyl groups in whole composition is from about 1.2 mol/mol to about 5 mol/mol.

39. The multi-layered composite according to claim 6, wherein the spherical particle fillers have a particle size D50 of from about 0.5 μm to about 40 μm.

40. The multi-layered composite according to claim 6, wherein the spherical particle fillers have a particle size D50 of from about 0.8 μm to about 30 μm.

41. The multi-layered composite according to claim 7, wherein the amount of component (D) is from about 1.5 wt % to about 25 wt %.

42. The multi-layered composite according to claim 7, wherein the amount of component (D) is from about 2 wt % to about 20 wt %.

43. The multi-layered composite according to claim 9, wherein R.sup.6 is an alkyl, aryl, aralkyl or alkylaryl group having 2 to 6 carbon atoms.

44. The multi-layered composite according to claim 43, wherein R.sup.6 is selected from the group consisting of a methyl, an ethyl, a phenyl, a phenylethyl and a 3-phenylpropyl groups.

45. The multi-layered composite according to claim 10, wherein the amount of unit T or unit D is higher than about 70 mol %.

46. The multi-layered composite according to claim 10, wherein the amount of unit T or unit D is higher than about 80 mol %.

47. The multi-layered composite according to claim 11, wherein the added spherical silicone resin particles are present in the silicone coating composition in a content of about 10 wt. % to about 20 wt. % based on the total weight of the dispersion.

48. The multi-layered composite according to claim 13, wherein the coat weight of the top coat layer is from about 10 gsm to about 200 gsm.

49. The multi-layered composite according to claim 13, wherein the coat weight of the top coat layer is from about 15 gsm to about 100 gsm.

50. The multi-layered composite according to claim 13, wherein the coat weight of the top coat layer is from about 15 gsm to about 40 gsm.

51. The multi-layered composite according to claim 17, wherein the adhesive promoter is present in an amount of from of about 0.5 wt. % to about 8 wt.

52. The multi-layered composite according to claim 17, wherein the adhesive promoter is present in an amount of from of about 0.8 wt. % to about 5 wt.

53. The silicone coating composite according to claim 22, wherein the at least one cross-linking organohydrogensiloxane has at least three Si—H groups.

54. The silicone coating composite according to claim 22, wherein the spherical particle fillers (D) have a particle size of from about 0.5 μm to about 40 μm.

55. The silicone coating composite according to claim 22, wherein the spherical particle fillers (D) have a particle size of from about 0.8 μm to about 30 μm.

56. The silicone coating composite according to claim 22, wherein the spherical particle fillers (D) are present in an amount of from about 2 wt % to about 40 wt %.

57. The silicone coating composite according to claim 22, wherein the spherical particle fillers (D) are present in an amount of from about 5 wt % to about 35 wt %.

58. The silicone coating composite according to claim 22, wherein under the proviso the at least one unit of units T and Q is unit Q and wherein two of units M, D and T comprise the hydrogen atom.

59. The silicone coating composite according to claim 25, wherein component (A) comprises from about 10 wt. % to about 60 wt. % of the alkenyl polysiloxane resin (A′).

60. The silicone coating composite according to claim 25, wherein component (A) comprises of from about 15 wt. % to about 50 wt. % of the alkenyl polysiloxane resin (A′).

Description

EXAMPLES

[0156] The invention will be further described with reference to following examples, wherein all parts refer to the parts by weight unless other indicated.

[0157] Measurement of the Properties:

[0158] The mechanical properties are determined with known techniques:

[0159] Hardness of the silicone elastomeric materials was measured by type A durometer in accordance with GB/T 531.1,

[0160] Tensile strength and elongation at break were measured in accordance with GB/T 6344, and Tear strength was measured in accordance with ASTM D624 B.

[0161] The viscosities are values measured with a rotational viscometer.

[0162] Abrasion-Resistance:

[0163] Test Equipment: Wyzenbeek

[0164] Test stander: ASTM D4157

[0165] Test abradant: 10# cotton duck

[0166] Test starting condition: Equilibrium is considered to have been reached when the increase in weight of the specimen in successive weighing made at intervals of not less than 2 h does not exceed 0.1% of the weight of the specimen.

[0167] Recording the maximum number of scrubbings on the coating of the specimen, over which more scrubbings would bring the change of the surface and thus the surface cannot be rated as the best Ranking 5 anymore. The maximum abrasion times was listed in the Wyzenbeek-row in table 1 (with unit “w” meaning per 10000 times).

[0168] Hand Feeling for Coated Fabric:

[0169] The hand feeling of coating film was evaluated by touch with finger, we made following standards for every test:

TABLE-US-00001 Level of hand feeling State description +++++ Feel better smooth and soft ++++ Good smooth and soft +++ Feel normal + tack

[0170] General Procedure for Preparing the Testing Sample:

[0171] Several silicone coating mixtures were prepared by mixing with varying compositions and amounts as listed in table 1 for respective examples, then applied on the surface of the casting paper with a coating weight of 20 gsm and it was cured in the oven at the temperature of 130° C. for 5 min.

[0172] After the silicone coating layer (i.e. top coat) was cured and dried, a second adhesive layer was coated on it and then a fabric is put on the second layer as the substrate using a roller without pressure. For all inventive and comparative examples, the same adhesive layer was prepared and used. The second adhesive layer composition was comprising 100 parts by weight of component AA, 4 parts by weight of component BB, 0.03 parts by weight of component CC, 27 parts by weight of fumed silica, 1.35 parts by weight of adhesive promotor and 0.4 parts by weight of crosslinking inhibitor. The coating weight of the second adhesive layer was 180 gsm and then the prepared composite was cured at the temperature of 140° C. for 10 min.

[0173] After finally peeling the casting paper, a three layered composite of silicone artificial leather was obtained.

Inventive Examples and Comparative Example

[0174] Raw Materials of the Top Coat, Silicone Coating Composition:

TABLE-US-00002 Component A-1 vinyl terminal-polydimethylsiloxane oil, vinyl content 0.08 wt %, viscosity 60,000 mpas Component A-2 Vinyl MQ resin, vinyl content 0.31 wt % Compoent B-1 Methyl hydrogen silicone oil, the SiH is in chain with content of 20 wt % Component B-2 methyl hydrogen MQ resin with SiH content of 24 wt % Component D-1 Fumed Silica, D50 = 4 μm Component D-2 T unit silicone resin, D50 = 4 μm Component D-3 Polyamide 6 resin particles, D50 = 20 μm Component D-4 Precipitated silica, D50 = 4.4 μm Component D-5 T unit silicone resin micropearl, D50 = 0.8 μm Component D-6 T unit silicone resin micropearl, D50 = 2 μm Component D-7 T unit silicone resin micropearl, D50 = 8 μm Component D-8 T unit silicone resin micropearl, D50 = 15 μm Component D-9 talc, D50 = 10 μm, lamellar material Component D-10 MDT unit silicone resin microperal (D unit is about 70 mol %), D50 = 10 μm Component D-11 A dispersion of Component D-10 in 80-90 wt % of D5 Component C platinum catalyst, 25 ppm by total weight of the composition Inhibitor ethynylcyclohexanol (ECH)

[0175] Raw Materials of the Silicone Adhesive Layer:

TABLE-US-00003 Component AA vinyl terminal-polydimethylsiloxane oil, vinyl content 0.08 wt %, viscosity 60,000 mpas Component BB Organohydrogensiloxane oil, SiH terminal-polydimethylsiloxane oil, SiH content 20 wt % Component CC platinum catalyst, 25 ppm by total weight of the composition Filler Fumed Silica, BET is around 300 g/m.sup.2 Adhesive promotor 3-glycidoxypropyl trimethoxy silane Inhibitor ethynylcyclohexanol (ECH)

TABLE-US-00004 TABLE 1 EX1 EX2 EX3 EX4 EX5 EX6 EX7 EX8 EX9 EX10 EX11 A-1 100 100 100 100 100 100 100 100 100 100 100 A-2 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 B-2 11.8 11.8 11.8 11.8 11.8 11.8 11.8 11.8 11.8 11.8 11.8 D-1 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 D-2 / 16.6 / / / / / / 1.86 7.44 27.9 D-3 / / 16.6 / / / / / / / / D-4 / / / 16.6 / / / / / / / D-5 / / / / 16.6 / / / / / / D-6 / / / / / 16.6 / / / / / D-7 / / / / / / 16.6 / / / / D-8 / / / / / / / 16.6 / / / C 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Inhibitor 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Coating 20 20 20 20 20 20 20 20 20 20 20 weight (gsm) Shore A 61 71 65 73 72 72 69 73 67 70 75 Hardness Tensile 6.1 7.1 7.31 8.4 6.7 7.4 7.7 6.5 7.0 7.4 7.1 strength/Mpa Elongation at 68 76 72.9 82.5 51 52 61 55 76.5 67.5 68.6 break/% Tear strength/ 7.0 10.4 11.2 14.6 9.1 8.7 9.6 8.5 10.8 7.9 8.4 KN/m Wyzenbeek 5 w 30 w 14 w 12 w 20 w 25 w 20 w 15 w 7 w 15 w 25 w Handfeeling +++ +++++ ++++ ++++ +++++ +++++ +++++ +++++ +++ +++++ +++++ EX 12 EX13 EX14 EX15 EX16 EX 17 EX 18 EX19 EX20 EX23 A-1 100 100 100 100 100 100 100 100 100 100 A-2 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 5.26 8.69 B-2 / 5.9 3.54 11.8 11.8 11.8 11.8 11.8 11.8 11.8 B-1 11.8 5.9 8.26 / / / / / / / D-1 7.7 7.7 7.7 24.3 / / / / / / D-2 16.6 16.6 16.6 / 24.3 1 50 / 16.6 16.6 D-3 / / / / / / / / / / D-4 / / / / / / / / / / D-5 / / / / / / / / / / D-6 / / / / / / / / / / D-7 / / / / / / / / / / D-8 / / / / / / / / / / D-9 / / / / / / / 16.6 / / C 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Inhibitor 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Coating 20 20 20 20 20 20 20 20 20 20 weight (gsm) Shore A 56 65 61 69 78 64 76 68 57 61 Hardness Tensile 7.1 7.0 6.8 8.1 7.7 6.8 7 6.3 6.8 6.9 strength/Mpa Elongation at 168 85 100 88 42 104 65 77 80 80 break/% Tear strength/ 9.5 10.0 9.8 11.1 6 6.5 12 10.6 9 9.2 KN/m Wyzenbeek 1.5 w 21 w 14 w 7 w 28 w 2 w 5 w 4 w 2 w 10 w Handfeeling +++ ++++ ++++ +++ +++++ +++ +++ +++ +++ ++++ EX21 EX22 A 100 100 A′ 49.7 49.7 B′ 11.8 11.8 D-1 7.7 7.7 D-2 / / D-3 / / D-4 / / D-5 / / D-6 / / D-7 / / D-8 / / D-9 / / D-10 / 16.6 D-11 16.6 / C 0.03 0.03 Inhibitor 0.4 0.4 Coating 20 20 weight (gsm) Shore A 69 65 Hardness Tensile 8 7.4 strength/Mpa Elongation at 72 77 break/% Tear strength/ 8.4 8.6 KN/m Wyzenbeek 30 W 15 W Handfeeling +++++ ++++