CN104861175B - A kind of modified resin aqueous liquid dispersion - Google Patents
A kind of modified resin aqueous liquid dispersion Download PDFInfo
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- CN104861175B CN104861175B CN201410382402.2A CN201410382402A CN104861175B CN 104861175 B CN104861175 B CN 104861175B CN 201410382402 A CN201410382402 A CN 201410382402A CN 104861175 B CN104861175 B CN 104861175B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The present invention relates to a kind of polysiloxane-modified polyester resin aqueous systems, wherein being more than or equal to 12 nonionic emulsifier containing HLB value, and contain ethylene oxide repeating units in the nonionic emulsifier；Polysiloxane-modified polyester resin is in discrete oily phase.It has the characteristics that solid content adjustable extent is wide, simple production process, stability are good, environmental-friendly, can be widely applied to paint field.
Description
Technical field
The present invention relates to a kind of modified resin aqueous liquid dispersions.It can be widely applied to paint field.
Background technique
Polysiloxane-modified resin is with a wide range of applications, especially in coating industry.It can be used for producing resistance to height
Thermo-paint, powdery paints, weather-proof protective coating, H class B insulation paint, appliance component sealing coating, impregnated glass colth, glass tube
Coating, wire enamel, metal plate coil coating etc..
The method of modifying of polysiloxane-modified resin has physical blending process and chemical copolymerization method.The production that physical blending process obtains
Product are easy to happen microphase-separated and reduce mechanical hardness.Chemical modification can by polycondensation, free radical polymerization and addition reaction,
The end of polysiloxane backbone or side chain connect upper other organic resins, form block, grafting or interpenetrating network copolymer；Or
With hydroxyl or the silane or siloxanes of alkoxy, low molecular weight polyester resin or in which mesosome with hydroxyl or alkoxy
(in the presence of a catalyst), condensation reaction is carried out.
Polysiloxanes can be completed in the solution in advance with reacting for resin, can also complete in film forming.In coatings industry,
When being modified with silicone intermediates to other organic resins, the ratio of silicone intermediates in the final product is general
Between 5-80wt%.When ratio is lower than 10wt%, modified effect is unobvious；Ratio is higher than 50wt%, then cost is too high.Poly- silicon
The modified alkyd resin of the main polysiloxane of the kind of siloxane modified resin, polyester resin, polyacrylate, epoxy resin,
Polyurethane etc..But the product of current polysiloxane-modified polyester resin is still based on solvent type, and the content of solvent is reachable
40wt% or more, production and application process have negative effect to environment and production line personnel health.
Summary of the invention
Present inventors have unexpectedly found that a kind of polysiloxane-modified polyester resin aqueous system, with solid content adjustable extent
Extensively, good, the environmental-friendly feature of simple production process, stability.
Realize that the technical solution of the object of the invention can be summarized as follows:
A kind of polysiloxane-modified polyester resin aqueous system, wherein being more than or equal to 12 non-ionic emulsifier containing HLB value
Agent, and contain ethylene oxide repeating units in the nonionic emulsifier；Polysiloxane-modified polyester resin is in discrete oily phase
In.
Water-based system as described above, wherein nonionic emulsifier is one or more of group as shown in formula (Ia) to (IV)
It closes,
R1[CH2CH2O]nH (Ia)
HO[CH2CH2O]mR* 1[CH2CH2O]nH (Ib)
HO[CH2CH2O]p[CH2CH(CH3)O]r[CH2CH2O]qH (II)
HO[CH2CH(CH3)O]d[CH2CH2O]e[CH2CH(CH3)O]fH (III)
Wherein R1Be general formula be R (C=O)kThe monoradical of O-, wherein R is the C5-C20 alkyl of unit price, and k is 0 or 1,
It is preferred that R1It is the alkoxy or phenolic group or alkoxy carbonyl group of monovalent C6-C20, more preferably hendecane epoxide, dodecane
Oxygroup, hexadecane epoxide, octadecane epoxide, octadecane oxygen carbonyl, nonyl phenolic group, octyl phenolic group, dodecyl phenolic group,
R* 1Be general formula be-R*(C=O)lThe group of two valences of O-, wherein R*It is the C5-C20 alkyl of two valences, l is 0 or 1,
And p is 0 or positive integer, m, n, q, r, d, e, f are positive integers, and p+q>r, d+f<e,
Formula (Ia), (Ib), (II), (III) number-average molecular weight Mn range are between 1000-30000g/mol；It is preferred that 5000-
Between 20000g/mol；
Wherein R5It is the alkylene of the C4-C24 of two valences, the preferably alkylidene of C6-C20, the Asia C6-C20 monoolefine, C6-C20
Sub- diolefin, the Asia C6-C20 alkatetraenes,
R6It is the alkyl of monovalent C4-C24, the preferably alkyl of C6-C20, C6-C20 monoolefine, C6-C20 diolefin, C6-
C20 alkatetraenes,
R7It is the alkyl of H, C1-C3, preferably H,
R8It is the alkyl of C6-C20, or
R9It is the alkyl of C6-C20, or
X, y, z is 0 or positive integer, and x, y, z is not 0 simultaneously；It is preferred that x+y+z >=36；
- EO- is ethylene oxide unit.
Water-based system as described above, wherein nonionic emulsifier is selected from one or more of following set: epoxy second
Alkane epoxy propane copolymer, polyoxyethylene stearic acid ester, Brij-721, C16-C18 alcohol polyoxyethylene ether, oxidation second
Alkene modified castor oil, ethylene oxide denatured rilanit special, nonylphenol polyoxyethylene ether；And nonionic emulsifier in the set
HLB value is more than or equal to 14.
Water-based system as described above, wherein nonionic emulsifier is ethylene oxide denatured castor oil and ethylene oxide epoxy
The mixture of propane block copolymer；And the HLB value of ethylene oxide denatured castor oil is more than or equal to 12.7, ethylene oxide epoxy third
The HLB value of alkane block copolymer is more than or equal to 14.
Water-based system as described above, wherein nonionic emulsifier is ethylene oxide denatured rilanit special and ethylene oxide
The mixture of propylene oxide block copolymer；And the HLB value of ethylene oxide denatured rilanit special is more than or equal to 13.1, epoxy second
The HLB value of alkane propylene oxide block copolymer is more than or equal to 14.
Water-based system as described above, wherein nonionic emulsifier is ethylene oxide denatured rilanit special and C16-C18
The mixture of alcohol polyoxyethylene ether；And the HLB value of ethylene oxide denatured rilanit special is poly- more than or equal to 13.1, C16-C18 alcohol
The HLB value of ethylene oxide ether is more than or equal to 18.8.
Water-based system as described above, wherein 0.16- of the dosage of nonionic emulsifier in entire water-based system quality
Between 15wt%；It is preferred that between 1-10wt%.
Water-based system as described above, wherein water is continuous phase, and water accounts for the mass percent of entire water-based system in 15-
Between 90wt%；It is preferred that between 20-50wt%.
Water-based system as described above, solid content is between 10-65wt% range；It is preferred that between 20-60wt%；It is more excellent
It selects between 30-55wt%.
Water-based system as described above, the system include lotion, emulsion and suspension；The system is preferably lotion,
Middle emulsion particle diameter is in 100nm-2000nm；More preferable oil-in-water emulsion of the emulsion particle diameter within the scope of 100nm-1000nm；Wherein
Particle size distribution span (span) is preferably between 1.2-2.4.
Water-based system as described above, wherein the acid value of polysiloxane-modified polyester resin is in 0.2-50mgKOH/g, it is more excellent
It selects between 2.5-25mgKOH/g.
Water-based system as described above, wherein polysiloxane fraction accounts for the content of polysiloxane-modified polyester resin in 5-
Between 80wt%；It is preferred that between 15-60wt%；Between more preferable 15-50wt%.
Water-based system as described above, it is active group that polysiloxane-modified polyester resin, which is containing alkoxy and/or hydroxyl,
The silicone intermediates of group are to the modified obtained product of polyester resin.
Water-based system as described above, wherein oil is mutually discontinuous phase, oil mutually may contain but be not limited to esters, ketone,
Hydro carbons, alcohol ether and/or alcohol ether esters and/or divalent ester mixture；Including ethyl acetate, butyl acetate, contain succinic acid two
Methyl esters, dimethyl glutarate, dimethyl adipate divalent ester mixture；Acetone, butanone, cyclohexanone；Aromatic hydrocarbon, butyl are molten
Fine agent, n-butanol；Glycol ether ester, propylene glycol esters；Preferably include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether vinegar
Acid esters, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethylene glycol ether acetate, diethylene glycol ether acetate,
2-Butoxyethyl acetate, butyl acetate.
Polysiloxane-modified polyester product can be solid, be also possible to liquid.It is solid polysiloxane-modified poly-
Ester should be first dissolved in solvent in advance, be made into homogeneous phase solution.Under normal circumstances, the less highly concentrated solution of solvent is preferably prepared.
Polysiloxane-modified polyester liquid, appropriate nonionic emulsifier are added in reaction kettle, stirred evenly at room temperature,
It is added water in reaction kettle under stirring, and appropriate preservative is added to get water-based system of the invention is arrived.In some cases,
In order to which polysiloxane-modified polyester liquid and nonionic emulsifier is better mixed uniformly, need when the two mixes while adding
Enter suitable quantity of water.
The present invention relates to the solid contents of water-based system to refer to, takes 2 ± 0.2g sample, is placed in the culture dish that diameter is 75mm
In, 30 minutes dry under the conditions of (150 ± 2) DEG C temperature, the ratio of obtained solid material mass and initial aqueous system quality.
Water-based system of the present invention should meet following stability indicator: in 6 months standing Storage periods of room temperature, letter
Single Mechanical stirring can redisperse at being applicable to industrial fluid.
The stability indicator that preferred lotion should meet in water-based system of the present invention is: storing 2 weeks under the conditions of 50 DEG C
It is not demulsified.Wherein emulsion particle diameter is in 100nm-2000nm；More preferable emulsion particle diameter is within the scope of 100nm-1000nm, wherein partial size
Being distributed span (span) is preferably between 1.2-2.4.
Polysiloxane-modified polyester resin is polyester or polyester intermediate containing alkoxy and/or hydroxyl, and contains alcoxyl
The silicone intermediates of base and/or hydroxyl, reaction is made under conditions of using catalyst or without using catalyst.The reaction
It is that cocondensation well-known to those skilled in the art is legal.Typical preparation method refers to " organosilicon product synthesis technology and application "
Come state's bridge, good fortune Song Min, Chemical Industry Press, in May, 2010 second edition, chapters and sections 8.4.2 is about polyester modification silicone moieties
Content.
The acid value of polysiloxane-modified polyester resin is suitable for the invention in 0.2-50mgKOH/g, more preferable 2.5-
Between 25mgKOH/g.
Being preferably used in modified silicone intermediates is siliceous alkanol (containing Si-OH functional group) and/or silane oxygen
The organopolysiloxane intermediate of base (containing Si-OR functional group), wherein mono- containing one or more M unit, D unit, T
Member, Q unit:
R3 aR4 bSiO1/2M unit
R3 aR4 bSiO2/2D unit
R3 aR4 bSiO3/2T unit
SiO4/2Q unit
R3、R4It is the C1-C20 alkyl that independently represents, is optionally mingled with hetero atom linking group, such as, but not limited to:
A is 0,1,2 or 3 integer, preferably 0, an integer of 1 or 2；
B is 0,1,2 or 3 integer, preferably 0, an integer of 1 or 2；And
In M unit, a+b=3,
In D unit, a+b=2, and
In T unit, a+b=1.
R3、R4It is independently of each other preferably C1-C18 alkyl, C6-C20 aryl, C7-C18 aryl alkyl, C5-C12 cycloalkanes
Base, C2-C18 alkenyl, glycol-based, epoxy group (oxygen atom is not direct to be connect with silicon atom), C1-C18 alkoxy, C2-C20 insatiable hunger
With alkyl (such as vinyl, allyl, acrylic, isopropenyl) and terminal C4-C18 alkenyl, alkynyl, vinyl ether group and allyl
Base ether.R3、R4It is more preferably methyl, ethyl, vinyl, allyl, methoxyl group, ethyoxyl and phenyl independently of each other.
The molecule contains or is formed the silsesquioxane being made of T unit and poly-phenyl silsesquioxane and/or poly- first
Base silsesquioxane.
The silicone intermediates can be by conventional end-group termination, such as trialkylsilkl, dialkyl silane alcohol radical, dioxane
Base alkoxysilyl, alkyl dialkoxy silicyl, trialkoxysilyl, dialkyl group vinyl silyl groups,
Diarye silyl, diaryl silanol group, diaryl alkoxysilyl, aryl dialkoxy silicyl, two virtues
Base vinyl silyl groups one of which or several end groups.
Preferred silicone intermediates are methoxyphenyl/methylpolysiloxane resins, wherein phenyl and methoxyl group
The molar ratio of (and/or alkyl) is at (0.5-2): 1, preferably (0.5-1.5): 1, more preferably (0.8-1.2): 1.Resin
The content of middle phenyl is between 20-50wt%.
Silicone intermediates can be at room temperature as liquid or solid polyorganosiloxane resin.It is suitable for the invention quotient
Industry polyorganosiloxane resin includes:SY231、SY300、IC232、IC368、IC678、IC836, company, SHIN-ETSU HANTOTAI KR211, KR212,
KR214, KR216, Dow Corning Z6018, Dow Corning3037, Dow Corning233, Dow Corning249 or
Person Dow Corning3074.
In silicone intermediates, alkoxy typically constitutes from silicone intermediates 15-18%, and hydroxyl typically constitutes from polysiloxanes
The 3-6% of intermediate, higher alkoxy and/or hydroxy radical content then represent stronger with pet reaction activity.
Polyester of the present invention is that there are numerous carboxylate groups to divide greatly as the heterochain of its skeleton structure component part
Sub- compound, it be different from other carboxylates constitute skeleton structure side groups containing ester polymer, such as cellulose esters, polyacrylic acid
Ester and polyvinyl ester.Polyester resin of the present invention is more preferably in the chain structure of main side containing the polyester resin of ester group.
Currently preferred polyester is that binary or polybasic carboxylic acid or its functional derivatives and binary or polyalcohol/phenol occur
What polycondensation reaction obtained.
Polyester appropriate is in a usual manner by the carboxylic acid (or its acid anhydride) with 2 or more acid functional groups and with 2
A or more polyhydroxy functional groups polyalcohol synthesis.The example of polyfunctional carboxylic acids (acid anhydride) appropriate include: succinic acid (acid anhydride),
Glutaric acid (acid anhydride), benzene -1,2,4- tricarboxylic acids, phthalic acid (acid anhydride), tetrahydrophthalic acid (acid anhydride), hexahydro O-phthalic
Sour (acid anhydride), interior bicyclic -2,2,1-5- heptyne -2,3- dicarboxylic acids, tetrachlorophthalic acid (acid anhydride), cyclohexane diacid, isophthalic diformazan
Acid, terephthalic acid (TPA), azelaic acid, maleic acid (acid anhydride), 1,3,5- benzenetricarboxylic acid, 3,6- dichloro phthalandione, tetrachlorophthalic acid, adipic acid,
The carboxylic acids such as decanedioic acid.The example of suitable polyfunctional alcohol includes: glycerol, trimethylolpropane, pentaerythrite, ethylene glycol, diethyl
Glycol, propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, heptandiol, hexylene glycol, ethohexadiol, 2- butyl -2- second
Base -1,3- propylene glycol, season pentanediol, trimethylpentanediol, 1,4 cyclohexane dimethanol etc..
The polyester mainly there is the carboxylic acid functional of the part-COOH still to have the hydroxy functional group of-OH base, depend on
The molar ratio of-COOH/-OH in the monomer mixture.Overwhelming majority polyester for use in the present invention substantially can for 2 or
The straight chain of person's more polyhydroxy or carboxylic acid functional, or can be for the branch more than 2.5 hydroxyls or carboxylic acid functional.It is more susceptible
Under condition, the applicable polyester with various structures unit.
Embodiment
In the following embodiments, if not otherwise specified, described part is mass parts.
Genapol X1005, fatty alcohol polyoxyethylene ether, wherein per molecule contains 100 ethylene oxide units, HLB value
It is 19；It is provided by Clariant company, is used directly as emulsifier；
Emulsogen EL360, ethylene oxide denatured castor oil, wherein per molecule contains 36 ethylene oxide units, HLB
Value is 12.7；It is provided by Clariant company, is used directly as emulsifier；
Eumulgin HPS, ethylene oxide denatured rilanit special, wherein per molecule contains 40 ethylene oxide units；
HLB value is 13.1；It is provided by Cognis company and is used directly as emulsifier；
Pluronic F127, SYNPERONIC PE/F68；HLB value is 14；It is provided by BASF AG；Before use
It is made into 10wt% aqueous solution；
Myrj S100；Stearic acid (C18) polyoxyethylene ester, wherein per molecule contains 100 ethylene oxide units；HLB value
It is 18.8；It is provided by Croda company；10wt% aqueous solution is made into before use；Brij S100, stearyl alcohol (C18) polyoxyethylene
Ether, wherein per molecule contains 100 ethylene oxide units；HLB value is 19；It is provided by Croda company；10wt% is made into before use
Aqueous solution；
EMULDAC AS80, linear C16-C18 alcohol polyoxyethylene ether, wherein per molecule contains 80 ethylene oxide units；
HLB value is 18.8；It is provided by Sasol company；It is used directly as emulsifier；
ETOCAS200-SO- (MV), ethylene oxide denatured castor oil, wherein per molecule contains 200 ethylene oxide units；
HLB value is 18；It is provided by Croda company；50% aqueous solution is made into before use；Aduxol HRIC-0200, the oxidation second of hydrogenation
Alkene modified castor oil, wherein per molecule contains 200 ethylene oxide units；HLB value is 18.1；By&AG company provides；50wt% aqueous solution is made into before use；
NPE-50, nonylphenol polyoxyethylene ether, wherein per molecule contains 50 ethylene oxide units；HLB value is 18.2；By
Sasol company provides；50wt% aqueous solution is made into before use；
JY7200, wherein methyl/phenyl polysiloxane of the group containing methoxy functional accounts for polysiloxane-modified polyester resin matter
The 40wt% of amount.The product is the solution of polysiloxane-modified polyester resin, and solid content 60wt%, solvent is propylene glycol first
Ether acetate (is abbreviated as PMA)；Wherein polyester resin part is trimethylolpropane, M-phthalic acid, phthalic anhydride, season
Pentanediol monomer polycondensation forms；Acid value is less than 8mgKOH/g；It is provided by Dongguan City Jun Yi Chemical Industry Science Co., Ltd；
JY7220, wherein methyl/phenyl polysiloxane of the group containing methoxy functional accounts for polysiloxane-modified polyester resin matter
The 20wt% of amount.The product is the solution of polysiloxane-modified polyester resin, and solid content 60wt%, solvent is PMA；Wherein
Polyester resin part is trimethylolpropane, M-phthalic acid, phthalic anhydride, and season pentanediol monomer polycondensation forms；Acid value
Less than 8mgKOH/g；It is provided by Dongguan City Jun Yi Chemical Industry Science Co., Ltd；
Polysiloxane-modified polyester resin A (being abbreviated as SMP A), wherein the poly- silicon of methyl/phenyl of the group containing methoxy functional
Oxygen alkane accounts for the 30wt% of polysiloxane-modified polyester resin quality.Solution solid content is 75wt%, and solvent is PMA.Wherein polyester
Resin portion is: neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol and phthalic anhydride, M-phthalic acid, to benzene two
The polycondensation product of formic acid.SMP A acid value is 2.9mg KOH/g, and the hydroxyl value of SMP A is between 25-500mg KOH/g；Molecular weight
MWBetween 15000-17000g/mol, Mw/Mn 6 makees standard specimen with polystyrene, and tetrahydrofuran is that solvent GPC tests to obtain；
By Changxing, chemical industrial company is provided；
Polysiloxane-modified polyester resin B (being abbreviated as SMP B), wherein the poly- silicon of methyl/phenyl of the group containing methoxy functional
Oxygen alkane accounts for the 15wt% of polysiloxane-modified polyester resin quality.Solution solid content be 60wt%, solvent be PMA, n-butanol and
Butyl cellosolve；Wherein polyester resin part is the polycondensation product of neopentyl glycol, phthalic anhydride, terephthalic acid (TPA)；SMP B
Acid value is less than 10mgKOH/g；By Changxing, chemical industrial company is provided；
MBS is the isothiazolinone preservative that THOR company, Britain provides.
Use HLB value in the present invention, i.e. hydrophile-lipophile balance value indicates the hydrophily of surfactant.
The calculating formula of HLB value are as follows:
Nonionic surfactant HLB value=(hydrophilic group part molal weight/surfactant molal weight) × (100/
5)
Table 1
Embodiment 1-7 obtains the solid content of SMP resin emulsion between 40-50wt%.
Non-ionic emulsifier agent solution and SMP A resin solution are sequentially added in reaction kettle, are stirred until homogeneous, under stiring
It adds water in reaction kettle, and appropriate preservative is added.Form the white emulsion having good stability.The grain of embodiment 1-7 lotion
Diameter is as shown above.
Furthermore another preparation method is to stir SMP solution A for a period of time under heating and vacuumized conditions, then should
Solution is added in the reaction kettle equipped with non-ionic emulsifier agent solution, is stirred until homogeneous, under stiring adds water and appropriate preservative
Enter in reaction kettle.This preparation method can properly increase the solid content of SMP A resin solution and reduce its organic solvent content.
Table 2
Table 3
| Raw material | Embodiment 14 | Embodiment 15 | Embodiment 16 |
| JY7200 (solid content 60%) | 52 |
| JY7220 (solid content 60%) | 52 | ||
| SMP B (solid content 60%) | 52 | ||
| PLURONIC F127 (10% aqueous solution) | 12.8 | 12.8 | 9.6 |
| ETOCAS200-SO- (MV) (50% aqueous solution) | 3.2 | 3.2 | 4.8 |
| MBS | 0.2 | 0.2 | 0.2 |
| Water | 31.8 | 31.8 | 33.4 |
| Total amount | 100 | 100 | 100 |
| D50/ μm of partial size | 0.61 | 0.48 | 0.43 |
Table 4
By non-ionic emulsifier agent solution and corresponding SMP resin solution (such as: SMP A, JY7200, JY7220 or SMP B)
It sequentially adds in reaction kettle, is stirred until homogeneous, add water in reaction kettle under stiring, be stirring evenly and then adding into appropriate anti-corrosion
Agent forms white emulsion.The particle size data of each lotion is as shown above.Lotion prepared by embodiment 13 is stood under the conditions of 50 DEG C
It one week, is slightly layered, lotion kenel is good after simple and mechanical stirring, is suitable for industrial production, meets emulsion-stabilizing of the invention
Property index.
The solid content of the polysiloxane-modified resin oil-in-water emulsion of embodiment 8-18 is between 30-50wt%.
Each embodiment product is coated uniformly on the experiment aluminium that Q-Lab company provides with 80 microns of bars under normal temperature conditions
On plate (A-36).About 20-30 microns of coating thickness (dry film after solidification, condition of cure be 150 DEG C 15 minutes).
With glossometer measurement glossiness and visual xanthochromia degree, it is as follows to obtain test data:
Table 5
| Sample ID | Comparative example* | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 12 | Embodiment 13 | Embodiment 14 |
| Initial gloss | 118.9 | 127.2 | 132.6 | 126 | 71.9 | 82.13 | 79.9 | 82.1 |
| 200℃/1h | It is yellow | It is yellow | It is colorless and transparent | It is colorless and transparent | It is colorless and transparent | It is colorless and transparent | It is colorless and transparent | Micro- Huang |
| Gloss 1 | 111.1 | 123.8 | 122.7 | 132.7 | 74.1 | 85.73 | 83.0 | 87.3 |
| 250℃/1h | It is deep yellow | Micro- Huang | It is yellow | It is colorless and transparent | It is yellow | Micro- Huang | It is yellow | It is yellow |
| Gloss 2 | 96.1 | 117.6 | 123.6 | 115.7 | 70.30 | 87.83 | 81.07 | 84.83 |
* comparative example is that (PVA2588,4% aqueous solution measure at 20 DEG C according to DIN53015 viscous 0.96%PVA2588
Degree is 25mPas, and 88% alcoholysis degree polyvinyl alcohol is made into the aqueous solution of 10wt% before use), 52%SMP A and 0.1%
The oil-in-water emulsion that Kathon LXE preservative and water are made into.
By above-mentioned test data as it can be seen that the embodiment of the present invention in anti-yellowing property better than use polyvinyl alcohol as divide
The comparative example of powder.
The present invention tests partial size using Mastersizer2000.
For the present invention, emulsion particle diameter is obtained based on laser diffraction-light scattering principle measurement.The volume of lotion is average
Partial size is weighted average of the emulsion particle diameter to emulsion particle volume, is based on following formula (p=4, q=3):
Emulsion particle diameter is distributed span (span) by the present invention is defined as: (D90-D10)/D50.
Wherein, D50 is the particle size values at 50% cumulative distribution.For example, if D50=0.68 μm, it is meant that 50%
Sample particle is greater than 0.68 μm, and 50% sample particle is less than 0.68 μm.D10 or D90 respectively indicates 10% or 90% iterated integral
Particle size values at cloth.For example, if D10=0.1 μm, it is meant that 10% sample particle is less than 0.1 μm；D90=1 μm, just
Mean 90% sample particle less than 1 μm.
The hardness-testing device that the present invention uses is Erichsen company production " Scratch Hardness Tester
Model291 " hardometer, according to ISO15184 standard testing hardness.The measurement of luster instrument that the present invention uses is Erichsen company
" LZM151 " of production, according to ISO2813 standard testing, numerical value listed by data is the result tested under the conditions of 60 ° in table.This hair
The bright color difference meter used is BYK Gardner company production " Color Guide45/0 ", according to GB/T11186.1-89 standard
Test.
Claims (22)
1. a kind of polysiloxane-modified polyester resin aqueous system, wherein it is more than or equal to 12 nonionic emulsifier containing HLB value,
And contain ethylene oxide repeating units in the nonionic emulsifier；Polysiloxane-modified polyester resin is in discrete oily phase；
Polysiloxane-modified polyester resin is polyester or polyester intermediate containing alkoxy and/or hydroxyl, and contains alkoxy and/or hydroxyl
The silicone intermediates of base, cocondensation, which is reacted, under conditions of using catalyst or without using catalyst is made；Polysiloxanes
Intermediate is the polyorganosiloxane resin for being at room temperature liquid or solid silane-containing alcohol and/or siloxy.
2. water-based system as described in claim 1, wherein nonionic emulsifier is one kind as shown in formula (Ia) to (IV) or several
The combination of kind,
R1[CH2CH2O]nH (Ia)
HO[CH2CH2O]mR*1[CH2CH2O]nH (Ib)
HO[CH2CH2O]p[CH2CH(CH3)O]r[CH2CH2O]qH (II)
HO[CH2CH(CH3)O]d[CH2CH2O]e[CH2CH(CH3)O]fH (III)
Wherein R1Be general formula be R (C=O)kThe monoradical of O-, wherein R is the C5-C20 alkyl of unit price, and k is 0 or 1,
R*1Be general formula be-R* (C=O)lThe group of two valences of O-, wherein R* is the C5-C20 alkyl of two valences, and l is 0 or 1,
And p is 0 or positive integer, m, n, q, r, d, e, f are positive integers, and p+q>r, d+f<e,
Formula (Ia), (Ib), (II), (III) number-average molecular weight Mn range are between 1000-30000g/mol；
Wherein R5It is the alkylene of the C4-C24 of two valences,
R6It is the alkyl of monovalent C4-C24,
R7It is the alkyl of H, C1-C3,
R8It is the alkyl of C6-C20, or
R9It is the alkyl of C6-C20, or
X, y, z is 0 or positive integer, and x, y, z is not 0 simultaneously；
- EO- is ethylene oxide unit.
3. water-based system as described in claim 1, wherein nonionic emulsifier is one kind as shown in formula (Ia) to (IV) or several
The combination of kind,
R1[CH2CH2O]nH (Ia)
HO[CH2CH2O]mR*1[CH2CH2O]nH (Ib)
HO[CH2CH2O]p[CH2CH(CH3)O]r[CH2CH2O]qH (II)
HO[CH2CH(CH3)O]d[CH2CH2O]e[CH2CH(CH3)O]fH (III)
Wherein R1It is the alkoxy or phenolic group or alkoxy carbonyl group of monovalent C6-C20,
R*1Be general formula be-R* (C=O)lThe group of two valences of O-, wherein R* is the C5-C20 alkyl of two valences, and l is 0 or 1,
And p is 0 or positive integer, m, n, q, r, d, e, f are positive integers, and p+q>r, d+f<e,
Formula (Ia), (Ib), (II), (III) number-average molecular weight Mn range are between 5000-20000g/mol；
Wherein R5It is alkylidene, the Asia the C6-C20 monoolefine of C6-C20, the Asia C6-C20 diolefin or the Asia C6-C20 alkatetraenes,
R6It is alkyl, the C6-C20 monoolefine of C6-C20, C6-C20 diolefin or C6-C20 alkatetraenes,
R7It is H,
R8It is the alkyl of C6-C20, or
R9It is the alkyl of C6-C20, or
X, y, z is 0 or positive integer, and x, y, z is not 0 simultaneously；And x+y+z >=36；
- EO- is ethylene oxide unit.
4. the water-based system as described in claims 1 or 2 or 3, wherein nonionic emulsifier be selected from one of following set or
It is several: SYNPERONIC PE/F68, polyoxyethylene stearic acid ester, Brij-721, C16-C18 alcohol polyoxy second
Alkene ether, ethylene oxide denatured castor oil, ethylene oxide denatured rilanit special, nonylphenol polyoxyethylene ether；And it is non-in the set
The HLB value of ionic emulsifying agent is more than or equal to 14.
5. water-based system as described in claim 1, wherein nonionic emulsifier is ethylene oxide denatured castor oil and epoxy second
The mixture of alkane propylene oxide block copolymer；And the HLB value of ethylene oxide denatured castor oil is more than or equal to 12.7, ethylene oxide
The HLB value of propylene oxide block copolymer is more than or equal to 14.
6. water-based system as described in claim 1, wherein nonionic emulsifier is ethylene oxide denatured rilanit special and ring
The mixture of oxidative ethane propylene oxide block copolymer；And the HLB value of ethylene oxide denatured rilanit special is more than or equal to 13.1,
The HLB value of ethylene oxide propylene oxide block copolymer is more than or equal to 14.
7. water-based system as described in claim 1, wherein nonionic emulsifier be ethylene oxide denatured rilanit special and
The mixture of C16-C18 alcohol polyoxyethylene ether；And the HLB value of ethylene oxide denatured rilanit special is more than or equal to 13.1, C16-
The HLB value of C18 alcohol polyoxyethylene ether is more than or equal to 18.8.
8. the water-based system as described in claim 1 or 5 or 6 or 7, wherein polysiloxane fraction accounts for polysiloxane-modified polyester tree
The content of rouge is between 5wt%-80wt%.
9. the water-based system as described in claim 1 or 5 or 6 or 7, wherein polysiloxane fraction accounts for polysiloxane-modified polyester tree
The content of rouge is between 15-50wt%.
10. the water-based system as described in claim 1 or 5 or 6 or 7, the wherein poly- silicon oxygen of alcoxyl fiduciary point in silicone intermediates
Alkane intermediate 15-18%.
11. the water-based system as described in claim 1 or 5 or 6 or 7, wherein silicone intermediates are methoxyphenyl/methyl
Polyorganosiloxane resin；The content of phenyl is between 20-50wt% in resin.
12. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, wherein the dosage of nonionic emulsifier is entire
Between the 0.16-15wt% of water-based system quality.
13. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, wherein the dosage of nonionic emulsifier is entire
Between the 1-10wt% of water-based system quality.
14. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, wherein water is continuous phase, and water accounts for entire aqueous body
The mass percent of system is between 15-90wt%.
15. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, wherein water is continuous phase, and water accounts for entire aqueous body
The mass percent of system is between 20-50wt%.
16. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, solid content is between 10-65wt% range.
17. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, solid content is between 30-55wt%.
18. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, which is lotion, and wherein emulsion particle diameter exists
100nm-2000nm。
19. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, which is oil-in-water emulsion, wherein lotion grain
Diameter is within the scope of 100nm-1000nm and particle size distribution span (span) is between 1.2-2.4.
20. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, wherein the acid of polysiloxane-modified polyester resin
Value is between 0.2-50mgKOH/g.
21. the water-based system as described in claims 1 or 2 or 3 or 5 or 6 or 7, wherein the acid of polysiloxane-modified polyester resin
Value is between 2.5-25mgKOH/g.
22. water-based system as claimed in claim 4, wherein the acid value of polysiloxane-modified polyester resin is in 2.5-25mgKOH/
Between g.
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| CN201410382402.2A CN104861175B (en) | 2014-02-20 | 2014-08-06 | A kind of modified resin aqueous liquid dispersion |
| PCT/EP2015/053106 WO2015124506A1 (en) | 2014-02-20 | 2015-02-13 | Aqueous dispersion of a modified resin |
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| CN106947376A (en) * | 2017-03-10 | 2017-07-14 | 津正颜科技（天津）有限公司 | A kind of waterborne polyester enamel-covered wire insulated paint and its production technology |
| EP3524651A1 (en) * | 2018-02-08 | 2019-08-14 | Evonik Degussa GmbH | Aqueous polyorganosiloxane hybrid resin dispersion |
| CN112513148B (en) * | 2018-07-26 | 2024-08-02 | 瓦克化学股份公司 | Modified resin aqueous dispersion |
| CN113174190A (en) * | 2021-04-25 | 2021-07-27 | 马玉国 | Durable paint |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0520466A2 (en) * | 1991-06-28 | 1992-12-30 | Dow Corning Toray Silicone Company, Limited | Silicone-modified water-based coating composition |
| CN1071941A (en) * | 1991-10-29 | 1993-05-12 | 陶布曼斯有限公司 | Solvent-free composition |
| CN1613893A (en) * | 2004-07-16 | 2005-05-11 | 南京大学 | Preparation of carboxy silicon oil emulsion |
| CN101175784A (en) * | 2005-05-13 | 2008-05-07 | 汉高两合股份公司 | Storage-stable emulsion containing a silyl-terminated polymer, useful as adhesive, sealant, surface coating and molding composition, also new polymers |
-
2014
- 2014-08-06 CN CN201410382402.2A patent/CN104861175B/en active Active
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0520466A2 (en) * | 1991-06-28 | 1992-12-30 | Dow Corning Toray Silicone Company, Limited | Silicone-modified water-based coating composition |
| CN1071941A (en) * | 1991-10-29 | 1993-05-12 | 陶布曼斯有限公司 | Solvent-free composition |
| CN1613893A (en) * | 2004-07-16 | 2005-05-11 | 南京大学 | Preparation of carboxy silicon oil emulsion |
| CN101175784A (en) * | 2005-05-13 | 2008-05-07 | 汉高两合股份公司 | Storage-stable emulsion containing a silyl-terminated polymer, useful as adhesive, sealant, surface coating and molding composition, also new polymers |
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