阅读说明：本技术 含水聚有机硅氧烷混杂树脂分散体 (Aqueous polyorganosiloxane hybrid resin dispersion ) 是由 M·赛弗里德 S·西尔伯 B-J·德甘斯 M·菲德尔 M·哈尔莱克 于 2020-04-01 设计创作，主要内容包括：本发明涉及含水聚有机硅氧烷混杂树脂分散体,其包含：-至少一种聚有机硅氧烷混杂树脂,-至少一种基于部分水解的聚乙酸乙烯酯的乳化剂,-其中基于所述聚有机硅氧烷混杂树脂分散体,所述分散体的固体含量为30.0重量％至70.0重量％,优选为45.0重量％至55.0重量％,并且基于所述聚有机硅氧烷混杂树脂分散体,残留溶剂含量为<6.0重量％,优选<2.5重量％,更优选<1.0重量％。(The present invention relates to aqueous polyorganosiloxane hybrid resin dispersions comprising: -at least one polyorganosiloxane hybrid resin, -at least one emulsifier based on partially hydrolyzed polyvinyl acetate, -wherein the dispersion has a solids content of 30.0 to 70.0 wt. -%, preferably of 45.0 to 55.0 wt. -%, based on the polyorganosiloxane hybrid resin dispersion, and a residual solvent content of <6.0 wt. -%, preferably <2.5 wt. -%, more preferably <1.0 wt. -%, based on the polyorganosiloxane hybrid resin dispersion.)

1. An aqueous polyorganosiloxane hybrid resin dispersion comprising:

-at least one polyorganosiloxane hybrid resin, wherein the polyorganosiloxane hybrid resin comprises the reaction product of a composition comprising:

component A), 5 to 95 parts by weight, preferably 10 to 70 parts by weight, of one or more polyorganosiloxanes of the formula,

R_aSi(OR')_bO_(4-a-b/2)formula (I)

Wherein 0< a <2, 0< b <2 and a + b <4,

optionally present component B), from 0 to 20 parts by weight, preferably from 1 to 10 parts by weight, of one or more linear and/or branched polyorganosiloxanes of the formula

R”O-[R'"₂Si-O]_n-formula (II)

Component C), 5 to 95 parts by weight, preferably 30 to 90 parts by weight, of an organic polymer,

wherein R is_aR ', R ' and R ' are each independently an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 20 carbon atoms, and n is a number in the range of 4 to 250,

at least one emulsifier based on partially hydrolyzed polyvinyl acetate,

-wherein the solid content of the dispersion is from 30.0 wt% to 70.0 wt%, preferably from 45.0 wt% to 55.0 wt%, based on the polyorganosiloxane hybrid resin dispersion, and the residual solvent content is <6.0 wt%, preferably <2.5 wt%, more preferably <1.0 wt%, based on the polyorganosiloxane hybrid resin dispersion.

2. Polyorganosiloxane hybrid resin dispersion according to claim 1, characterized in that the organic polymer is selected from polyepoxides, polyesters, polyacrylates and/or polymethacrylates and copolymers thereof, polyurethanes, cellulose derivatives, polysulfones, polyethersulfones, polyphenylene sulfides and polyphenylene oxides, polyamides, polyamideimides, polyimides, polyethers, aromatic and aliphatic glycidyl-functional polymers, aromatic and aliphatic glycidyl-functional oligomers, phenoxy resins, polycarbonates, ketone-aldehyde resins, polyvinyl resins selected from polyvinyl alcohols, polyglycerols, polyvinyl acetates and (partial) hydrolysates and derivatives thereof, phenolic resins, fluoropolymers, alkyd resins and mixtures thereof.

3. Polyorganosiloxane hybrid resin dispersion according to claim 1 or 2, characterized in that the organic polymer contains hydroxyl groups and/or acidic hydrogens.

4. Polyorganosiloxane hybrid resin dispersion according to any of claims 1-3, characterized in that the emulsifier is partially hydrolyzed polyvinyl acetate with a degree of alcoholysis between 10 and 99% (mol/mol), preferably between 50 and 95% (mol/mol), more preferably between 70 and 90% (mol/mol).

5. Polyorganosiloxane hybrid resin dispersion according to any of claims 1-4, characterized in that the viscosity of the partially hydrolysed polyvinyl acetate is 1-50mPa s, preferably 1-40mPa s, more preferably 1-30mPa s, measured as a 4% aqueous solution of polyvinyl acetate at 20 ℃ according to DIN 53015.

6. Polyorganosiloxane hybrid resin dispersion according to any of the preceding claims, characterized in that it comprises further emulsifiers selected from anionic, cationic, zwitterionic or nonionic emulsifiers.

7. Polyorganosiloxane hybrid resin dispersion according to any of the preceding claims, characterized in that the dispersion has a flash point of >30.0 ℃, preferably >60.0 ℃ and more preferably >90.0 ℃ by the method in the specification.

8. Polyorganosiloxane hybrid resin dispersion according to any of the preceding claims, characterized in, that the weight ratio of the polyorganosiloxane hybrid resin to the emulsifier or emulsifier system is between 5-50, preferably between 7-40, more preferably between 10-30.

9. Polyorganosiloxane hybrid resin dispersion according to any of the preceding claims, characterized in that it comprises further additives selected from defoamers, degassing agents, rheological additives, preservatives, substrate wetting agents, crosslinking agents, drying aids, catalysts, antioxidants, antiskinning agents, antisettling agents, thickeners, coalescents, film-forming aids, fillers, pigments and/or dispersants.

10. Polyorganosiloxane hybrid resin dispersion according to any of the preceding claims, characterized in that the preservative used is a fungicide, bactericide, insecticide, algicide and/or herbicide.

11. Polyorganosiloxane hybrid resin dispersion according to any of the preceding claims, characterized in that the mean volume weighted diameter of the polyorganosiloxane hybrid resin particles is between 0.1-10.0 μ ι η, preferably between 0.1-2.0 μ ι η, more preferably between 0.2-1.0 μ ι η, most preferably between 0.2-0.7 μ ι η, measured according to ISO 13320: 2009.

12. A method of preparing an aqueous polyorganosiloxane hybrid resin dispersion comprising the steps of:

emulsifying a polyorganosiloxane hybrid resin solution comprising an organic or semi-organic solvent with an emulsifier solution comprising at least one partially hydrolyzed polyvinyl acetate based emulsifier,

-removing the solvent.

13. Method according to any of the preceding claims, characterized in that an aqueous emulsifier solution or an aqueous emulsifier system solution is used, wherein the concentration is 5-40 wt. -%, preferably 10-30 wt. -%, more preferably 15-25 wt. -%, based on the emulsifier solution.

14. The process according to any of the preceding claims, characterized in that water is additionally added in step a).

15. Method according to any of the preceding claims, characterized in that the solid content of the aqueous polyorganosiloxane hybrid resin dispersion is adjusted after step b).

16. A method according to any of the preceding claims, characterized in that the polyorganosiloxane hybrid resin comprises the reaction product of a composition comprising:

component A), 5 to 95 parts by weight, preferably 10 to 70 parts by weight, of one or more polyorganosiloxanes of the formula

R_aSi(OR')_bO_(4-a-b/2)Formula (I)

Wherein 0< a <2, 0< b <2 and a + b <4,

-optionally present component B), from 0 to 20 parts by weight, preferably from 1 to 10 parts by weight, of one or more linear and/or branched polyorganosiloxanes of the formula

R”O-[R'"₂Si-O]_n-formula (II)

Component C), 5 to 95 parts by weight, preferably 30 to 90 parts by weight, of an organic polymer,

wherein the content of the first and second substances,

R_ar ', R ' and R ' are each independently an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 20 carbon atoms, and n is a number in the range of 4 to 250.

17. The method according to any of the preceding claims, characterized in that the organic polymer comprises an organic polymer containing hydroxyl groups, preferably selected from the group consisting of polyepoxides, polyesters, polyacrylates and/or polymethacrylates and copolymers thereof, polyurethanes, cellulose derivatives, polysulfones, polyethersulfones, polyphenylene sulfides and oxides, polyamides, polyamideimides, polyimides, polyethers, aromatic and aliphatic glycidyl functional polymers, aromatic and aliphatic glycidyl functional oligomers, phenoxy resins, polycarbonates, ketone-aldehyde resins, polyvinyl resins selected from polyvinyl alcohols, polyglycerols, polyvinyl acetates and (partial) hydrolysates and derivatives thereof, phenolic resins, fluoropolymers, alkyd resins and mixtures thereof.

18. The process according to any one of the preceding claims, characterized in that the emulsifier is a partially hydrolyzed polyvinyl acetate having a degree of alcoholysis between 10% and 99% (mol/mol), preferably between 50% and 95% (mol/mol), more preferably between 70% and 90% (mol/mol).

19. The method according to any of the preceding claims, characterized in that the viscosity of the partially hydrolyzed polyvinyl acetate is 1-50 mPa-s, preferably 1-40 mPa-s, more preferably 1-30 mPa-s, measured as a 4% aqueous solution of polyvinyl acetate at 20 ℃ according to DIN 53015.

20. The process according to any one of the preceding claims, characterized in that it further comprises other emulsifiers selected from anionic, cationic, zwitterionic or nonionic emulsifiers.

21. A method according to any of the preceding claims, characterized in that the solvent is at least one organic solvent or at least one semi-organic solvent that has been used in the preparation of the polyorganosiloxane hybrid resin.

22. The process according to any one of the preceding claims, wherein the organic solvent or mixture thereof has a boiling point in the range of 50 ℃ to 150 ℃, preferably 90 ℃ to 120 ℃.

23. The method according to any one of the preceding claims, characterized in that the solvent is removed by means of distillation with or without stripping gas under reduced pressure, steam distillation, or by means of a membrane process, thin-film evaporator or counter-current process.

24. A method according to any of the preceding claims, characterised in that the polyorganosiloxane hybrid resin solution has a polyorganosiloxane hybrid resin concentration of 40.0-95.0 wt. -%, preferably 60.0-70.0 wt. -%, based on the polyorganosiloxane hybrid resin solution.

25. A method according to any of the preceding claims, characterized in that the flash point of the aqueous polyorganosiloxane hybrid resin dispersion prepared by the method can be raised.

26. Use of the polyorganosiloxane hybrid resin dispersion according to any of claims 1-11 in coating materials, as well as coatings and paints, substrate coatings, semi-finished products, adhesives, inks, sealants, compounded matrices and sizes.

27. Substrate, in particular baking pan, baking can, pan, metal can, etc., coated with a composition comprising a dispersion according to any of claims 1 to 11.

Examples

Preparation of aqueous polyorganosiloxane hybrid dispersions according to the invention

To prepare the aqueous polyorganosiloxane hybrid dispersion according to the present invention, a solvent-based polyorganosiloxane hybrid solution is first prepared. The solvent is then removed by the process of the invention.

1. Preparation of solvent-based polyorganosiloxane hybrid solution with polyester (hereinafter referred to as silicone-polyester hybrid solution)

1.1 preparation of the polyorganosiloxanes as component A

Solvents used: methyl isobutyl ketone (MIBK), diethyl carbonate (DEC), Methyl Propyl Ketone (MPK), ethyl acetate (EtAc), isobutyl acetate (iBuAc), ethyl isobutyrate (EtiBu)

First, three polyorganosiloxanes POS 1, POS 2 and POS 3 were prepared according to EP 0157318 with the parameters of Table 1 below.

POS 4 is a commercially available polyorganosiloxane from Dow Corning.

TABLE 1

1.2 preparation of hydroxy-functional polyesters as component C

The hydroxy-functional polyester PES 1-PES 5 was prepared by esterification of trimethylolpropane, isophthalic acid and ethylene glycol by the method described in DE 3728414C 1. The solids content and the viscosity were adjusted using the solvents according to table 2.

TABLE 2

1.3 preparation of solvent-based Silicone-polyester hybrid solution (variant 1)

The silicone-polyester hybrid solutions SiPES 6-SiPES 11 were prepared by the method according to EP 0092701.

The silicone-polyester hybrid solution SiPES 12 was prepared by the method according to EP 1072660.

In this case, components A and C in tables 1 and 2 were used. Table 3 shows other relevant data.

TABLE 3

1.4 preparation of solvent-based Silicone-polyester hybrid solution (variant 2)

The silicone-polyester hybrid solution SiPES1-SiPES 5 was prepared by the method according to example 1 of DE 102013218981.

In this case, an organic polymer is used as the monomer. Table 4 shows the data relating to the silicone-polyester hybrid solution SiPES1-SiPES 5.

TABLE 4

1.5 solvent-based, epoxide-based polyorganosiloxane hybrid solutions (hereinafter referred to as organosilicon-polyepoxide hybrid solutions)

Commercial purchase using from Evonik IndustriesEW。

2. Preparation of polyorganosiloxane hybrid dispersions

The above-described solvent-based silicone-polyester hybrid solution (variants 1 and 2) and the above-described solvent-based silicone-polyepoxide hybrid solution, which is referred to as a polyorganosiloxane hybrid resin in the following method, are used.

2.1 method 1, the invention:

first 100.0 g of4-88 in demineralized water to 20% solution. Subsequently, 360.0 grams of the polyorganosiloxane hybrid resin dissolved in an appropriate amount of solvent was added. The speed of the stirrer system here was 1000 rpm. The result was a high viscosity paste, which was stirred at 1000rpm for an additional 60 minutes once the addition of resin was complete. Subsequently, 140.0 grams of demineralized water was added. In the next step, the solvent is removed by distillation. For this purpose, the temperature is raised to 50 ℃ and the pressure is reduced to 40 mbar. Subsequently, the solids content of the dispersion was determined. The solids content of the dispersion was then adjusted to 50.0% by adding demineralized water with stirring.

2.2 method 2, the invention:

the same as in Process 1, except that the emulsifier solution is

3-80 in deionized water.

2.3 method 3, the invention:

the same as in Process 1, except that the emulsifier solution is

18-88 in deionized water.

2.4 method 4, the invention:

the same as in Process 1, except that the emulsifier solution is

A 20% solution of KL-03 in deionized water.

2.5 method 5, the invention:

the same as in Process 1, except that the emulsifier solution is

KL-05 in20% solution in deionized water.

2.6 method 6, the invention:

same as method 1 except that 70.0 g of4-88 in deionized water at 20% and 30.0 gramsA50% solution of 15-S-5 in deionized water was first charged to a room temperature vessel.

The particle size, flash point and residual solvent content of each of the dispersions E1-E30 prepared were determined. These values can be found in table 5.

All dispersions were adjusted to a solids content of 50 wt.%.

TABLE 5

The residual solvent content of the dispersion according to the invention is less than 6% by weight. In all cases, the flash point of the dispersions according to the invention was higher than that of the comparative example (VE 24). Especially in the case of the inventive dispersion with a residual solvent content < 1% by weight, a flash point >100 ℃ is reported, since the dispersion boils here due to the water content and therefore the flash point cannot be determined.

Comparative example VE24 is a dispersion having a residual solvent content of 6.1 wt.% and a solids content of 50 wt.%. To prepare VE24 with this residual solvent content, the process according to the invention is expediently ended as early as possible. The flash point decreases accordingly.

It has thus been found that the method according to the invention makes it possible to increase the flash point of aqueous polyorganosiloxane hybrid resin dispersions.

3. Is demarcated from WO 2015/091901 (hereinafter referred to as "Wacker")

Silicone-modified polyester resins having a solvent content of 40 wt.% according to Wacker examples 5, 6, 7, 10, 11 and 12 were used and dispersions were prepared by the "Wacker" method.

For this purpose, the silicone polyester resin is distilled under reduced pressure at a maximum of 90 ℃ until the resin mass (resin mass) exhibits a viscosity at which the resin can still be processed. Processability is required in order to carry out emulsification in the next step. Since WO 2015/091901 does not disclose any details regarding temperature and duration, a temperature below the boiling point of water is used. The solid content was then determined:

it has been found that at solids contents exceeding 85% by weight, the resin mass is no longer processable. It is no longer emulsifiable.

At a maximum solids content of 80 wt.%, the resin mass still has sufficient processability to be used for preparing a 30 wt.% solids dispersion based on the polyorganosiloxane hybrid resin dispersion. This dispersion theoretically leads to a residual solvent content of 6% by weight. It is conceivable to reduce the residual solvent content of the dispersion by dilution with additional water, but this correspondingly reduces the solids content of the dispersion.

It is therefore not possible to use the process according to WO 2015/091901 in order to obtain the dispersion according to the invention.

Performance testing

1. Application and curing method

1.1 method 1: 2-component isocyanate crosslinking

The dispersions E1 to E15 according to the invention were mixed with3100 at 3: 1 and pulled to Q-Lab by means of a spiral coating rodAluminum color test panels (alloy 3003H 14; 0.025' thick (0.6 mm); bare ground surface). The wet film thickness was 100. mu.m. After drying at room temperature for 24 hours, the result was clear and noneThe film of defects had a dry film thickness of 50 μm. The test panels were aged for 10 days at 23 ℃ and 65% relative humidity.

1.2 method 2: thermal crosslinking

The dispersions E16-E23 and E25-E30 of the invention were drawn to Q-Lab by means of a spiral-coating rod

Aluminum color test panels (alloy 3003H 14; 0.025' thick (0.6 mm); bare polished surface). The wet film thickness was 100. mu.m. After drying at room temperature for 0.5 h, the result was a clear, defect-free film with a dry film thickness of 50 μm. After this flash time at room temperature, the air dried test panels were baked in an air circulation oven at 250 ℃ for 15 minutes.

Similarly, solvent-based SiPES1, SiPES 2, SiPES 8, SiPES 9, and SiPES 12 are applied and cured.

4. Measurement of pendulum hardness

By means of

The films were characterized by pendulum hardness (DIN 53157).

The values can be seen in table 6.

Table 6: hardness of pendulum bar

It has been found that the aqueous dispersions according to the invention have pendulum hardness values which are as good as those of the solvent-based polyorganosiloxane hybrid resins. Pendulum hardness is important as it gives a direct conclusion about the durability of the final coatings using the polyorganosiloxane hybrid resin dispersions of the invention.