CN113604096B - Fluorocarbon wetting agent compound system - Google Patents
Fluorocarbon wetting agent compound system Download PDFInfo
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- CN113604096B CN113604096B CN202110847555.XA CN202110847555A CN113604096B CN 113604096 B CN113604096 B CN 113604096B CN 202110847555 A CN202110847555 A CN 202110847555A CN 113604096 B CN113604096 B CN 113604096B
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
A fluorocarbon wetting agent compound system relates to the technical field of water-based paint, the compound system consists of a fluorocarbon wetting agent, a non-fluorocarbon wetting agent, a nonionic surfactant and a cosurfactant, wherein the contents of the components are as follows in sequence according to mass ratio: 5-40 parts of fluorocarbon wetting agent; 30-60 parts of non-fluorocarbon wetting agent; 5-50 parts of nonionic surfactant; 20-60 parts of cosurfactant, and the compound system is more efficient than singly using the fluorocarbon wetting agent through the synergistic interaction of the fluorocarbon wetting agent, the non-fluorocarbon wetting agent, the nonionic surfactant and the cosurfactant, greatly reduces the cost and has ideal wetting effect in a water-based coating system.
Description
Technical Field
The invention relates to the technical field of water-based paint, in particular to a fluorocarbon wetting agent compound system.
Background
Wettability is a representation of the ability of a liquid substance to bind to a solid and to wet, spread, and penetrate the surface of the solid. The liquid with good wettability can be easily spread on the solid surface and can easily permeate into every fine gap on the solid surface. The wetting performance is related to the surface tension of solids and liquids. The smaller the surface tension of the liquid, the larger the surface tension of the solid, the better the wettability of the liquid to the solid, and the liquid can form a large spreading area on the surface of the solid. Wetting ability can be quantitatively expressed in terms of the contact angle θ that a droplet forms on the solid plane (as shown in fig. 1). The smaller the contact angle, the better the wettability of the liquid with respect to the solid, and obviously, when the contact angle θ is zero, the liquid has the best wettability with respect to the solid. θ=90° is a critical criterion, and when the contact angle θ <90 ° is less than the contact angle θ, spontaneous wetting of the liquid occurs, whereas when θ >90 ° is not possible. As shown in fig. 1, θ <90 ° on the left, wet well, θ >90 ° on the right, no wet.
In the paint industry, to ensure adhesion between a water-based paint and a substrate, the surface tension between the substrate and the water-based paint needs to meet certain requirements. The wetting effect of the test substrate wetting agent can generally be determined by measuring the surface tension after addition. The smaller the surface tension of a solid, the greater the young's equilibrium contact angle of the same liquid, the more difficult it is to wet. For the same solid surface, the greater the surface tension of the liquid, the greater its equilibrium contact angle and the harder it is to wet. Aqueous paints and inks use water as the primary dispersion medium, and the surface tension of water is much greater than that of organic solvents, and far exceeds that of various common substrates. At this time, the situation that the wetting effect of the water-based paint on the base material is poor is extremely easy to occur, so that the defects of poor film spreadability, surface defects, poor adhesive force and the like are caused, and particularly, the base material with low surface energy cannot be wetted at all, so that the coating is difficult. Therefore, the wetting of the substrate by the aqueous coating is often the primary problem. Two approaches are generally taken to improve wettability: the first method is to treat the surface of the base material and remove greasy dirt, dust dirt and the like; the steel surface can be subjected to polishing, sand blasting and other treatments; some plastic substrates may be corona treated, flame sprayed, acid oxidized, etc. to increase the surface energy of the substrate and enhance wettability. The second approach is to add a substrate wetting agent to reduce the surface tension of the coating, particularly the interfacial tension between the coating and the substrate. The method for adding the substrate wetting agent is most commonly used, and the basic requirements on the substrate wetting agent are high efficiency of reducing surface tension, good system compatibility, general water dissolution, low foam, unstable foam, low sensitivity to water, effective prevention or elimination of shrinkage cavity, effective improvement of the pore-forming property, high efficiency (small addition amount), auxiliary improvement of leveling and fluidity, good long-acting property in a formula, and no recoating trouble and adhesion reduction.
The main types of common substrate wetting agents are anionic surfactants, nonionic surfactants, polyether modified polysiloxane compounds, acetylenic diol compounds and the like, and the static surface tension of aqueous solutions of the substrate wetting agents is usually 20-35 dynes, as shown in table 1, and the typical 0.1% aqueous solution of the substrate wetting agents has the surface tension tested at 25 ℃, which can achieve the basic wetting effect on the conventional substrate.
TABLE 1
| Species of type | Static surface tension | Dynamic surface tension |
| Nonionic block copolymers | 35 dyne | - |
| Anionic sulfonates | 28 dyne | 31 dyne |
| Alkyne diol base material wetting agent | 26 dyne | 28 dyne |
| Polyether modified polysiloxane | 20.5-22 dynes | 60-65 dyne |
| High molecular weight silicone surfactant | 35 dyne | - |
However, some special substrates, such as polytetrafluoroethylene surfaces, paraffin surfaces, and glass cement surfaces, do not achieve the desired wetting effect. Some substrates have greasy dirt on the surface, and the functions of wetting and shrinkage cavity prevention cannot be achieved by adopting the conventional substrate wetting agents. Some porous substrates, such as wood, require the ability of a coating or ink to enter the conduit, and the surface tension is not reduced to an adequate extent or is not as satisfactory with conventional substrate wetting agents such as those described above. Although fluorocarbon wetting agents exist in the market, the fluorocarbon wetting agents refer to hydrocarbon surfactants in which hydrogen atoms in hydrocarbon chains are completely or partially replaced by fluorine atoms, and the surface tension of solvents can be obviously reduced at extremely low concentration, the fluorocarbon wetting agents have high production cost, high market price and no universal applicability, and therefore, the fluorocarbon wetting agents have to be improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a fluorocarbon wetting agent compound system, which comprises the following specific schemes:
the fluorocarbon wetting agent compound system consists of a fluorocarbon wetting agent, a non-ionic surfactant and a cosurfactant, wherein the contents of the components are as follows in sequence according to mass ratio:
5-40 parts of fluorocarbon wetting agent;
30-60 parts of non-fluorocarbon wetting agent;
5-50 parts of nonionic surfactant;
20-60 parts of cosurfactant.
Further, the fluorocarbon wetting agents include anionic, cationic, nonionic, and amphoteric fluorocarbon wetting agents.
Further, the fluorocarbon wetting agent adopts an anionic fluorocarbon wetting agent.
Further, the anionic fluorocarbon wetting agent comprises a carboxylate (R f COO - M + ) Sulfonate (R) f SO 3 - M + ) Sulfate type (R) f OSO 3 - M + ) Phosphate type (R) f OP(O)O 2 2- M 2+ )；
Wherein M is + ＝Na + 、K + 、Li + 、NH 4 + 、N(C m H 2m+1 ) 4+ 、NH(C m H 2m+1 ) 3+ (m＝1-4)、NH(CH 2 CH 2 OH) 3+ 、NH 2 (CH 2 CH 2 OH) 2+ Or NH 3 CH 2 CH 2 OH + ；
Wherein R is f ＝CF 3 (CF 2 ) n CH 2 CH 2 -(n＝3-17)。
Further, the non-fluorocarbon wetting agent comprises a low molecular weight organosilicon wetting agent, a low molecular weight organic sulfonate wetting agent, a fatty alcohol polyoxyethylene ether phosphate wetting agent, an alkyne diol wetting agent or an alkyne diol polyether wetting agent.
Further, the general formula of the low molecular weight organosilicon wetting agent is:
y≥1，x+y≤6；R＝-CH 2 CH 2 CH 2 -O-(EO) m (PO) n -K；
wherein eo= -CH 2 CH 2 -O-；
PO＝-CH(CH 3 )CH 2 O-；
K= -OH or-CH 3 or-CH 2 CH 2 CH 3 or-C (=O) -CH 3 。
Further, the general formula of the low molecular organic sulfonate wetting agent is: RSO (RSO) 3 - M + ；
Wherein R is saturated straight-chain alkyl, saturated branched alkyl or unsaturated alkyl, and has a carbon number of 4-18, wherein M + ＝Na + 、K + 、Li + 、NH 4 + 、N(C m H 2m+1 ) 4+ 、NH(C m H 2m+1 ) 3+ (m＝1-4)、NH(CH 2 CH 2 OH) 3+ 、NH 2 (CH 2 CH 2 OH) 2+ Or NH 3 CH 2 CH 2 OH + 。
Further, the general formula of the fatty alcohol polyoxyethylene ether phosphate wetting agent is as follows: r- (EO) n OP(O)O 2 2- M 2+ ；
Wherein R is saturated straight-chain alkyl or saturated branched alkyl, the carbon number is 4-18, EO= -CH 2 CH 2 O-, n=0-5, where M + ＝Na + 、K + 、Li + 、NH 4 + 、N(C m H 2m+1 ) 4+ 、NH(C m H2 m+1 ) 3+ (m＝1-4)、NH(CH 2 CH 2 OH) 3+ 、NH 2 (CH 2 CH 2 OH) 2+ Or NH 3 CH 2 CH2OH + 。
Further, the nonionic surfactant is long-chain alkyl polyoxyethylene ether, and the general formula of the nonionic surfactant is as follows: r- (EO) n-OH;
wherein R is alkyl alcohol or alkyl amine, EO= -CH 2 CH 2 O-。
Further, the cosurfactant is a lower alcohol or a lower ether.
Compared with the prior art, the invention has the following beneficial effects:
(1) The compound system is more efficient than singly using the fluorocarbon wetting agent through the synergistic interaction of the fluorocarbon wetting agent, the non-fluorocarbon wetting agent, the nonionic surfactant and the cosurfactant, greatly reduces the cost and has ideal wetting effect in a water-based coating system.
The wetting agent compound system prepared according to the formula, 0.1% aqueous solution, the minimum static surface tension tested at 25 ℃ can reach 15.2 dyne, and the addition of the wetting agent compound system into paint or water can sharply reduce the static surface tension of the system, so that an excellent wetting effect is generated, the wetting agent compound system is very effective in preventing and eliminating shrinkage cavities generated by pollution, and the porous base material such as wood is extremely obvious in improving the access and permeability.
Drawings
FIG. 1 is a graph showing the effect of a liquid on a solid surface at a contact angle in the background of the invention;
FIG. 2 is a graph showing the effect of the foam stability test of the addition of a wetting agent to an emulsion.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The fluorocarbon wetting agent compound system consists of a fluorocarbon wetting agent, a non-fluorocarbon wetting agent, a nonionic surfactant and a cosurfactant, wherein the contents of the components are as follows in sequence according to mass ratio:
5-40 parts of fluorocarbon wetting agent;
30-60 parts of non-fluorocarbon wetting agent;
5-50 parts of nonionic surfactant;
20-60 parts of cosurfactant.
Fluorocarbon wetting agents include anionic, cationic, nonionic and amphoteric fluorocarbon wetting agents, with the fluorocarbon wetting agents preferably being anionic.
The anionic fluorocarbon wetting agent comprises a carboxylate (R f COO - M + ) Sulfonate (R) f SO 3 - M + ) Sulfate type (R) f OSO 3 - M + ) Phosphate type (R) f OP(O)O 2 2- M 2+ )；
Wherein M is + ＝Na + 、K + 、Li + 、NH 4 + 、N(C m H 2m+1 ) 4+ 、NH(C m H 2m+1 ) 3+ (m＝1-4)、NH(CH 2 CH 2 OH) 3+ 、NH 2 (CH 2 CH 2 OH) 2+ Or NH 3 CH 2 CH 2 OH + ；
Wherein R is f ＝CF 3 (CF 2 ) n CH 2 CH 2 -(n＝3-17)。
The non-fluorocarbon wetting agent comprises a low molecular weight organosilicon wetting agent, a low molecular weight organic sulfonate wetting agent, a fatty alcohol polyoxyethylene ether phosphate wetting agent, an alkyne diol wetting agent or an alkyne diol polyether wetting agent.
The general formula of the low molecular weight organosilicon wetting agent is:
y≥1，x+y≤6；R＝-CH 2 CH 2 CH 2 -O-(EO) m (PO) n -K；
wherein eo= -CH 2 CH 2 -O-；
PO＝-CH(CH 3 )CH 2 O-；
K= -OH or-CH 3 or-CH 2 CH 2 CH 3 or-C (=O) -CH 3 。
The general formula of the low molecular organic sulfonate wetting agent is: RSO (RSO) 3 - M + ；
Wherein R is saturated straight-chain alkyl, saturated branched alkyl or unsaturated alkyl, and has a carbon number of 4-18, wherein M + ＝Na + 、K + 、Li + 、NH 4 + 、N(C m H 2m+1 ) 4+ 、NH(C m H 2m+1 ) 3+ (m＝1-4)、NH(CH 2 CH 2 OH) 3+ 、NH 2 (CH 2 CH 2 OH) 2+ Or NH 3 CH 2 CH 2 OH + 。
The low molecular organic sulfonate wetting agent is preferably selected from: sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, sodium dioctyl dibutyrate sulfonate, sodium alpha-alkenyl sulfonate.
The general formula of the fatty alcohol polyoxyethylene ether phosphate wetting agent is as follows: r- (EO) n OP(O)O 2 2- M 2+ ；
Wherein R is saturated straight-chain alkyl or saturated branched alkyl, the carbon number is 4-18, EO= -CH 2 CH 2 O-, n=0-5, where M + ＝Na + 、K + 、Li + 、NH 4 + 、N(C m H 2m+1 ) 4+ 、NH(C m H 2m+1 ) 3+ (m＝1-4)、NH(CH 2 CH 2 OH) 3+ 、NH 2 (CH 2 CH 2 OH) 2+ Or NH 3 CH 2 CH 2 OH + 。
The fatty alcohol polyoxyethylene ether phosphate wetting agent is preferably selected from the group consisting of: isooctyl alcohol phosphate sodium salt, ethylene glycol monoisooctyl ether phosphate sodium salt, diethylene glycol monoisooctyl alcohol phosphate sodium salt, isooctyl alcohol phosphate sodium salt (eo=3), isooctyl alcohol phosphate sodium salt (eo=5).
The alkyne diol wetting agent or alkyne diol polyether wetting agent is preferably butyne diol, hexyne diol, decyne diol, dodyne diol, and ethoxylated polyether derivatives (eo=1 to 30) corresponding to each alkyne diol, preferably dodyne diol and dodyne diol polyoxyethylene ether (eo=15).
The nonionic surfactant is long-chain alkyl polyoxyethylene ether, and the general formula of the nonionic surfactant is: r- (EO) n-OH;
wherein R is alkyl alcohol or alkyl amine, EO= -CH 2 CH 2 O-。
The nonionic surfactant is preferably selected from: dodecyl polyoxyethylene ether (eo=3), dodecyl polyoxyethylene ether (eo=5), dodecyl polyoxyethylene ether (eo=7), and dodecyl polyoxyethylene ether (eo=9).
The cosurfactant is a lower alcohol or lower ether. The cosurfactant is preferably selected from: methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, n-pentanol, isopentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol, glycerol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether.
Based on the above, the present invention makes the following examples 1 to 12.
The non-fluorocarbon wetting agent used in all embodiments specifically adopts a low molecular weight organosilicon wetting agent, a low molecular weight organic sulfonate wetting agent or a fatty alcohol polyoxyethylene ether phosphate wetting agent, and can be one or the combination of the two. The silicones in table 2 are: x=3, y=1, r= -CH 2 CH 2 CH 2 -O-(EO) 7 (PO) 1 -CH 3 Low molecular weight silicone wetting agents of (2). The fast T in Table 2 is a low molecular weight organic sulfonate wetting agent, specifically dioctyl sodium sulfonate dibutyrate. JFC-3 in Table 2 is fatty alcohol polyoxyethylene ether phosphateThe ester salt wetting agent is specifically isooctyl alcohol phosphate sodium salt (eo=3).
The fluorocarbon wetting agent used in all examples is specifically a sulfonate (R f SO 3 - M + ). The fluorine table a in table 2 specifically uses sodium heptadecafluorooctyl sulfonate, and the fluorine table b specifically uses sodium heptadecafluorooctyl ethyl sulfonate.
The nonionic surfactant used in all examples was specifically dodecyl polyoxyethylene ether (eo=7), and AEO-7 in table 2 was fatty alcohol polyoxyethylene ether.
The cosurfactant used in all examples is a lower alcohol, in particular butanol.
The formulation of the specific complex wetting agents of examples 1-12 is shown in Table 2.
Table 2 formula of fluorocarbon wetting agent compounding system
The fluorocarbon wetting agent, the non-fluorocarbon wetting agent, the nonionic surfactant and the cosurfactant were mixed in the proportions shown in table 2 to obtain a compound system with definite concentration and composition. As can be seen from table 2, the total parts of fluorocarbon wetting agent is 30 parts, the total parts of non-fluorine wetting agent is 20 parts, the non-ionic surfactant is 10 parts, and the cosurfactant is 40 parts.
The performance test method of the fluorocarbon wetting agent compound system prepared in examples 1-12 is as follows:
(1) Surface tension test method of wetting agent: the static surface tension was measured by a platinum plate method, and a 0.1% aqueous solution was prepared, and a lower static surface tension indicates a stronger wetting ability with respect to the substrate. The results of the test are shown in table 3:
TABLE 3 static surface tension of 0.1% aqueous solutions of wetting agents
As can be seen from Table 3, the wetting agents formulated according to examples 1-12, 0.1% aqueous solutions, have a minimum static surface tension of 15.2 dynes and a maximum static surface tension of no more than 19 dynes when tested at 25 ℃. Because both the dyne value and the contact angle are methods for evaluating the wettability of the solid surface, the higher the free energy of the surface is, the better the wetting of a water drop on the solid surface is, the smaller the contact angle is, the lower the free energy of the surface is, the better the wetting of a water drop on the solid surface is, the larger the contact angle is, compared with the method in the prior art in Table 1, the dyne value of the fluorocarbon wetting agent in the invention is greatly lower than that of each typical substrate wetting agent in Table 1, and the wetting effect of the compound fluorocarbon wetting agent in the invention is greatly improved compared with the existing wetting agent. The fluorocarbon wetting agent compound system of the invention does not use expensive fluorocarbon wetting agent alone while improving the wetting effect, but simultaneously introduces a plurality of non-fluorocarbon wetting agents, nonionic surfactants and cosurfactants, and combines synergistic effect together, thus relatively reducing the production cost.
In examples 1-12, the fluorocarbon wetting agent used a sulfonate salt (R f SO 3 - M + ) The non-fluorocarbon wetting agent uses one or two of a low molecular organic silicon wetting agent, a low molecular organic sulfonate wetting agent or a fatty alcohol polyoxyethylene ether phosphate wetting agent, and the non-ionic surfactant and the cosurfactant are limited to one, so that under the condition of meeting control variables, the synergistic effect of the non-fluorocarbon wetting agent and the fluorocarbon wetting agent can be exerted when the fluorocarbon wetting agent and the non-fluorocarbon wetting agent specifically adopt different wetting agents, and the finally displayed wetting effect is not influenced.
In specific application, the fluorocarbon wetting agent can be added into paint or water to drastically reduce the static surface tension of the system, thereby generating excellent wetting effect, being very effective in preventing and eliminating shrinkage cavities generated by pollution, and improving the porosity and permeability of porous substrates such as wood.
(2) The foam inhibition performance test method comprises the following steps: the substrate wetting agent can greatly reduce the surface tension, so that the substrate wetting agent has a negative effect of stabilizing foam when applied to an aqueous system, and is often matched with a defoaming agent. However, by adjusting the hydrophilicity of each component in the base material wetting agent to decrease the hydrophilicity, an unstable foam product can be obtained.
Specifically, 80 g of Wantipro 0616 emulsion and more than 0.4 g of wetting agent corresponding to examples 1-12 in the present invention are added into a 100 ml transparent plastic bottle, the mixture is put into a dispersor DAS 200 oscillator for 10 minutes after being sealed, the mixture is taken out and placed still for 1 minute, the height of the liquid level is observed, and then the foam stability of the wetting agent is evaluated. The higher the liquid level, the stronger the foam stability of the wetting agent; the lower the liquid level, the less stable the wetting agent is. The data tested are shown in table 4:
table 4 results of foam stability test of wetting agent added to emulsion
The pictures tested are shown in figure 2.
In combination with the results of table 4 and the case of fig. 2, the compounded systems of 6 of examples 1-12 meet the basic requirements of a wetting agent and are unstable after application in an emulsion.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (1)
1. The fluorocarbon wetting agent compound system is characterized by comprising a fluorocarbon wetting agent, a non-ionic surfactant and a cosurfactant, wherein the contents of the components are in sequence according to the mass ratio:
20 parts of fluorocarbon wetting agent;
30 parts of non-fluorocarbon wetting agent;
10 parts of nonionic surfactant;
40 parts of cosurfactant;
the fluorocarbon wetting agent adopts sodium heptadecafluorooctyl sulfonate;
the non-fluorocarbon wetting agent consists of 15 parts of low molecular weight organic silicon and 15 parts of low molecular weight organic sulfonate wetting agent; the structural formula of the low molecular organic silicon is as follows:
X＝3，y＝1；R＝-CH 2 CH 2 CH 2 -O-(EO) 3 (PO) 1 -CH 3 the method comprises the steps of carrying out a first treatment on the surface of the The low molecular organic sulfonate wetting agent is dioctyl sodium dibutyrate sulfonate;
AEO-7 is adopted as the nonionic surfactant;
the cosurfactant is butanol.
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