CN106243273A - A kind of hydroxyl acrylic emulsion with nucleocapsid structure and preparation method and application - Google Patents
A kind of hydroxyl acrylic emulsion with nucleocapsid structure and preparation method and application Download PDFInfo
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- CN106243273A CN106243273A CN201610616909.9A CN201610616909A CN106243273A CN 106243273 A CN106243273 A CN 106243273A CN 201610616909 A CN201610616909 A CN 201610616909A CN 106243273 A CN106243273 A CN 106243273A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a kind of hydroxyl acrylic emulsion with nucleocapsid structure and preparation method and application, this emulsion be at following five kinds of vinyl monomers in the presence of initiator and emulsifying agent, emulsion is polymerized, and the kind of monomer and the consumption of each monomer percentage ratio shared by monomer total amount is as follows: the 1. vinyl monomer 40 65% without other functional functional group；2. the vinyl monomer 5 30% of hydroxyl；3. the vinyl monomer 2 5% containing epoxy radicals；The most carboxylic vinyl monomer 1 7%；5. the vinyl monomer 1 3% containing polyfunctionality (>=2)；Described initiator amount is the 0.2 1.5% of monomer total amount；The total consumption of emulsifying agent is the 1 5% of monomer total amount；Above percentage ratio is all weight percentage.The aqueous double-component coating that this hydroxyl acrylic emulsion is prepared with water cross-linking agent, VOC content is low, and amount of solid content is high, and the hardness of film, the pliability that are formed have concurrently, has the various patience of excellence, for coatings of the aluminium profiles, alternative traditional solvent based coating.
Description
Technical field
The present invention relates to paint field, more particularly, it relates to a kind of hydroxyl acrylic emulsion with nucleocapsid structure and
Its preparation method and application.
Background technology
Aluminum and alloy thereof have a good corrosion resistance, and electrical and thermal conductivity and the advantage such as easily processed into type, so aluminum closes
Gold is at national defence, Aero-Space, traffic instrument, both mechanically and electrically device, and the field such as home decoration is widely used.But due to gold
Belong to aluminum the most oxidized and turn black dimmed, affect its attractive in appearance and service life, therefore to the protection of Al alloy parts with decorate non-
The most necessary.
Generally use solvent based coating and powdery paints to be coated in aluminium shape surface in industry and play protection and the effect of decoration
Really, but oil paint is producing, is allocating and often discharge benzene class, the poisonous and hazardous Organic substance of aldehydes (VOC) in work progress,
Have a strong impact on health and the ecological environment of people, add in recent years, along with the increasingly stringent of environmental requirement, water in global range
Property coating obtain very fast development.Water paint is nontoxic with it, free from extraneous odour, do not fire and the advantage such as easy cleaning, has had become as tradition
The main succedaneum of solvent based coating, but restricted by itself preparating mechanism, the resistance to medium of film and hardness are according to routine
Method is difficult to be effectively improved, and in the case, people have started the water-based hydroxyl that can cross-link the firming agent added
The research of resin.Latex type hydroxy acryl acid resin synthesizes with solvent method, neutralize into salt, the hydroxy resin of water-dispersion type
And water soluble hydroxy resin-phase ratio, low cost, solid content is higher, it is important to VOC (VOC) content is few,
Obtain domestic and international research unit and the extensive concern of coating producer and play an active part in research and development.
Chinese patent CN 105038426A discloses a kind of Gao Gu, low VOC non-toluene solvent type acrylic resin, this resin
Butyl acetate and propylene glycol methyl ether acetate is used to carry out polymerization as solvent and prepare resin, although this resin is without benzene system,
Have relatively low VOC, but than the emulsion with water as medium, VOC emission is the biggest.Chinese patent 104194440A is open
A kind of normal temperature solidified water resistant coating, this resin uses N-[2-(2-methyl-4-oxopentyl) and acrylic acid series raw material at the work of initiator
Use lower polymerization, use adipic dihydrazide to be cross-linked, and it is prepared finally to stablize emulsion with diacetone.Although this emulsion energy room temperature is solid
Changing, various patience have also been obtained certain improvement, but combination property is poorer than heat curing-type emulsion, and is not used to metal baking finish
On, Chinese patent CN104293047A discloses a kind of acrylic-amino baking vanish, and this acrylic acid baking vanish uses amino resins solidification
Make paint film have good hardness, adhesive force, resistance to impact and weatherability, but the paint film of amino solidification is than urethane cures
Paint film richness, pliability are poor, and urethane cures temperature is lower.Chinese patent CN200510134997.0 discloses one
Planting the emulsion-type Hydroxylated acrylic resin with core-shell configuration, this resin introduces oh group can be as the hydroxyl of dual-component coating
Resin, but owing to its patience that limits of polymerization technique Yu material choice can not get higher improvement, for the family that patience is higher
Rustproof lacquer is more difficult to be met.
Summary of the invention
The technical problem to be solved in the present invention is, for the drawbacks described above of prior art, it is provided that one has nucleocapsid knot
Hydroxyl acrylic emulsion of structure and preparation method and application.This hydroxyl acrylic emulsion is double with the aqueous of water cross-linking agent preparation
Component coating, VOC content is low, and amount of solid content is high, and the hardness of film, the pliability that are formed have concurrently, has the various resistance to of excellence
Property, for coatings of the aluminium profiles, alternative traditional solvent based coating.
The technical solution adopted for the present invention to solve the technical problems is: provide a kind of hydroxy with nucleocapsid structure
Yogurt liquid, it is that emulsion is polymerized, the kind of monomer at following five kinds of vinyl monomers in the presence of initiator and emulsifying agent
The consumption of class and each monomer percentage ratio shared by monomer total amount is as follows: the alkenes 1., without other functional functional group
Monomer 40-65%；2., the vinyl monomer 5-30% of hydroxyl；3., the vinyl monomer 2-5% containing epoxy radicals；4., carboxylic
Vinyl monomer 1-7%；5., containing the vinyl monomer 1-3% of polyfunctionality (>=2)；
Described initiator amount is the 0.2-1.5% of monomer total amount；
Described emulsifying agent is nonionic emulsifier, anionic and nonionic type emulsifying agent and anionic emulsifier, the use of three
Amount ratio is (1.0-1.5): (0.8-1.0): 0.3；The total consumption of emulsifying agent is the 1-5% of monomer total amount；
Above percentage ratio is all weight percentage.
The hydroxyl acrylic emulsion with nucleocapsid structure of the present invention, wherein, following monomer consumption is in monomer total amount
Percentage ratio shared by is preferably: the vinyl monomer of hydroxyl 2. 10-20%；Vinyl monomer containing epoxy radicals 3. 3-5%；Containing carboxylic
The vinyl monomer of base 4. 1-2%；Vinyl monomer 5. 1-3% containing polyfunctionality (>=2).
The hydroxyl acrylic emulsion with nucleocapsid structure of the present invention, wherein, described without other functional sense
1. the vinyl monomer of group is two or more in (methyl) esters of acrylic acid class monomer, aromatic series vinyl monomer；
2. the vinyl monomer of described hydroxyl is any in (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate
One or more.
The hydroxyl acrylic emulsion with nucleocapsid structure of the present invention, wherein, the described vinyl monomer containing epoxy radicals
3. be in (methyl) glycidyl acrylate, allyl glycidyl any one or more than one.
The hydroxyl acrylic emulsion with nucleocapsid structure of the present invention, wherein, described carboxylic vinyl monomer is 4.
Be in acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid any one or more than one.
The hydroxyl acrylic emulsion with nucleocapsid structure of the present invention, wherein, the described alkene containing polyfunctionality (>=2)
5. class monomer is glycol diacrylate, BDO diacrylate, 1,6-hexanediyl ester, neopentyl glycol
Diacrylate, trimethylolpropane trimethacrylate, ethoxyquin (N=3,9,15,21) trimethylolpropane trimethacrylate,
Third oxidation (N=3,4,5) trimethylolpropane trimethacrylate in any one or more than one.
The hydroxyl acrylic emulsion with nucleocapsid structure of the present invention, wherein, in described hydroxyl acrylic emulsion, institute
State initiator be in persulfate or azo compound any one or more than one；Described emulsifying agent is that nonionic is anti-
Answering property emulsifying agent, without APEO nonionic emulsifier, without APEO anionic and nonionic type emulsifying agent, anionic reactive emulsifier, alkane
Base sulfonate, alkyl sulfate, three kinds in alkylbenzenesulfonate, alkyl succinate or more than three kinds.
The hydroxyl acrylic emulsion with nucleocapsid structure of the present invention, wherein, its outward appearance is milky white sub-translucent indigo plant
Light liquid, viscosity 100-2000mPa.s, solids content 42-44%, pH value 7.0-8.5, particle diameter 0.05-0.2 μm, volatility has
Machine compound VOC content ＜ 0.1%, hydroxyl value is 10-100mgKOH/g, more than 6 months storage period.
The present invention also provides for the preparation method of a kind of hydroxyl acrylic emulsion as above with nucleocapsid structure, first by
The partial monosomy and the emulsifying agent that form emulsion particle stratum nucleare prepare stratum nucleare pre-emulsion, and in the presence of initiator, polymerization prepares stratum nucleare
Emulsion, then uniformly drips shell mix monomer, is polymerized in the presence of initiator, neutralized, filters, discharging is has core
The hydroxyl acrylic emulsion of shell structure, specifically comprises the following steps that
(1) preparation of stratum nucleare pre-emulsion: by partial monosomy 1., partial monosomy 4. and all monomers 5., at emulsifying agent
Effect under be dispersed in water, obtain stratum nucleare pre-emulsification monomer mixture；
(2) preparation of shell pre-emulsion: by remaining monomer 1., 4. and all monomer 2., 3., at the work of emulsifying agent
It is dispersed in water under with, obtains shell pre-emulsification monomer mixture；
(3) emulsifying agent and initiator are joined in reaction medium water, be placed in 500ml flask and stir, and heat up
To 75～80 DEG C, the stratum nucleare pre-emulsion of dropping 1%-10% part by weight, rotary speed maintains 100-300rpm, continuously stirred
0.5-1 hour, treat that emulsion becomes blue phase, it is thus achieved that seed emulsion；
(4) then toward dropping residue stratum nucleare pre-emulsion and initiator solution in flask, after dropping, it is incubated 75～80
DEG C, maintain 0.5-1.0 hour；
(5) then in flask, drip shell pre-emulsion and initiator solution, after dripping off, be incubated 75-80 DEG C of maintenance
2.0-2.5 hour；
(6) being cooled to 40 DEG C, the ammonia of 1.0-2.5g is blended in the emulsion in flask until by the pH value of liquid in beaker
Being modulated to 7.5-8.0, filtration, discharging are the hydroxyl acrylic emulsion with nucleocapsid structure.
The present invention also provides for the application of a kind of hydroxyl acrylic emulsion as above with nucleocapsid structure, is applied to aluminum
Material incrustation coating.
Implementing hydroxyl acrylic emulsion with nucleocapsid structure and preparation method and application of the present invention, having following has
Benefit effect:
(1) present invention has the hydroxyl acrylic emulsion of nucleocapsid structure, and the nucleocapsid structure of its uniqueness makes it have following excellent
Point: will there is the core part of multi-functional alkene introducing emulsion so that it is core has microgel structure, improves core part resin
Molecular weight, also obtains semi-intercrossing network emulsion (semi-LIPN), during emulsion film forming, along with the diffusion of strand simultaneously
Forming a big semi-intercrossing network, along with the addition of firming agent, cross-linking reaction gradually occurs, and forms second network, obtains
Thermosetting full interpenetrating networks film, and then it is greatly enhanced hardness and the patience of resin；Simultaneously consciously will be containing hydroxyl, ring
Epoxide (methyl) acrylic monomers or a combination of both thing introduce the shell part of emulsion, and active group so can be made fully to be distributed
On the surface of emulsion, increase reaction probabilities, be effectively improved the combination properties such as the use rate of group, raising resistance to water, adhesive force；
(2) water paint by the preparation of the present invention above-mentioned hydroxyl acrylic emulsion there is hydroxy functional group both can toast
Solidification also from solidization, and can introduce epoxy functionality, drastically increases the patience of resin, is particularly well-suited to aluminium
On, its VOC content extremely low (<0.1), the hardness of film (2H) formed, pliability and weather resisteant (>1000 hours) improve,
Alternative traditional solvent based coating.
Detailed description of the invention
Below, in conjunction with detailed description of the invention, the present invention is described further:
In the present invention, if not refering in particular to, all of part, percentage ratio are unit of weight, the equipment used and raw material etc.
All it is commercially available or commonly used in the art.Method in following embodiment, if no special instructions, is the normal of this area
Rule method.
A kind of hydroxyl acrylic emulsion with nucleocapsid structure, it is in initiator and emulsifying at following five kinds of vinyl monomers
In the presence of agent, emulsion is polymerized, and the kind of monomer and the consumption of each monomer percentage shared by monomer total amount is such as
Under: the vinyl monomer 40-65% 1., without other functional functional group；2., the vinyl monomer 5-30% of hydroxyl；3., contain
The vinyl monomer 2-5% of epoxy radicals；4., carboxylic vinyl monomer 1-7%；5., containing the vinyl monomer 1-of polyfunctionality (>=2)
3%；Preferably, the percentage ratio that following monomer consumption is shared in monomer total amount is preferably: the vinyl monomer of hydroxyl 2. 10-
20%；Vinyl monomer containing epoxy radicals 3. 3-5%；Carboxylic vinyl monomer 4. 1-2%；, alkenes containing polyfunctionality (>=2)
Monomer 5. 1-3%.
Described initiator amount is the 0.2-1.5% of monomer total amount；Described initiator is persulfate or azo chemical combination
In thing any one or more than one；
Described emulsifying agent is nonionic emulsifier, anionic and nonionic type emulsifying agent and anionic emulsifier, the use of three
Amount ratio is (1.0-1.5): (0.8-1.0): 0.3；The total consumption of emulsifying agent is the 1-5% of monomer total amount；Described emulsifying agent right and wrong
Reaction of ionic type emulsifying agent, without APEO nonionic emulsifier, without APEO anionic and nonionic type emulsifying agent, anionic reactivity breast
Agent, alkylsulfonate, alkyl sulfate, three kinds in alkylbenzenesulfonate, alkyl succinate or more than three kinds.
Described monomer be 1. in (methyl) esters of acrylic acid class monomer, aromatic series vinyl monomer two kinds or two kinds with
On；
2. the vinyl monomer of described hydroxyl is any in (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate
One or more.
3. the described vinyl monomer containing epoxy radicals is in (methyl) glycidyl acrylate, allyl glycidyl
Any one or more than one.
4. described carboxylic vinyl monomer is acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid
In any one or more than one.
The described vinyl monomer containing polyfunctionality (>=2) is 5. glycol diacrylate, BDO diacrylate
Ester, 1,6-hexanediyl ester, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, ethoxyquin (N=
3,9,15,21) trimethylolpropane trimethacrylate, appointing in third oxidation (N=3,4,5) trimethylolpropane trimethacrylate
Meaning one or more than one.
Its outward appearance is milky white sub-translucent blue light liquid, viscosity 100-2000mPa.s, solids content 42-44%, pH value
7.0-8.5, particle diameter 0.05-0.2 μm, VOC VOC content ＜ 0.1%, hydroxyl value is 10-100mgKOH/g, storage
Deposit the phase more than 6 months.
The present invention also provides for the preparation method of a kind of hydroxyl acrylic emulsion as above with nucleocapsid structure, first by
The partial monosomy and the emulsifying agent that form emulsion particle stratum nucleare prepare stratum nucleare pre-emulsion, and in the presence of initiator, polymerization prepares stratum nucleare
Emulsion, then uniformly drips shell mix monomer, is polymerized in the presence of initiator, neutralized, filters, discharging is has core
The hydroxyl acrylic emulsion of shell structure, specifically comprises the following steps that
(1) preparation of stratum nucleare pre-emulsion: by partial monosomy 1., partial monosomy 4. and all monomers 5., at emulsifying agent
Effect under be dispersed in water, obtain stratum nucleare pre-emulsification monomer mixture；
(2) preparation of shell pre-emulsion: by remaining monomer 1., 4. and all monomer 2., 3., at the work of emulsifying agent
It is dispersed in water under with, obtains shell pre-emulsification monomer mixture；
(3) emulsifying agent and initiator are joined in reaction medium water, be placed in 500ml flask and stir, and heat up
To 75～80 DEG C, the stratum nucleare pre-emulsion of dropping 1%-10% part by weight, rotary speed maintains 100-300rpm, continuously stirred
0.5-1 hour, treat that emulsion becomes blue phase, it is thus achieved that seed emulsion；
(4) then toward dropping residue stratum nucleare pre-emulsion and initiator solution in flask, after dropping, it is incubated 75～80
DEG C, maintain 0.5-1.0 hour；
(5) then in flask, drip shell pre-emulsion and initiator solution, after dripping off, be incubated 75-80 DEG C of maintenance
2.0-2.5 hour；
(6) being cooled to 40 DEG C, the ammonia of 1.0-2.5g is blended in the emulsion in flask until by the pH value of liquid in beaker
Being modulated to 7.5-8.0, filtration, discharging are the hydroxyl acrylic emulsion with nucleocapsid structure.
The present invention also provides for the application of a kind of hydroxyl acrylic emulsion as above with nucleocapsid structure, and it is applied to
Aluminium material surface decorative paint.
Embodiment 1-3
Formula is shown in Table 1
Table 1 is composition and the consumption of the required material of embodiment 1-3
Embodiment 1-3 synthesis technique:
Material (1) and 30% material (2) are added in 500ml four-hole boiling flask, is warming up to 80 DEG C, add the material of 10%
(3) polymerase 10 obtains seed emulsion in .5 hour, then drips the mixed liquor of remaining material (2) and material (3) in 1 hour, insulation
0.5 hour, then drip the mixed liquor of material (4) and material (5), within 2 hours, drip off, drip off insulation 2 hours, be then cooled to 40
DEG C, add material (6) and neutralize, stir, filter discharging.
Comparative example
Comparative example 1 is with conventional emulsifier, the hydroxy acryl acid emulsion that routinely prepared by emulsion polymerization technique, and is not added with
Enter the vinyl monomer containing polyfunctionality (>=2) and the acrylic monomers with epoxy radicals.
Table 2 is composition and the consumption of the required material of comparative example 1
Comparative example 2 is the hydroxy acryl acid resin prepared with solution polymerization process, and adds the propylene with epoxy radicals
Acid monomers.
Table 3 is composition and the consumption of the required material of comparative example 2
Below, the performance parameter of the hydroxyl acrylic emulsion that comparing embodiment 1-3 and comparative example 1-2 prepare sees below
Table:
Table 4 is the performance parameter of embodiment 1-3 and the hydroxyl acrylic emulsion of comparative example 1-2
Below, the hydroxyl acrylic emulsion that above-described embodiment 1-3 and comparative example 1-2 obtain is made decorative paint, be coated with
Material formula is as follows:
The most above-mentioned hydroxyl acrylic emulsion, consumption is 40-60 part；
2. water cross-linking agent, consumption is 6-15 part；
3. cosolvent, consumption is 0.1-0.5 part
4. aqueous adhesive force accelerator, consumption is 0.1-0.3 part；
5. nertralizer, consumption is 0.1-0.4 part；
6. catalyst, consumption is 0.2-0.6 part；
7. titanium dioxide, R-902, consumption is 10-20 part；
8. water, surplus；
Described water cross-linking agent can be a kind of or mixture of two kinds in amino resins, watersoluble closed type isocyanates,
Preferably the two mixture.
Described catalyst can be p-methyl benzenesulfonic acid, dinonylnaphthalene disulfonic acid, phosphoric acid, DBSA, two Laurels
Acid dibutyl tin, zinc naphthenate etc..
Described cosolvent can be ethylene glycol monobutyl ether, glycol monoethyl ether, n-butyl alcohol, isobutanol, propylene glycol monobutyl ether, two
One or more in ethylene glycol monobutyl ether, preferably propylene glycol monobutyl ether.
Described aqueous adhesive force accelerator can be the A-1600 of Foshan He Mu Si resin company limited.
Described nertralizer can be ammonia, N, N-dimethylethanolamine, diethanolamine, triethanolamine, 2-methyl 2-aminopropan
Alcohol, preferably N, N-dimethylethanolamine.
Below, by above-mentioned its paint film property of the coating containing embodiment 1-3 and the hydroxyl acrylic emulsion of comparative example 1-2
Test, test result such as table 5:
The gloss of paint film uses Guangzhou style to reach the Glossmeter 60 ° test that company limited produces；
Paint film impact property presses the method for GB/T 1732-1993, uses BGD302 paint film shock-testing；
Film thickness presses former GB 1764-1979 method, uses QUANIX 4500 type boomerang to measure；
Hardness of paint film presses GB/T 6739-2006 method；Employing pencil hardness method is tested；
Paint film decay resistance presses GB T1771-2007 method, uses Heng Yu Instrument Ltd. HY-952A series saline
Nanospray experiment machine measures；
Paint film adhesion is pressed GB/T 9286-1998 method and is measured.Employing cross-hatching is tested；
The method of the wet attachment of paint film, uses HWS12 type electric-heated thermostatic water bath, and temperature is set as that 100 DEG C are boiled test board, then
Test with cross-hatching.
Table 5 is its paint film property of coating containing embodiment 1-3 and the hydroxyl acrylic emulsion of comparative example 1-2
Result shows: the described hydroxyl acrylic emulsion coating prepared containing the present invention is at hardness, pliability, adhesive force and resistance to
Wait property on basically identical with in the performance of traditional solvent-borne hydroxy acryl acid resin coating, but in VOC emission, environmental conservation
Aspect has huge advantage, and has than traditional hydroxy acryl acid emulsion coatings properties and significantly improve.
Table 6 firming agent/resin proportioning impact on hardness of paint film
| M (firming agent)/m (resin) | 1:2 | 1:3 | 1:4 |
| Pencil hardness >=H | 2H | 2H | H |
Result shows: in above-mentioned hydroxy acrylic acid formulation for coating material, the addition of firming agent is the biggest, the pencil hardness of paint film
The biggest.
Table 7 firming agent/resin proportioning impact on paint film water boiling resistance performance
| M (firming agent)/m (resin) | 1:2 | 1:3 | 1:4 |
| The water boiling resistance time/hour >= | 2 | 3 | 1 |
Result shows: in above-mentioned hydroxy acrylic acid formulation for coating material, the addition of firming agent is the biggest, paint film water boiling resistance time
Between the longest, but, the hardness of paint film crosses the pliability of conference strong influence paint film, is unfavorable for the bending process of aluminium later stage, makes
The quick-fried paint of bending part departs from, Comprehensive Experiment result: firming agent preferred 1:3 with the mass ratio of resin is advisable.
It will be apparent to those skilled in the art that can technical scheme as described above and design, make other various
Corresponding change and deformation, and all these change and deformation all should belong to the protection domain of the claims in the present invention
Within.
Claims (10)
1. a hydroxyl acrylic emulsion with nucleocapsid structure, it is characterised in that it is to draw at following five kinds of vinyl monomers
Sending out in the presence of agent and emulsifying agent, emulsion is polymerized, and the kind of monomer and the consumption of each monomer are shared in monomer total amount
Percentage ratio as follows: the vinyl monomer 40-65% 1., without other functional functional group；2., the vinyl monomer 5-of hydroxyl
30%；3., the vinyl monomer 2-5% containing epoxy radicals；4., carboxylic vinyl monomer 1-7%；5., containing polyfunctionality (>=2)
Vinyl monomer 1-3%；
Described initiator amount is the 0.2-1.5% of monomer total amount；
Described emulsifying agent is nonionic emulsifier, anionic and nonionic type emulsifying agent and anionic emulsifier, the amount ratio of three
Example is (1.0-1.5): (0.8-1.0): 0.3；The total consumption of emulsifying agent is the 1-5% of monomer total amount；
Above percentage ratio is all weight percentage.
The hydroxyl acrylic emulsion with nucleocapsid structure the most according to claim 1, it is characterised in that following monomer consumption
Percentage ratio shared in monomer total amount is preferably: the vinyl monomer of hydroxyl 2. 10-20%；Vinyl monomer containing epoxy radicals is 3.
3-5%；Carboxylic vinyl monomer 4. 1-2%；Vinyl monomer 5. 1-3% containing polyfunctionality (>=2).
The hydroxyl acrylic emulsion with nucleocapsid structure the most according to claim 1, it is characterised in that described without other
1. the vinyl monomer of functional functional group is two kinds or two in (methyl) esters of acrylic acid class monomer, aromatic series vinyl monomer
More than Zhong；
2. the vinyl monomer of described hydroxyl is any one in (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate
Or more than one.
The hydroxyl acrylic emulsion with nucleocapsid structure the most according to claim 1, it is characterised in that described containing epoxy radicals
Vinyl monomer be 3. in (methyl) glycidyl acrylate, allyl glycidyl any one or more than one.
The hydroxyl acrylic emulsion with nucleocapsid structure the most according to claim 1, it is characterised in that described carboxylic
Vinyl monomer be 4. in acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid any one or a kind of
Above.
The hydroxyl acrylic emulsion with nucleocapsid structure the most according to claim 1, it is characterised in that described containing multifunctional
The vinyl monomer of degree (>=2) is 5. glycol diacrylate, BDO diacrylate, 1,6-hexanediyl
Ester, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, ethoxyquin (N=3,9,15,21) trimethylolpropane
Triacrylate, third oxidation (N=3,4,5) trimethylolpropane trimethacrylate in any one or more than one.
The hydroxyl acrylic emulsion with nucleocapsid structure the most according to claim 1, it is characterised in that described hydroxy
In yogurt liquid, described initiator be in persulfate or azo compound any one or more than one；Described emulsifying agent
Be non-reaction of ionic type emulsifying agent, without APEO nonionic emulsifier, without APEO anionic and nonionic type emulsifying agent, anionic reaction
Property emulsifying agent, alkylsulfonate, alkyl sulfate, three kinds in alkylbenzenesulfonate, alkyl succinate or more than three kinds.
The hydroxyl acrylic emulsion with nucleocapsid structure the most according to claim 1, it is characterised in that its outward appearance is breast
White sub-translucent blue light liquid, viscosity 100-2000mPa.s, solids content 42-44%, pH value 7.0-8.5, particle diameter 0.05-0.2 μ
M, VOC VOC content ＜ 0.1%, hydroxyl value is 10-100mgKOH/g, more than 6 months storage period.
9. the preparation method of a hydroxyl acrylic emulsion as claimed in claim 1 with nucleocapsid structure, it is characterised in that
First being prepared stratum nucleare pre-emulsion by the partial monosomy and emulsifying agent forming emulsion particle stratum nucleare, in the presence of initiator, polymerization prepares
Stratum nucleare emulsion, then uniformly drips shell mix monomer, is polymerized in the presence of initiator, neutralized, and filtration, discharging are tool
There is the hydroxyl acrylic emulsion of nucleocapsid structure, specifically comprise the following steps that
(1) preparation of stratum nucleare pre-emulsion: by partial monosomy 1., partial monosomy 4. and all monomers 5., at the work of emulsifying agent
It is dispersed in water under with, obtains stratum nucleare pre-emulsification monomer mixture；
(2) preparation of shell pre-emulsion: by remaining monomer 1., 4. and all monomer 2., 3., under the effect of emulsifying agent
It is dispersed in water, obtains shell pre-emulsification monomer mixture；
(3) emulsifying agent and initiator are joined in reaction medium water, be placed in 500ml flask and stir, and be warming up to 75
～80 DEG C, the stratum nucleare pre-emulsion of dropping 1%-10% part by weight, rotary speed maintains 100-300rpm, continuously stirred 0.5-
1 hour, treat that emulsion becomes blue phase, it is thus achieved that seed emulsion；
(4) then toward dropping residue stratum nucleare pre-emulsion and initiator solution in flask, after dropping, it is incubated 75～80 DEG C,
Maintain 0.5-1.0 hour；
(5) then in flask, drip shell pre-emulsion and initiator solution, after dripping off, be incubated 75-80 DEG C and maintain 2.0-2.5
Hour；
(6) being cooled to 40 DEG C, the ammonia of 1.0-2.5g is blended in the emulsion in flask until being modulated by the pH value of liquid in beaker
For 7.5-8.0, filtration, discharging are the hydroxyl acrylic emulsion with nucleocapsid structure.
10. the application of a hydroxyl acrylic emulsion as claimed in claim 1 with nucleocapsid structure, it is characterised in that should
For aluminium material surface decorative paint.
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