WO2020019225A1

WO2020019225A1 - Aqueous dispersion of modified resins

Info

Publication number: WO2020019225A1
Application number: PCT/CN2018/097152
Authority: WO
Inventors: Zheng LI (Andreas); Wenlong Li
Original assignee: Wacker Chemie Ag
Priority date: 2018-07-26
Filing date: 2018-07-26
Publication date: 2020-01-30
Also published as: CN112513148A

Abstract

An aqueous dispersion of modified resins, which comprising a nonionic emulsifier with an HLB value of greater than or equal to 12 and silicone modified polyester resins, can be widely used in the coating field.

Description

An Aqueous Dispersion of Modified Resins

Field of the Invention

The present invention relates to an aqueous dispersion of modified resins, which can be widely used in the coating field.

Background of the Invention

Silicone modified resins have a wide variety of applications, especially in the coating field. For example, they can be used in heat-resistant coatings, powder coatings, weather-resistant protective coatings, H level insulation paints, sealing coatings for electronic components, impregnated glass cloths, glass tube coatings, wire enamel coatings and metal coil coatings.

The modification methods of silicone modified resins include physical blending methods and chemical reaction methods. Products obtained via the physical blending methods are subject to the micro-phase separation, which impairs the mechanical hardness. In chemical modification methods, organic resins are added to the backbone terminals end or side chain of silicones through condensation, free radical polymerization or addition reaction, which results silicone-organic hybrid resins in the forms of forming block copolymers, graft copolymers or interpenetrating network polymers. Or the condensation reactions can happen between the silane or siloxane containing hydroxyl groups or alkoxy groups, and the polyester resins with low molecular weight containing hydroxyl groups or alkoxy groups or intermediate products thereof, in the presence of catalysts.

Reactions between silicones and resins can occur in solution in advance, as well as in the film formation. When using silicone intermediates to modify other organic resins in the coating industry, the concentration of the silicone intermediates in the final products is normally around 5-80 wt%. If the concentration is lower than 10 wt%, the performance improvement will not be so obvious. However, the cost will be too high when the concentration is higher than 50 wt%in resin. The varieties of the silicone modified resins mainly include the silicone modified alkyd resins, polyester resins, polyacrylates, epoxy resins and polyurethanes. However, the present products of the silicone modified polyester resins are mainly based on organic solvent and the concentration of solvent could be 35 wt%or even more. This leads to adverse influence on environment and the health of the product line personnel during the production and application process.

Summary of the Invention

The present invention accidentally discovered a water based system of silicone modified polyester resins, which possesses multiple advantages, including high stability and excellent yellowing resistance. By selecting a suitable emulsifier, the water based system can also be used to prepare food-contact containers.

The technical protocols to achieve the invention goals can be concluded as below:

A water based system of silicone modified polyester resins, comprising a nonionic emulsifier with an HLB value of greater than or equal to 12, wherein the nonionic emulsifier contains repeating ethylene oxide (EO) units;

the silicone modified polyester resins are in a discontinuous oil phase; the silicone modified polyester resins are the co-condensation reaction products of the polyester resins containing alkoxy groups and/or hydroxyl groups or intermediates thereof, and silicone intermediates (a) containing alkoxy groups and/or hydroxyl groups, in the presence or absence of catalysts, wherein the silicone intermediates (a) could be silicone resins containing alkoxy groups and/or hydroxyl groups, and

furthermore, the discontinuous oil phase also contains silicone intermediates (b) in an amount of 1-50 wt%, preferably 1-30 wt%, more preferably 1-20 wt%, more preferably 1-10 wt%, more preferably 3-8 wt%, more preferably 5-7 wt%, based on the total weight of the water based system.

The water based system above, wherein the silicone intermediates (b) means that there is no chemical bond between the silicone intermediates (b) and the silicone-modified polyester resins, polyesters or polyester intermediates.

The water based system above, wherein the silicone intermediates (b) means: after the water based system stored under 23℃ more than 12 months, parts of reactive groups in the silicone intermediates (b) react with the silicone-modified polyester resins, polyesters or polyester intermediates, said reactive groups less than or equal to 50%, preferably less than or equal to 30%, more less than or equal to 10%, based on 100 mol%of all reactive groups in the silicone intermediates (b) .

The water based system above, wherein the silicone intermediates (a) are used in an amount of 5-80 wt%, preferably 15-60 wt%, more preferably 15-50 wt%, based on the weight of the silicone modified polyester resins.

The water based system above, wherein the silicone intermediates (b) are used in an amount of 5-25 wt%, preferably 8-20 wt%, more preferably 10-18 wt%, based on the weight of the silicone modified polyester resins.

The water based system above, wherein the silicone modified polyester resins are used in an amount of 10-50 wt%, preferably 30-45 wt%, based on the total weight of the water based system.

The water based system above, wherein the silicone intermediates (a) and/or silicone intermediates (b) have a melting point of lower than or equal to 85℃, preferably lower than or equal to 23℃, more preferably lower than or equal to 5 ℃, at one atmosphere of pressure.

The water based system above, wherein the alkoxy and/or hydroxyl content of the silicone intermediates (a) is greater than or equal to 3 wt%, preferably greater than or equal to 10 wt%and less than or equal to 30 wt%, more preferably greater than or equal to 12 wt%and less than or equal to 20 wt%, based on the total weight of the silicone intermediates (a) .

The water based system above, wherein the alkoxy and/or hydroxyl content of the silicone intermediates (b) is greater than or equal to 3 wt%, preferably greater than or equal to 10 wt%and less than or equal to 30 wt%, more preferably greater than or equal to 12 wt%and less than or equal to 20 wt%, based on the total weight of the silicone intermediates (b) .

A higher alkoxy and/or hydroxyl content indicates that the silicone intermediates (a) are more reactive with the polyesters or polyester intermediates.

The water based system above, wherein the hydroxyl content in the silicone intermediates (b) is less than or equal to 10wt%, preferably less than or equal to 5wt%, more preferably less than or equal to 3wt%, based on the weight of the silicone intermediates (b) .

The water based system above, wherein the silicone intermediates (a) and/or silicone intermediates (b) have methyl groups and/or phenyl substituents.

The water based system above, wherein the silicone intermediates (a) and/or silicone intermediates (b) have a weight average molecular weight (Mw) of 500-3000 g/mol, preferably 900-2000 g/mol.

The water based system above, wherein the silicone intermediates (b) and silicone intermediates (a) are the same or different.

The water based system above, wherein the oil phase contains silicone modified polyester resins, solvents and silicone intermediates (b) .

The water based system above, wherein the oil phase does not contain emulsifiers.

The water based system above, wherein the single nonionic emulsifier or the combination of all nonionic emulsifiers has a calculated HLB value of greater than or equal to 17, preferably greater than or equal to 18, preferably greater than or equal to 18.5, more preferably greater than or equal to 18.5 and less than or equal to 22, more preferably greater than or equal to 18.5 and less than or equal to 20.

The water based system above, wherein the nonionic emulsifier is one, or a combination, of what are represented by formulas (Ia) to (IV) :

R ₁ [CH ₂CH ₂O] _nH (Ia)

HO [CH ₂CH ₂O] _mR* ₁ [CH ₂CH ₂O] _nH (Ib)

HO [CH ₂CH ₂O] _p [CH ₂CH (CH ₃) O] _r [CH ₂CH ₂O] _qH (II)

HO [CH ₂CH (CH ₃) O] _d [CH ₂CH ₂O] _e [CH ₂CH (CH ₃) O] _fH (III)

where R ₁ is a monovalent group with the general formula R (C=O) _kO–, where R is a monovalent C5-C20 hydrocarbon group and k is 0 or 1,

preferably R ₁ is a C6-C20 alkoxy group or a phenolic or carboalkoxy group, more preferably undecyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, octadecyloxycarbonyl , nonylphenol, and octylphenol, dodecylphenol groups,

R* ₁ is a divalent group with the general formula –R* (C=O) ₁O–, where R*is a divalent C5-C20 hydrocarbon group and l is 0 or 1,

p is 0 or a positive integer and m, n, q, r, d, e or f is a positive integer, with p+q>r and d+f<e,

the number average molecular weight (Mn) of (Ia) , (Ib) , (II) and (III) ranges from 1000 to 30000 g/mol, preferably from 3000 to 20000 g/mol,

where R ₅ is a divalent C4-C24 hydrocarbon group, preferably C6-C20 alkylene, C6-C20 alkenylene, C6-C20 alkadienylene, and C6-C20 alkatetraenylene groups,

R ₆ is a monovalent C4-C24 hydrocarbon group, preferably C6-C20 alkyl, C6-C20 alkenyl , C6-C20 alkadienyl and C6-C20 alkatetraenyl,

R ₇ is H or a C1-C3 alkyl group, preferably H,

R ₈ is a C6-C20 hydrocarbon group, or

R ₉ is a C6-C20 hydrocarbon group, or

x, y and z are 0 or positive integers, but they are not equal to 0 at the same time, preferably x+y+z≥36,

-EO-is ethylene oxide unit.

The water based system above, wherein the nonionic emulsifier is one or more members selected from the group consisting of ethylene oxide-propylene oxide copolymers, polyoxyethylene stearate esters, polyoxyethylene stearyl ethers, C16-C18 alcohol polyoxyethylene ethers, C12-C14 alcohol polyoxyethylene ethers, C16-C18 fatty acid polyoxyethylene ester, C12-C14 fatty acid polyoxyethylene ester, ethoxylated castor oils, ethoxylated hydrogenated castor oils and nonylphenol polyoxyethylene ethers, all having a caculated HLB value of greater than or equal to 17.

The water based system above, wherein the nonionic emulsifier is a linear or branched C16-C18 alcohol polyoxyethylene ether and/or a linear or branched C12-C14 alcohol polyoxyethylene ether; preference is given to those having 100-160 EO units, when the hydrophobic segment is a linear or branched C12-14 alcohol, or those having 120-180 EO units, when the hydrophobic segment is a linear or branched C16-18 alcohol; and greater preference is given to linear or branched C12-14-EO120, linear or branched C12-14-EO100 and linear or branched C16-18-EO120.

The water based system above, wherein the nonionic emulsifier is used in an amount of 0.16-3 wt%, preferably 0.5-2.5 wt%, more preferably 1-2 wt%, based on the total weight of the water based system.

The water based system above, wherein the weight ratio of all oil phases to the emulsifiers ranges from 30 to 50, preferably from 35-50, more preferably from 40-50, more preferably from 45-50.

The water based system above, wherein water is present as a continuous phase in an amount of 15-90 wt%, preferably 25-40 wt%, more preferably 35-40 wt%based on the total weight of the water based system.

The water based system above, wherein solid content is 10-65 wt%, preferably 20-60 wt%, and more preferably 40-55 wt%, based on the total weight of the water based system.

The water based system above, including emulsion or suspension, wherein preference is given to emulsions having a particle size of 100-2000 nm, and greater preference is given to oil-in-water emulsions having a particle size of 200-500 nm

The water based system above, wherein the acid value of the silicone modified polyester resins is 0.2-50 mg KOH/g, preferably 0.5-25 mg KOH/g, more preferably 0.5-10 mg KOH/g, more preferably 2.5-10 mg KOH/g.

According to the water based system as mentioned above, the oil phase is discontinuous and may include, but is not limited to, alcohols, ethers, esters, ketones, alkanes, alcohol ethers and/or alcohol-ether-esters and/or dibasic esters or the mixture thereof, including ethyl acetate, butyl acetate and the mixtures of dibasic esters containing dimethyl succinate, dimethyl glutarate and dimethyl adipate; acetone, butanone, cyclohexanone; aromatic hydrocarbons, butyl cellosolve, butyl alcohol; and alcohol-ether-esters of ethylene glycol series, alcohol-ether-esters of propylene glycol series; preferably including one or a mixture of several ones selected from among butanol, 2-butoxyethanol, 2-butoxyethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol methyl ether propionate, di (propylene glycol) methyl ether acetate, ethylene glycol monoethyl ether acetate, di (2-ethoxyethoxy) ethyl acetate, 2-butoxyethyl acetate and di (2-butoxyethoxy) ethyl acetate.

The products of the silicone modified polyester resins could be either solid or liquid. The solid silicone modified polyester resins should be dissolved in the solvents in advance, forming a homogeneous phase solution. Normally, a high concentration solution with less solvent is preferred. The solvent is a mixture of the above alcohols, ethers, esters, ketones, alkanes, alcohol ethers and/or alcohol-ether-esters and/or dibasic esters.

The water based system in the present invention is prepared through the following steps of: feeding the silicone modified polyester resin solution, silicone intermediates (b) and appropriate amount of nonionic emulsifiers into a reaction kettle, mixing well at room temperature, adding in water while stirring as well as appropriate amount of preservatives. In order to ensure a more homogeneous mixture in some conditions, appropriate amount of water should be added while the silicone modified polyester resin solution and nonionic emulsifiers are mixed.

The solid content of the water based system in the present invention is measured in such a way that 2±0.2 g of the water based system is taken as a sample into a petri dish with the diameter of 75 mm and desiccated for 60 minutes at 150±2 ℃ to obtain solids, the weight ratio of which to the initial sample is then calculated.

The silicone modified polyester resins are the reaction products of the polyester resins containing alkoxy groups and/or hydroxyl groups or intermediates thereof, and silicone intermediates (a) containing alkoxy groups and/or hydroxyl groups, in the presence or absence of catalysts. This reaction is the co-condensation method well known to those skilled in the art. As for typical preparation method, please refer to the content on the polyesters modified silicone resins in Chapter 8.4.2 of “Synthesis Technology and Products Application of Silicone Products” by Guoqiao Lai, Songmin Xing, Chemical Industry Press, May 2010, Second Edition.

The preferred silicone intermediates (a) or silicone intermediates (b) are silicone resins (silicone resins refer to Chapter 4, Sections 4.1 and 4.2 of “Silane Coupler and Silicone Resin” by Wenrun Huang, Sichuan Science and Technology Press, 2010, First Edition) containing silanol groups (containing the Si-OH functional groups) and/or Si-alkoxy groups (containing the Si-OR functional groups) , comprising one or more of M unit, D unit, T unit and Q unit:

R ³ _aR ⁴ _bSiO _1/2 M unit

R ³ _aR ⁴ _bSiO _2/2 D unit

R ³ _aR ⁴ _bSiO _3/2 T unit

SiO _4/2 Q unit

R ³ and R ⁴ each independently represent C1-C20 hydrocarbon groups, optionally mixed with hetero atom linking groups, including but not limited to:

where a is an integer among 0, 1, 2 or 3, preferably 0, 1 or 2;

b is an integer among 0, 1, 2 or 3, preferably 0, 1 or 2; and

in M unit, a+b=3,

in D unit, a+b=2, and

in T unit, a+b=1.

Preferably, R ³ and R ⁴ each independently represent C1-C18 alkyl groups, C6-C20 aryl groups, C7-C18 aryl-alkyl groups, C5-C12 cycloalkyl groups, C2-C18 alkenyl groups, diol groups, epoxy groups (the oxygen atoms don’t connect directly to the silicon atoms) , C1-C18 alkoxy groups, unsaturated C2-C20 hydrocarbon groups (like vinyl, allyl, propenyl, isopropenyl groups) , and the terminal C4-C18 alkenyl, alkynyl, vinyl ether and allyl ether groups. More preferably, R ³ and R ⁴ each independently represent methyl, ethyl, vinyl, allyl, methoxy, ethoxy and phenyl groups.

The molecule may contain or form silsesquioxane and poly-phenyl silsesquioxane and/or poly-methyl silsesquioxane, which consist of T units.

These silicone intermediates of can be terminated by regular terminal groups, such as one or more of trialkylsilyl, dialkylsilanol, dialkylalkoxysilyl, alkyl dialkoxysilyl, trialkoxysilyl, dialkylvinylsilyl, triaryl silyl, diarylsilanol, diarylalkoxysilyl, aryl dialkoxysilyl, diarylvinylsilyl.

The preferred silicone intermediates (a) or silicone intermediates (b) are methoxy phenyl/methyl silicone resins, wherein the mole ratio of phenyl to (methoxy and/or alkyl) is (0.5-2) : 1, preferably (0.5-1.5) : 1, even more preferably (0.8-1.2) : 1. The phenyl groups are present in the resin in an amount of 20-50 wt%.

The commercial silicone intermediates suitable for the present invention include:

SY 231,

601,

SY300,

IC 232,

IC 368,

IC 678,

IC 836, Shin-Etsu KR211, KR212, KR214, KR216, Dow Corning Z 6018, Dow Corning 3037, Dow Corning 233, Dow Corning 249 or Dow Corning 3074.

The polyesters in the present invention are the hetero chain macromolecular compounds with many carboxylic ester groups as their backbone components. They are different from other ester-containing polymers with carboxylic ester groups as their backbone side chains, such as cellulose esters, polyacrylates and polyvinyl acetates. The polyester resins in the present invention are preferably the polyester resins containing ester groups in both main and side chains.

The preferable polyesters in the present invention can be obtained through the condensation between the dibasic or polybasic carboxylic acids or their functional derivatives, and the dibasic or polybasic alcohol/phenols.

The suitable polyesters can be regularly synthesized by carboxylic acids (or anhydrides thereof) containing 2 or more acidic-functional groups, and alcohols containing 2 or more hydroxyl-functional groups. The examples of the suitable multifunctional carboxylic acids (or anhydrides) include: succinic acid (or anhydride) , glutaric acid (or anhydride) , benzene-1, 2, 4-tricarboxylic acid, phthalic acid (or anhydride) , tetrahydrophthalic acid (or anhydride) , hexahydrophthalic acid (or anhydride) , inner bicycle-2, 2, 1-5-enanthine-2, 3-dicarboxylic acid, tetrachlorophthalic acid (or anhydride) , cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, azelaic acid, maleic acid (or anhydride) , trimesic acid, 3, 6-dichlorophthalic aicd, tetrachlorophthalic aicd, adipic acid and sebacic acid. The examples of the suitable multifunctional alcohols include: glycerol, trimethylol propane, pentaerythritol, ethylene glycol, diethylene glycol, propanediol, 1, 3-propylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, heptanediol, hexanediol, octanediol, 2-butyl-2-ethyl-1, 3-propanediol, neopentyl glycol, trimethyl pentanediol, cyclohexanedimethanol.

It depends on the mole ratio of -COOH/-OH in monomers mixture whether the polyester mainly contains carboxylic acid functional groups with -COOH or hydroxyl functional groups with -OH. Most of polyesters suitable for the present invention are basically the straight chains with 2 or more hydroxyl or carboxylic acid functional groups, or the side chains with more than 2.5 hydroxyl or carboxylic acid functional groups. In more cases, the polyesters with various structural units are suitable.

Detailed Description of the Preferred Embodiments

All percentages, ratios, parts and proportions are by weight unless otherwise specified.

SILRES IC 232 from Wacker Chemicals, a silicone intermediate (b) , substituted by a methylphenyl group, having a molecular weight (Mw) of about 1200 g/mol and containing about 13-15 wt%methoxy and/or hydroxyl;

SILRES IC 678 from Wacker Chemicals, a silicone intermediate (b) , substituted by a phenyl group, having a molecular weight (Mw) of about 900 g/mol and containing about 13-15 wt%methoxy and/or hydroxyl;

SILRES 601 from Wacker Chemicals, a silicone intermediate (b) , substituted by a phenyl group, containing about 5 wt%hydroxyl;

Pluronic F127 from BASF, a block copolymers based on ethylene oxide and propylene oxide, having an HLB value of 22 according its technical Bulletin, and used as 15 wt%water solution;

Lutensol AT 80 from BASF, a linear C16-C18 alcohol polyoxyethylene ether containing 80 ethylene oxide (EO) units in one molecular chain, having a calculated-HLB value of 18.2 and used as 10wt%water solution;

ETOCAS 200-SO- (MV) from Croda, an ethoxylated castor oil containing 200 EO units in one molecule chain, having an HLB value of 18.1 according its technical Bulletin, and used as 50wt%water solution.

C12-14-EO100 from Zhejiang Huangma Technology Co., LTD, a C12-C14 secondary alcohol polyoxyethylene ether containing 100 EO units in one molecular chain, having a calculated HLB value of 18.8 and used as 10wt%water solution;

C12-14-EO120 from Zhejiang Huangma Technology Co., LTD, a C12-C14 secondary alcohol polyoxyethylene ether containing 120 EO units in one molecular chain, having a calculated HLB value of 19 and used as 10wt%water solution;

Silicone modified polyester resin solution 1 (SMP 1 Solution) , 50734-S-60 from Eternal Chemical, in which the methoxy-functional methyl/phenyl silicone is present in an amount of 30 wt%based on the silicone modified polyester, the solid content is 60 wt%, and the solvent consists of 34 wt%propylene glycol monomethyl ether acetate (PMA) , 3 wt%n-butanol and 3 wt%ethylene glycol butyl ether, wherein the polyester resin is the condensation product of polyhydric diol and polybasic anhydride , and SMP 1 has an acid value of lower than 10 mg KOH/g.

Silicone modified polyester resin solution 2 (SMP 2 Solution) , SPE2388 from Kestro, in which the methoxy-functional methyl/phenyl silicone is present in an amount of 25 wt%based on the silicone modified polyester, the solid content is 64.5wt%, and the solvent is PMA, wherein the polyester resin is the condensation product of polyhydric diol and polybasic anhydride, and SMP 2 has a hydroxyl value of 0-200 mg KOH/g.

Silicone modified polyester resin solution 3 (SMP 3 Solution) from Eternal Chemical, in which the methoxy-functional methyl/phenyl silicone is present in an amount of 30 wt%based on the silicone modified polyester, the solid content is 70 wt%, and the solvent is PMA, wherein the polyester resin is the condensation product of neopentyl glycol, 2-ethyl-2-butyl-1, 3-propanediol, phthalic anhydride, isophthalic acid, and terephthalic acid, and SMP 3 has an acid value of 3.2 mg KOH/g, a hydroxyl value of 25-500 mg KOH/g, and a molecular weight (Mw) of 15000-17000 g/mol with an Mw/Mn ratio of 6, as measured by GPC test using polystyrene as standard and THF as eluent.

MBS is an isothiazolinone-based preservative, provided by Thor Company.

In the present invention, the emulsifier hydrophilicity is shown as HLB value, i.e. Hydrophilic Lipophilic Balance. For those emulsifiers whose HLB value can be not provided by producers, a calculated HLB value refers to following empirical formula for aliphatic alcohol polyoxyethylene ether emulisifiers:

The calculated HLB value of nonionic emulsifier = (mole weight of hydrophilic portion /mole weight of emulsifier) × (100/5)

Table 1

Table 2

	Ex. 2	Ex. 4	Ex. 5	Ex. 7	Ex. 8	Ex. 9
SMP1 solution	58.07	58.07	56.85	57.09	57.09	57.09
SILRES IC 232	5.12			5.04	5.04	5.04
SILRES 601			5.28
SILRES IC 678		5.12
Lutensol AT 80	1.08	1.08		1.51
ETOCAS 200-SO	0.43	0.43
C12-14-EO100			1.26		1.26
C12-14-EO120						1.26
MBS	0.08	0.08	0.08	0.08	0.08	0.08
water	35.22	35.22	36.53	36.28	36.53	36.53
Total	100	100	100	100	100	100

Oil phase/emulsifier wt/wt	41.85	41.85	49.31	41.15	49.31	49.31

Storage stability at 50 ℃ (weeks)	2.5	2.5	3	3	4	5
Particle (Z-average)	308	310	714	386	326	326

As shown by the examples and comparative examples in Table 1, the water based systems containing the silicone intermediate (b) significantly outperform their unmodified counterparts in terms of stability. As can be seen from Comparative Examples 2.2 and 3.2, the silicone intermediate (b) is difficult to be prepared to stable emulsions under the same conditions. For this reason, after the samples of Comparative Examples 2.2 and 3.2 were prepared and the stirring stopped, the resulting systems were demulsified, and therefore the particle size could not be measured with an instrument.

The sample prepared in Example Ex. 1 can also be used to make food-contact cookwares.

Examples Ex. 8 and Ex. 9 use emulsifiers with higher calculated HLB values. The stability of these samples obtained from Ex. 8 and Ex. 9 are better.

At room temperature, evenly coat the product of each example with 80-μm wire bar coaters on experimental aluminum plates (A-36) provided by Q-Lab. The dried coating thickness is about 12-18 μm (dry film after curing at 280 ℃ for 10 minutes) .

Measure the yellowing degree of the coating, obtaining the test data as below:

Table 3

	Ex. 6	C. Ex. 6
SMP1 Solution	57.6	60.7
SILRES IC 232	5.1	/
Pluronic F127	1.78	1.87
MBS	0.10	0.11
Water	35.42	37.32
Total	100	100

Oil phase/emulsifier wt/wt	35.22	32.45
Coating thickness μm	14	12

280℃ 1h Yellowing dE	5.59	6.29
280℃ 3h Yellowing dE	7.76	11.21
280℃ 5h Yellowing dE	10.89	12.56

The smaller the yellowing value dE, the lower the yellowing degree of the samples. Based on the test data above, Example Ex. 6 is better than Comparative example 6 free of the silicone intermediate (b) in the performance of yellowing resistance.

In the present invention, the particle size is measured with Malvern Mastersizer 2000 and Zetasizer Nano ZS90.

The particle size of emulsions in the present invention is measured according to the laser diffraction and light scattering. The volume based particle size is calculated based on following formula (p=4, q=3) :

The span of the particle size distribution in the present invention is defined as: (D90-D10) /D50,

where D50 is defined as the value of the particle size at 50%in the cumulative distribution. For example, if D50=0.68 μm, then 50%of the particles in the sample are larger than 0.68 μm, and 50%smaller than 0.68 μm. D10 or D90 is defined as the value of the particle size at 10%or 90%in the cumulative distribution respectively. For example, if D10=0.1 μm, then 10%of the particles in the sample are smaller than 0.1μm; if D90=1 μm, then 90%of the particles in the sample are smaller than 1μm.

The gloss was measured with the gloss meter “Spectro-Guide 45/0” by BYK according to ISO2813. The data listed in the table were the measurement results at 60°. The color difference is measured with the colorimeter “Spectro-Guide 45/0” by BYK according to GB/T11186.1-89.

Claims

A water based system of silicone modified polyester resins, comprising a nonionic emulsifier with a HLB value of greater than or equal to 12, wherein the nonionic emulsifier contains repeating ethylene oxide (EO) units;

the silicone modified polyester resins are in a discontinuous oil phase; the silicone modified polyester resins are the co-condensation reaction products of the polyester resins containing alkoxy groups and/or hydroxyl groups or intermediates thereof, and silicone intermediates (a) containing alkoxy groups and/or hydroxyl groups, in the presence or absence of catalysts, wherein the silicone intermediates (a) could be silicone resins containing alkoxy groups and/or hydroxyl groups, and

furthermore, the discontinuous oil phase also contains silicone intermediates (b) in an amount of 1-50 wt%, preferably 1-30 wt%, more preferably 1-20 wt%, more preferably 1-10 wt%, more preferably 3-8 wt%, more preferably 5-7 wt%, based on the total weight of the water based system.
The water based system according to Claim 1, wherein the silicone intermediates (a) are used in an amount of 5-80 wt%, preferably 15-60 wt%, more preferably 15-50 wt%, based on the weight of the silicone modified polyester resins.
The water based system according to Claim 1 or 2, wherein the silicone intermediates (b) are used in an amount of 5-25 wt%, preferably 8-20 wt%, more preferably 10-18 wt%, based on the weight of the silicone modified polyester resins.
The water based system according to any in Claim 1-3, wherein the alkoxy and/or hydroxyl content of the silicone intermediates (b) is greater than or equal to 3 wt%, preferably greater than or equal to 10 wt%and less than or equal to 30 wt%, more preferably greater than or equal to 12 wt%and less than or equal to 20 wt%, based on the total weight of the silicone intermediates (b) .
The water based system according to any in Claim 1-4, wherein the hydroxyl content in the silicone intermediates (b) is less than or equal to 10wt%, preferably less than or equal to 5wt%, more preferably less than or equal to 3wt%, based on the weight of the silicone intermediates (b) .
The water based system according to any in Claim 1-5, wherein the silicone intermediates (a) and/or silicone intermediates (b) have methyl groups and/or phenyl substituents.
The water based system according to any in Claim 1-6, wherein the single nonionic emulsifier or the combination of all nonionic emulsifiers has a calculated HLB value of greater than or equal to 17, preferably greater than or equal to 18, preferably greater than or equal to 18.5, more preferably greater than or equal to 18.5 and less than or equal to 22, more preferably greater than or equal to 18.5 and less than or equal to 20.
The water based system according to any in Claim 1-7, wherein the nonionic emulsifier is one, or a combination, of what are represented by formulas (Ia) to (IV) :

R ₁ [CH ₂CH ₂O] _nH                                       (Ia)

HO [CH ₂CH ₂O] _mR* ₁ [CH ₂CH ₂O] _nH                         (Ib)

HO [CH ₂CH ₂O] _p [CH ₂CH (CH ₃) O] _r [CH ₂CH ₂O] _qH          (II)

HO [CH ₂CH (CH ₃) O] _d [CH ₂CH ₂O] _e [CH ₂CH (CH ₃) O] _fH    (III)

where R ₁ is a monovalent group with the general formula R (C=O) _kO–, where R is a monovalent C5-C20 hydrocarbon group and k is 0 or 1,

preferably R ₁ is a C6-C20 alkoxy group or a phenolic or carboalkoxy group, more preferably undecyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, octadecyloxycarbonyl , nonylphenol, and octylphenol, dodecylphenol groups,

R* ₁ is a divalent group with the general formula –R* (C=O) ₁O–, where R*is a divalent C5-C20 hydrocarbon group and l is 0 or 1,

p is 0 or a positive integer and m, n, q, r, d, e or f is a positive integer, with p+q>r and d+f<e,

the number average molecular weight (Mn) of (Ia) , (Ib) , (II) and (III) ranges from 1000 to 30000 g/mol, preferably from 3000 to 20000 g/mol,

where R ₅ is a divalent C4-C24 hydrocarbon group, preferably C6-C20 alkylene, C6-C20 alkenylene, C6-C20 alkadienylene, and C6-C20 alkatetraenylene groups,

R ₆ is a monovalent C4-C24 hydrocarbon group, preferably C6-C20 alkyl, C6-C20 alkenyl , C6-C20 alkadienyl and C6-C20 alkatetraenyl,

R ₇ is H or a C1-C3 alkyl group, preferably H,

R ₈ is a C6-C20 hydrocarbon group, or

R ₉ is a C6-C20 hydrocarbon group, or

x, y and z are 0 or positive integers, but they are not equal to 0 at the same time, preferably x+y+z≥36,

-EO-is ethylene oxide unit.
The water based system according to any in Claim 1-8, wherein the nonionic emulsifier is one or more members selected from the group consisting of ethylene oxide-propylene oxide copolymers, polyoxyethylene stearate esters, polyoxyethylene stearyl ethers, C16-C18 alcohol polyoxyethylene ethers, C12-C14 alcohol polyoxyethylene ethers, C16-C18 fatty acid polyoxyethylene ester, C12-C14 fatty acid polyoxyethylene ester, ethoxylated castor oils, ethoxylated hydrogenated castor oils and nonylphenol polyoxyethylene ethers, all having an calculated HLB value of greater than or equal to 17.
The water based system according to any in Claim 1-9, wherein the nonionic emulsifier is a linear or branched C16-C18 alcohol polyoxyethylene ether and/or a linear or branched C12-C14 alcohol polyoxyethylene ether; preference is given to those having 100-160 EO units, when the hydrophobic segment is a linear or branched C12-14 alcohol, or those having 120-180 EO units, when the hydrophobic segment is a linear or branched C16-18 alcohol; and greater preference is given to emulsifiers with linear or branched C12-14 alcohol having 120 EO units, linear or branched C12-14 alcohol having 100 EO units and linear or linear or branched C16-18 alcohol having 120 EO units.
The water based system according to any in Claim 1-10, wherein the nonionic emulsifier is used in an amount of 0.16-3 wt%, preferably 1-2 wt%, based on the total weight of the water based system.
The water based system according to any in Claim 1-11, wherein the weight ratio of all oil phases to the emulsifiers ranges from 30 to 50, preferably from 35-50, more preferably from 40-50, more preferably from 45-50.
The water based system according to any in Claim 1-12, wherein solid content is 10-65 wt%, preferably 20-60 wt%, and more preferably 40-55 wt%, based on the total weight of the water based system.
The water based system according to any in Claim 1-13, wherein the acid value of the silicone modified polyester resins is 0.2-50 mg KOH/g, preferably 0.5-25 mg KOH/g, more preferably 0.5-10 mg KOH/g, more preferably 2.5-10 mg KOH/g.