CN104212293B - Waterborne acrylic acid antifogging coating and preparation method thereof - Google Patents
Waterborne acrylic acid antifogging coating and preparation method thereof Download PDFInfo
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Abstract
The invention provides a waterborne acrylic acid antifogging coating and a preparation method thereof. The antifogging coating comprises a prime coating and a top coating, wherein the top coating comprises an acrylic emulsion, a coalescing agent, a flattening agent, a thickener and a defoaming agent, the acrylic emulsion is prepared by carrying out emulsion polymerization on monomer raw materials comprising alkyl acrylate, polyol (methyl) acrylate, acrylic acid, methacrylic acid and a crosslinking monomer, the prime coating comprises an organic-silicone-modified acrylic emulsion, a coalescing agent, a flattening agent, a thickener and a defoaming agent and the organic-silicone-modified acrylic emulsion is prepared by carrying out emulsion polymerization on monomer raw materials comprising methyl methacrylate, styrene, alkyl acrylate, an organic silicone monomer and a crosslinking monomer. The waterborne acrylic acid antifogging coating disclosed by the invention is obtained by combining the prime coating and the top coating, and the antifogging coat prepared from the antifogging coating has the advantages of good adhesion force, water resistance and antifogging property.
Description
Technical field
The present invention relates to technical field of coatings, be specifically related to a kind of water soluble acrylic acid anti-fog coating and preparation method thereof.
Background technology
Transparent base such as glass, transparent resin material in use, when there is a fixed difference difference in base material both sides, low temperature
When the saturated vapor pressure of side substrate surface moisture content is less than the vapour pressure of surrounding, steam is assembled to substrate surface and with small
The form of the globule forms mist, light is formed refraction and diffusion, thus significantly reduces the light transmittance of base material, thus special at some
Application such as windshield, lens etc., have widespread demand to the base material with anti-fog function.
The main direction of studying that antifogging coating is current antifog technology is formed, including dredging at substrate surface coating anti-fog coating
Aqueous antifogging coating and hydrophilic antifogging coating.Wherein, the coating that esters of acrylic acid coating is formed is hydrophilic antifogging coating
One of principal item, but existing acrylate coatings is poor to the adhesive force of base material, it usually needs base material is carried out special activation
Processing or increase priming coat, coating flows due to poor water resistance through long-time current scour rear surface hydrophilic substance simultaneously
Lose, cause the anti-fog effect of coating persistence bad, it is impossible to fully meet application request.
Summary of the invention
In order to solve the problem that above-mentioned prior art exists, the present invention provides a kind of water soluble acrylic acid anti-fog coating and system thereof
Preparation Method, the composite coating pair that this coating is formed after including subbing and investment precoat, subbing and investment precoat solidification
Base material has good adhesive force, makes coating entirety have the resistance to water of excellence and continue hydrophilic antifogging performance.
The technical solution used in the present invention is:
A kind of water soluble acrylic acid anti-fog coating, including subbing and investment precoat, described subbing comprises organosilicon
Modified acrylic acid emulsion, coalescents, levelling agent, thickening agent and defoamer, described investment precoat comprises acrylic emulsion, film forming
Auxiliary agent, levelling agent, thickening agent and defoamer；
Described organosilicon-modified acrylic emulsion is by including methyl methacrylate, styrene, alkyl acrylate, having
The raw material monomer of machine silicon monomer and cross-linking monomer prepares through emulsion polymerization, and described organic silicon monomer is vinyl alkoxy silicon
Alkane, described alkyl acrylate is ethyl acrylate, n-propyl, n-butyl acrylate, the most own ester of acrylic acid, acrylic acid
One or more in different monooctyl ester；
Described acrylic emulsion is by including alkyl acrylate, polyhydric alcohol (methyl) acrylate, acrylic acid, metering system
Acid and cross-linking monomer raw material monomer through emulsion polymerization prepare, described alkyl acrylate selected from n-butyl acrylate, third
One or more in olefin(e) acid ethyl ester, Isooctyl acrylate monomer.
The water soluble acrylic acid anti-fog coating of the present invention includes there is base material the subbing of excellent adhesive attraction and hydrophilic
Investment precoat forms, and all with corresponding emulsion as main component, and the coating formed by subbing improves surface layer and base material
Adhesive force, make the coating prepared by the coating of the present invention have good anti-fog performance and resistance to water.
Preferably, the glass transition temperature of described organosilicon-modified acrylic emulsion is 25-30 DEG C, described propylene yogurt
The glass transition temperature of liquid is 25-30 DEG C.
Preferably, the solid content of described organosilicon-modified acrylic emulsion is 47-50%.
Preferably, the solid content of described acrylic emulsion is 40-46%.
Preferably, in the raw material monomer of described acrylic emulsion, described alkyl acrylate include n-butyl acrylate and
Isooctyl acrylate monomer.
In the present invention, (methyl) acrylate of hydroxyl represents the acrylate of hydroxyl and/or the methyl-prop of hydroxyl
Olefin(e) acid ester, (methyl) acrylate containing epoxy radicals represents the acrylate containing epoxy radicals and/or the metering system containing epoxy radicals
Acid esters, (methyl) acrylic acid represents acrylate and/or methacrylate.
In the raw material monomer of described acrylic emulsion, cross-linking monomer is (methyl) acrylate of hydroxyl, containing epoxy radicals
(methyl) acrylate, hydroxyl acrylamide in one or more.
Preferably, in the raw material monomer of described acrylic emulsion, cross-linking monomer is selected from acrylic acid-hydroxyl ethyl ester, acrylic acid-hydroxyl
Propyl ester, methacrylic acid-hydroxypropyl acrylate, glycidyl methacrylate, N-butoxymethyl acrylamide, N-methylol acryloyl
One or more in amine, by adding cross-linking monomer, hydrophilic that the coating making investment precoat be formed has had and resistance to water.
In the present invention, polyhydric alcohol (methyl) acrylate represents polyalcohol acrylate and/or polyhydric alcohol methacrylic acid
Ester.
Preferably, in the raw material monomer of described acrylic emulsion, polyhydric alcohol (methyl) acrylate is selected from three (metering systems
Acid) trihydroxymethylpropanyl ester, trimethylolpropane trimethacrylate, diethylene glycol double methacrylate, ethylene glycol bisthioglycolate (metering system
Acid) ester, one or more in pentaerythritol triacrylate, can improve after the stability of reaction system and film forming base material table
The adhesive force in face.
Preferably, the raw material monomer of described organosilicon-modified acrylic emulsion also includes double bond containing ketone carbonyl compound,
Subbing comprises the compound with two or more hydrazide groups, described in there are two or more hydrazide groups
Hydrazide group in compound is 1:(0.6-1 with the mol ratio of the ketone carbonyl in double bond containing ketone carbonyl compound).
It is further preferred that described double bond containing ketone carbonyl compound is N-[2-(2-methyl-4-oxopentyl), methacrylic acid acetyl
One or more in epoxide ethyl ester, methyl vinyl ketone, described in there is the compound of two or more hydrazide groups be
One or more in carbon acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide, grass acid dihydrazide.
In the raw material monomer of described organosilicon-modified acrylic emulsion, organic silicon monomer is vinyl alkoxy silane, institute
State alkoxyl and include methoxyl group, ethyoxyl or isopropoxy, preferably ethyoxyl.
Preferably, in the raw material monomer of described organosilicon-modified acrylic emulsion, cross-linking monomer includes the (first of hydroxyl
Base) acrylate, (methyl) acrylate of epoxy radicals, one or more in (methyl) acrylic acid.(methyl) of hydroxyl
In the preferred acrylic acid of acrylate-hydroxyl ethyl ester, acrylic acid-hydroxypropyl acrylate, methacrylic acid-hydroxypropyl acrylate one or more；Containing epoxy
The preferred glycidyl methacrylate of (methyl) acrylate of base.
Preferably, described acrylic emulsion is by including that the following raw material monomer counted by weight is prepared into through emulsion polymerization
Arrive:
Described acrylic acid: the mass ratio of methacrylic acid is 2:(1-2).
The raw material monomer of described organosilicon-modified acrylic emulsion includes double bond containing ketone carbonyl compound, subbing bag
When containing the compound with two or more hydrazide groups, it is preferable that the consumption of described double bond containing ketone carbonyl compound is
2-5 weight portion.
Preferably, the raw material monomer of described acrylic emulsion also includes methacrylate cyclohexyl, C9 versatic acid ethylene
More than one in ester, isobornyl methacrylate, isobornyl acrylate, can improve resistance to water and the film of polymer
Glossiness, consumption is 8-20 weight portion.
The present invention improves propylene by cross-linking monomer with acrylic acid, the combination of monomers of methacrylic acid and increase monomer consumption
The hydrophilic of acid resin copolymerization product, forms transparent hydrophilic acrylic after making the investment precoat film forming containing this acrylic emulsion
Coating.
Preferably, described organosilicon-modified acrylic emulsion is by including that the following raw material monomer counted by weight is through emulsion
Polymerization prepares:
Preferably, the raw material monomer of described organosilicon-modified acrylic emulsion also includes cyclohexyl methacrylate, C9Uncle
More than one in ethylene carbonate, isobornyl methacrylate, isobornyl acrylate, consumption is 5-20 weight portion.
Preferably, described subbing includes organosilicon-modified acrylic emulsion and the 5-12 weight of 170-185 weight portion
The coalescents of part.
Coalescents in described subbing without particular restriction, preferably alcohol ester 12, propylene glycol mono-oleate, diisopropyl
One or more in alcohol adipate ester, water-soluble silicon oil.Subbing also can contain other conventional coating additives, without special
Limit, commonly using in preparing including the coating such as thickening agent, levelling agent, defoamer and antifungus agent, antifreeze, anticorrosive additive
Auxiliary agent.
Preferably, described subbing is 400-2000mPa s the dynamic viscosity value of 25 DEG C.
Preferably, described investment precoat includes that the acrylic emulsion of 165-175 weight portion and the film forming of 10-25 weight portion help
Agent.
Coalescents in described investment precoat without particular restriction, preferably alcohol ester 12, propylene glycol mono-oleate, diisopropyl
More than one in alcohol adipate ester, water-soluble silicon oil.Containing other conventional coating additives in investment precoat, without particular restriction,
Auxiliary agent conventional in varnish preparation including thickening agent, levelling agent, defoamer etc., and antifungus agent, antifreeze, anticorrosive additive
Deng, concrete material and consumption do not have particular/special requirement.
Preferably, described investment precoat is 400-2000mPa s the dynamic viscosity value of 25 DEG C.
The preparation method of the water soluble acrylic acid anti-fog coating of the present invention, including preparation and the system of subbing of investment precoat
Standby, the preparation of investment precoat comprises the following steps:
(1) emulsifying agent is mixed with water, add alkyl acrylate, cross-linking monomer, methacrylic acid, acrylic acid, polynary
Alcohol (methyl) acrylate and initiator solution carry out emulsifying, obtain pre-emulsion；
(2) emulsifying agent is mixed with water, add initiator solution and account for pre-emulsion gross mass 5%-12% in step (1)
Pre-emulsion, temperature reaction, obtain seed emulsion, described in account for the pre-breast of pre-emulsion gross mass 5%-12% in step (1)
Changing liquid with the mass ratio of water in this step is 1:(5-10)；
(3) in seed emulsion, dropping residue pre-emulsion carries out polyreaction, and dropping process reaction temperature is 78-83
DEG C, it is warming up to 83-85 DEG C after being added dropwise to complete and continues reaction 1-1.5h, cooling, regulate pH to 7～8, obtain acrylic emulsion；
(4) coalescents, levelling agent, thickening agent, defoamer being mixed with acrylic emulsion, control ph is 8～9,
To investment precoat.
In the present invention, emulsifying agent is without particular restriction.
Preferably, in described step (1), emulsifying agent is the composite emulsifying of reactive emulsifier and anionic emulsifier
Agent, described reactive emulsifier is selected from allyloxy hydroxide sodium dimercaptosulphanatein, methallyl hydroxide sodium dimercaptosulphanatein, sodium vinyl sulfonate, alkane
One or more in base amide vinyl sulfonic acid sodium, sodium p styrene sulfonate, described anionic emulsifier is selected from dodecyl
Sodium sulfate, enuatrol, sodium abietate, sodium laurate, dodecylbenzene sodium sulfonate, alkyl phenol polyether sulfosuccinic acid monoesters sodium salt
In one or more.
Preferably, in described step (2), emulsifying agent is reactive emulsifier and ionic emulsifying agent and/or nonionic
The compound emulsifying agent of emulsifying agent, described reactive emulsifier selected from allyloxy hydroxide sodium dimercaptosulphanatein, methallyl hydroxide sodium dimercaptosulphanatein,
One or more in sodium vinyl sulfonate, alkylamide vinyl sulfonic acid sodium, sodium p styrene sulfonate, described ionic emulsifying agent
For polyoxyethylenated alcohol sodium sulfate and/or alkyl phenol polyether sulfosuccinic acid monoesters sodium salt.
Preferably, in step (2), described temperature reaction is to be warming up to 75-80 DEG C, is incubated 5-after question response liquid flooding blue light
10min。
Described initiator solution is the aqueous solution of initiator, and described initiator is persulfate thermal decomposition initiating, including
Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate etc..
Preferably, the time of described dropping is 2.5-4h.
Preferably, the preparation of described subbing comprises the following steps:
Emulsifying agent is mixed with water, by methyl methacrylate, styrene, organic silicon monomer, alkyl acrylate, crosslinking
Monomer and initiator solution carry out emulsifying, obtain pre-emulsion；
Emulsifying agent is mixed with water, adds initiator solution and account for the pre-emulsion of pre-emulsion gross mass 15%-25%,
Temperature reaction, has reacted and has obtained seed emulsion, and in seed emulsion, dropping residue pre-emulsion carries out polyreaction, drips
The reaction temperature of journey is 80-85 DEG C, be warming up to after being added dropwise to complete 85-90 DEG C continue reaction 1-1.5h, cooling, regulation pH to 7～
8, obtain organosilicon-modified acrylic emulsion；
Coalescents, levelling agent, thickening agent, defoamer being mixed with organosilicon-modified acrylic emulsion, control ph is 8
～9, obtain subbing.
In the present invention, emulsifying agent is without particular restriction.
Preferably, in described pre-emulsion preparation process, described emulsifying agent is reactive emulsifier and anionic emulsifying
The compound emulsifying agent of agent, described reactive emulsifier is selected from allyloxy hydroxide sodium dimercaptosulphanatein, methallyl hydroxide sodium dimercaptosulphanatein, second
One or more in sodium olefin sulfonate, alkylamide vinyl sulfonic acid sodium, sodium p styrene sulfonate, described anionic emulsifier
Selected from sodium lauryl sulphate, enuatrol, sodium abietate, sodium laurate, dodecylbenzene sodium sulfonate, alkyl phenol polyether sulfo group amber
One or more in amber acid monoester sodium salt.
Preferably, in described seed emulsion preparation process, emulsifying agent is for including reactive emulsifier and ionic emulsifying agent
And/or the compound emulsifying agent of nonionic emulsifier, described reactive emulsifier is selected from allyloxy hydroxide sodium dimercaptosulphanatein, methyl alkene
One or more in third hydroxide sodium dimercaptosulphanatein, sodium vinyl sulfonate, alkylamide vinyl sulfonic acid sodium, sodium p styrene sulfonate.Institute
Stating ionic emulsifying agent is polyoxyethylenated alcohol sodium sulfate and/or alkyl phenol polyether sulfosuccinic acid monoesters sodium salt.
The present invention further provides the application of described water soluble acrylic acid anti-fog coating, be used for preparing antifogging coating, method is
Base material coats subbing, obtains bottom after surface drying, be coated with investment precoat, after solidification, obtain antifogging coating.Described should
In with, surface drying after coating subbing, make gained bottom not affect the coating of investment precoat.
Preferably, the thickness of described bottom is 15-20 μm, and the thickness of described antifogging coating is 30-50 μm.
The technique effect that the present invention is useful: the water soluble acrylic acid anti-fog coating of the present invention includes that base material is had excellent adhesive attraction
Subbing and investment precoat, all with corresponding polymer emulsion as main component, gained coating formed composite coating tool
There is good adhesive force, resistance to water and lasting anti-fog performance (coating surface is less than 20 ° at the contact angle of 25 DEG C with water), can apply
In antifog technical field, and raw material is easy to get, and preparation technology is simple, safety and environmental protection, it is simple to industrialization.
Detailed description of the invention
The present invention is further detailed by specific embodiment given below.
Embodiment 1
The preparation method of investment precoat, including following operating procedure:
Prepare surface layer acrylic emulsion:
Weigh 2.5g Ammonium persulfate. to be dissolved in 40g deionized water and obtain initiator solution；
Weigh 1.0g sodium lauryl sulphate, 2.0g sodium p styrene sulfonate mixes with 140g deionized water, adds propylene
Acid N-butyl 142.5g, Isooctyl acrylate monomer 40g, three (methacrylic acid) trihydroxymethylpropanyl ester 60g, methacrylic acid 45g,
Acrylic acid 22.5g, hydroxyethyl methylacrylate 99g, N hydroxymethyl acrylamide 22.5g and 30g initiator solution, obtain pre-breast
Change liquid；
Weigh 2.5g alkyl phenol polyether sulfosuccinic acid monoesters sodium salt (MS-1 emulsifying agent, Hai'an, Jiangsu Province petrochemical industry
Factory), 2.5g sodium p styrene sulfonate mix with 360g deionized water and be warming up to 80 DEG C, add 10g initiator solution and 60.5g be pre-
Emulsion, insulation reaction 10min after the general obvious blue light of emulsion, obtain seed emulsion；
Dropping residue pre-emulsion in seed emulsion, dropping process reaction temperature is 80 DEG C, and time for adding is 3h, dropping
It is warming up to 85 DEG C after completing, after insulation reaction 1.5h, is cooled to 45 DEG C, adjust pH value to 7 with ammonia, filter after continuing stirring 10min
Discharging, obtains acrylic emulsion, and solid content is 44.7%, uses differential scanning calorimetry (DSC) according to GB19466-2 test breast
The glass transition temperature of liquid is 25.5 DEG C；
By antifungus agent 0.2g, defoamer 1.0g, coalescents water-soluble silicon oil 10g, levelling agent, (BPLE/B, rubs field in Shanghai
Chemical Co., Ltd.) 5g, thickening agent Rm-8w6g, antifreeze Polyethylene Glycol (200) 6g with 171g acrylic emulsion mix, ammonification
Water regulation pH value is 8, and stirring is filtered, obtained investment precoat, uses NDJ-1 rotary viscosimeter to test its power at 25 DEG C
Viscosity number is 1200mPa s.
Embodiment 2
The preparation method of investment precoat, including following operating procedure:
Prepare acrylic emulsion:
Weigh 2.5g Ammonium persulfate. to be dissolved in 40g deionized water and obtain initiator solution；
Weigh 1.0g sodium lauryl sulphate, 2.0g sodium p styrene sulfonate mixes with 170g deionized water, adds propylene
Acid N-butyl 137.5g, Isooctyl acrylate monomer 30g, three (methacrylic acid) trihydroxymethylpropanyl ester 45g, C9Tertiary ethylene carbonate
30g, methacrylic acid 45g, acrylic acid 22.5g, hydroxyethyl methylacrylate 69g, N hydroxymethyl acrylamide 22.5g and 30g
Initiator solution, obtains pre-emulsion；
Weigh 2.5g alkyl phenol polyether sulfosuccinic acid monoesters sodium salt (MS-1 emulsifying agent, Hai'an, Jiangsu Province petrochemical industry
Factory), 2.5g sodium p styrene sulfonate mix with 390g deionized water and be warming up to 80 DEG C, add 10g initiator solution and 40.3g be pre-
Emulsion, insulation reaction 10min after the general obvious blue light of emulsion, obtain seed emulsion；
Dropping residue pre-emulsion in seed emulsion, dropping process reaction temperature is 80 DEG C, and time for adding is 3h, dropping
It is warming up to 85 DEG C after completing, after insulation reaction 1.5h, is cooled to 45 DEG C, adjust pH value to 7 with ammonia, filter after continuing stirring 10min
Discharging, obtains acrylic emulsion, and solid content is 40.6%, uses differential scanning calorimetry (DSC) according to GB19466-2 test breast
The glass transition temperature of liquid is 26.5 DEG C；
By antifungus agent 0.2g, defoamer 1.0g, coalescents water-soluble silicon oil 10g, levelling agent, (BPLE/B, rubs field in Shanghai
Chemical industry) 5g, thickening agent Rm-8w6g, antifreeze Polyethylene Glycol (200) 6g with 171g acrylic emulsion mix, and adds ammonia regulation pH
Value is 8, stirring, filters, obtains investment precoat, uses NDJ-1 rotary viscosimeter to test it and the dynamic viscosity value of 25 DEG C is
1100mPa·s。
Embodiment 3
The preparation method of investment precoat, including following operating procedure:
Prepare acrylic emulsion:
Weigh 2.5g Ammonium persulfate. to be dissolved in 40g deionized water and obtain initiator solution；
Weigh 1.0g sodium lauryl sulphate, 2.0g sodium p styrene sulfonate mixes with 140g deionized water, adds propylene
Acid N-butyl 137.5g, Isooctyl acrylate monomer 40g, three (methacrylic acid) trihydroxymethylpropanyl ester 85g, methacrylic acid 25g,
Acrylic acid 25g, hydroxyethyl methylacrylate 91.5g, N hydroxymethyl acrylamide 22.5g and 30g initiator solution, obtain pre-breast
Change liquid；
Weigh 1.5g alkyl phenol polyether sulfosuccinic acid monoesters sodium salt (MS-1 emulsifying agent, Hai'an, Jiangsu Province petrochemical industry
Factory), polyoxyethylenated alcohol sodium sulfate 1.0g, 2.5g sodium p styrene sulfonate mixes with 360g deionized water and is warming up to 80
DEG C, add 10g initiator solution and 62g pre-emulsion, insulation reaction 10min after the general obvious blue light of emulsion, obtain seed breast
Liquid；
Dropping residue pre-emulsion in seed emulsion, dropping process reaction temperature is 80 DEG C, and time for adding is 3h, dropping
It is warming up to 85 DEG C after completing, after insulation reaction 1.5h, is cooled to 45 DEG C, adjust pH value to 7 with ammonia, filter after continuing stirring 10min
Discharging, obtains acrylic emulsion, and solid content is 44.4%, uses differential scanning calorimetry (DSC) according to GB19466-2 test breast
The glass transition temperature of liquid is 26.7 DEG C；
By antifungus agent 0.2g, defoamer 1.0g, coalescents water-soluble silicon oil 10g, levelling agent BPLE/B5g, thickening agent
Rm-8w6g, antifreeze Polyethylene Glycol (200) 6g with 171g acrylic emulsion mix, and adjust pH value to be 8 with ammonia, and stirring is filtered,
Obtaining investment precoat, using NDJ-1 rotary viscosimeter to test it the dynamic viscosity value of 25 DEG C is 1200mPa s.
Embodiment 4
The preparation method of subbing, including following operating procedure:
Prepare organosilicon-modified acrylic emulsion:
Weigh 2.5g Ammonium persulfate. to be dissolved in 40g deionized water and obtain initiator solution；
Weigh 1.0g sodium lauryl sulphate, 2.0g alkylamide vinyl sulfonic acid sodium (DNS-86) stirs with 140g deionized water
Mix mixing, add methyl methacrylate 230g, cyclohexyl methacrylate 43g, n-butyl acrylate 150g, vinyl front three
TMOS 48g, acrylic acid 4g and 30g initiator solution, stir 20min, obtain pre-emulsion；
Weigh 2.5g polyoxyethylenated alcohol sodium sulfate, 2.5g alkylamide vinyl sulfonic acid sodium (DNS-86) goes with 330g
Ionized water mix and blend, is warming up to 80 DEG C, adds 10g initiator solution and 164g pre-emulsion, after the general obvious blue light of emulsion
Insulation reaction 10min, obtains seed emulsion；
Dropping residue pre-emulsion in seed emulsion, dropping process reaction temperature is 85 DEG C, drips off in 2h, heats up
To 88 DEG C, after continuing insulation 1.5h, it is cooled to 45 DEG C, adjusts pH value to 7～8 with ammonia, filter discharging, obtain organic-silicon-modified third
Olefin(e) acid emulsion, solid content is 48.6%, uses differential scanning calorimetry (DSC) according to the vitrification of GB19466-2 test emulsion
Transition temperature is 27.8 DEG C.
By organosilicon-modified acrylic emulsion 180g, antifungus agent 0.2g, defoamer 1.0g, hydrone barrier 1.0g, one-tenth
Film auxiliary agent water-soluble silicon oil 5g, levelling agent (BPLE/B, rub field chemical industry in Shanghai) 5g, thickening agent Rm-8w6g, antifreeze Polyethylene Glycol
(200) 6g mixing, recording pH value is 8, stirring, filters, obtains subbing, use NDJ-1 rotary viscosimeter test its
The dynamic viscosity value of 25 DEG C is 1500mPa s.
Embodiment 5
The preparation method of subbing, including following operating procedure:
Prepare organosilicon-modified acrylic emulsion:
Weigh 2.5g Ammonium persulfate. to be dissolved in 40g deionized water and obtain initiator solution；
Weigh 1.0g sodium lauryl sulphate, 2.0g alkylamide vinyl sulfonic acid sodium (DNS-86) stirs with 120g deionized water
Mix mix homogeneously, add methyl methacrylate 200g, C9 tertiary ethylene carbonate 40g, n-butyl acrylate 167g, styrene
42g, vinyltrimethoxy silane 36g, acrylic acid 6g, be dissolved in by 6g N-[2-(2-methyl-4-oxopentyl) that 20g deionized water obtains molten
Liquid and 30g initiator solution, stirring, obtain pre-emulsion；
Weigh 1.5g alkyl phenol polyether sulfosuccinic acid monoesters sodium salt (MS-1 emulsifying agent, Hai'an, Jiangsu Province petrochemical industry
Factory), polyoxyethylenated alcohol sodium sulfate 1.0g, 2.5g alkylamide vinyl sulfonic acid sodium (DNS-86) and 330g deionized water mix
Closing stirring, be warming up to 80 DEG C, add 10g initiator solution and 111.7g pre-emulsion, after the general obvious blue light of emulsion, insulation is anti-
Answer 10min, obtain seed emulsion；
Dropping residue pre-emulsion in seed emulsion, dropping process reaction temperature is 85 DEG C, drips off, be warming up in 2h
88 DEG C, after insulation 1.5h, it is cooled to 45 DEG C, adjusts pH value to 7 with ammonia, add 5g adipic dihydrazide and be dissolved in what 10g water obtained
Solution, filters discharging, obtains organosilicon-modified acrylic emulsion, and solid content is 49.7%, uses differential scanning calorimetry (DSC)
Glass transition temperature according to GB19466-2 test emulsion is 26.3 DEG C.
By organosilicon-modified acrylic emulsion 180g, antifungus agent 0.2g, defoamer 1.0g, hydrone barrier 1.0g, one-tenth
Film auxiliary agent water-soluble silicon oil 5g, levelling agent (BPLE/B, rub field chemical industry in Shanghai) 5g, thickening agent Rm-8w6g, Polyethylene Glycol (200)
6g mixes, and adding ammonia regulation pH value is 8, and stirring is filtered, obtained subbing, use NDJ-1 rotary viscosimeter test its
The dynamic viscosity value of 25 DEG C is 1400mPa s.
Testing example
1-4 aqueous is obtained with the investment precoat of embodiment 1～3 preparation and the subbing combination of embodiment 4～5 preparation
Acrylic acid anti-fog coating, is shown in Table 1.Acrylic acid antifogging coating, preparation method is prepared respectively by 1-4 water soluble acrylic acid anti-fog coating
For: by subbing under 0.3～0.5MPa air pressure with seven apertures in the human head high atomization spray gun for paint be sprayed at 50mm × 50mm, thickness is 1mm
On the glass substrate that ethanol is crossed, after about 0.5h surface drying, obtain the bottom that thickness is 15-25 μm, then spraying surface coating,
Solidifying 2h in 80 DEG C, obtain No. 1-4 testing sample with antifogging coating, total coating thickness is 30-50 μm.
Measure the adhesive force after coating film forming according to GB9286-98 hundred lattice testing standard, be designated as the adhesive force of 0d.
Lasting adhesive force, resistance to water and the protracted hydrophilicity of test antifogging coating, method is: be placed in by gained testing sample
In 25 DEG C of water, make the antifogging coating of 2/3 area be dipped in 3d in water, observe the degree that antifogging coating turns white and comes off, investigate antifog
The resistance to water of coating；The immersed part antifogging coating contact angle at 25 DEG C with water is tested, before not soaking after being taken out by sample
Contact angle contrasts, and contact angle uses contact angle measurement (model is JGW-360A) to measure, and investigates the lasting hydrophilic of antifogging coating
Property；Test the adhesive force of immersed part antifogging coating after being taken out by sample, contrast with the adhesive force before not soaking, investigate antifog painting
The lasting adhesive force of layer.
Test result is shown in Table 1.
Table 1
As seen from the data in Table 1, the present invention is combined by subbing and investment precoat and obtains aqueous anti-fog coating, it prepare
Antifogging coating there is good adhesive force and resistance to water, still preferable through long-time submerging test postadhesion power, face simultaneously
Layer hydrophilic improves, thus ensure that the lasting anti-fog performance of antifogging coating, is a kind of environment-friendly type continuing anti-fog performance excellence
Anti-fog coating.
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert
Being embodied as of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the present invention's
Protection domain.
Claims (10)
1. a water soluble acrylic acid anti-fog coating, including subbing and investment precoat, described subbing comprises organosilicon and changes
Property acrylic emulsion, coalescents, levelling agent, thickening agent and defoamer, described investment precoat comprises acrylic emulsion, film forming helps
Agent, levelling agent, thickening agent and defoamer；
Described organosilicon-modified acrylic emulsion is by including methyl methacrylate, styrene, alkyl acrylate, organosilicon list
The raw material monomer of body and cross-linking monomer prepares through emulsion polymerization, and described organic silicon monomer is vinyl alkoxy silane, institute
Stating alkyl acrylate is that ethyl acrylate, n-propyl, n-butyl acrylate, the most own ester of acrylic acid, acrylic acid are different pungent
One or more in ester；
Described acrylic emulsion by include alkyl acrylate, polyhydric alcohol (methyl) acrylate, acrylic acid, methacrylic acid and
The raw material monomer of cross-linking monomer prepares through emulsion polymerization, and described alkyl acrylate is selected from n-butyl acrylate, acrylic acid
One or more in ethyl ester, Isooctyl acrylate monomer.
2. water soluble acrylic acid anti-fog coating as claimed in claim 1, it is characterised in that described organosilicon-modified acrylic emulsion
Glass transition temperature is 25-30 DEG C, and the glass transition temperature of described acrylic emulsion is 25-30 DEG C.
3. water soluble acrylic acid anti-fog coating as claimed in claim 1, it is characterised in that the solid content of described acrylic emulsion is
40-46%.
4. water soluble acrylic acid anti-fog coating as described in any one of claim 1-3, it is characterised in that described acrylic emulsion is by wrapping
Include the following raw material monomer counted by weight to prepare through emulsion polymerization:
Described acrylic acid: the mass ratio of methacrylic acid is 2:(1-2).
5. water soluble acrylic acid anti-fog coating as described in any one of claim 1-3, it is characterised in that described polyhydric alcohol (methyl) third
Olefin(e) acid ester is selected from trimethylolpropane tris (methacrylic acid) ester, trimethylolpropane trimethacrylate, diethylene glycol bis-propylene
One or more in acid esters, ethylene glycol bisthioglycolate (methacrylic acid) ester, pentaerythritol triacrylate.
6. water soluble acrylic acid anti-fog coating as described in any one of claim 1-3, it is characterised in that described organic-silicon-modified propylene
Yogurt liquid is by including that the following raw material monomer counted by weight prepares through emulsion polymerization:
7. water soluble acrylic acid anti-fog coating as described in any one of claim 1-3, it is characterised in that described organic-silicon-modified propylene
The raw material monomer of yogurt liquid also includes double bond containing ketone carbonyl compound, described subbing also comprise have two or two with
The compound of upper hydrazide group.
8. water soluble acrylic acid anti-fog coating as described in any one of claim 1-3, it is characterised in that described investment precoat includes
The acrylic emulsion of 165-175 weight portion and the coalescents of 10-25 weight portion.
9. the preparation method of water soluble acrylic acid anti-fog coating as described in any one of claim 1-3, it is characterised in that described surface layer
The preparation of coating comprises the following steps:
(1) emulsifying agent is mixed with water, add alkyl acrylate, cross-linking monomer, methacrylic acid, acrylic acid, polyhydric alcohol (first
Base) acrylate and initiator solution carry out emulsifying, obtains pre-emulsion；
(2) emulsifying agent is mixed with water, add initiator solution and account for the pre-of pre-emulsion gross mass 5%-12% in step (1)
Emulsion, temperature reaction, obtain seed emulsion, described in account for the pre-emulsion of pre-emulsion gross mass 5%-12% in step (1)
It is 1:(5-10 with the mass ratio of water in this step)；
(3) in seed emulsion, dropping residue pre-emulsion carries out polyreaction, and dropping process reaction temperature is 78-83 DEG C, drips
It is warming up to 83-85 DEG C after having added and continues reaction 1-1.5h, cooling, regulate pH to 7～8, obtain acrylic emulsion；
(4) coalescents, levelling agent, thickening agent, defoamer being mixed with acrylic emulsion, control ph is 8～9, obtains face
Coating.
10. the preparation method of water soluble acrylic acid anti-fog coating as described in any one of claim 1-3, it is characterised in that the described end
The preparation of coating comprises the following steps:
Emulsifying agent is mixed with water, by methyl methacrylate, styrene, organic silicon monomer, alkyl acrylate, cross-linking monomer
And initiator solution carries out emulsifying, obtain pre-emulsion；
Emulsifying agent is mixed with water, adds initiator solution and account for the pre-emulsion of pre-emulsion gross mass 15%-25%, heating up
Reaction, has reacted and has obtained seed emulsion, and in seed emulsion, dropping residue pre-emulsion carries out polyreaction, dropping process
Reaction temperature is 80-85 DEG C, is warming up to 85-90 DEG C and continues reaction 1-1.5h, cooling, regulate pH to 7～8 after being added dropwise to complete,
To organosilicon-modified acrylic emulsion；
Coalescents, levelling agent, thickening agent, defoamer being mixed with organosilicon-modified acrylic emulsion, control ph is 8～9,
Obtain subbing.
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| CN108359046A (en) * | 2018-02-01 | 2018-08-03 | 广州市斯洛柯高分子聚合物有限公司 | A kind of organosilicon-modified acrylic emulsion and preparation method thereof |
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| CN117801158B (en) * | 2023-12-22 | 2024-06-25 | 佛山市三水顺能化工有限公司 | Organosilicon modified acrylic resin, preparation method and application thereof |
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