CN108047926A - A kind of aqueous double-component varnish and preparation method thereof - Google Patents
A kind of aqueous double-component varnish and preparation method thereof Download PDFInfo
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- CN108047926A CN108047926A CN201711353620.3A CN201711353620A CN108047926A CN 108047926 A CN108047926 A CN 108047926A CN 201711353620 A CN201711353620 A CN 201711353620A CN 108047926 A CN108047926 A CN 108047926A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of aqueous double-component varnish and preparation method thereof.The aqueous double-component varnish is by two component of A, B with (2.5~3.5)：1 mass ratio is mixed to get, and wherein component A includes the following component according to parts by weight：25~40 parts of water-based acrylic resin, 25~40 parts of aqueous polyester resin, 0.1~1 part of substrate wetting agents, 0.1~1 part of levelling agent, 0.1~1 part of antifoaming agent, 0.1~1 part of ultra-violet absorber, 0.1~1 part of fungicide, 5~10 parts of cosolvent, 0.1~1 part of thickener, 2~5 parts of carboxymethyl chitosan；B component includes the following component according to parts by weight：40~60 parts of isocyanate curing agent, 0.1~1 part of adhesion promoter, 40~60 parts of cosolvent.Plumpness, gloss, levelability, application property and the terms of mechanics performance of the varnish can reach the standard of high-performance oil varnish, higher than existing water varnish, and have the advantages that low VOCs.
Description
Technical field
The invention belongs to coating preparation field, in particular to a kind of automobile-used aqueous double-component varnish.
Background technology
Coating refers to that secured, object of the formation with some strength solid film can be combined with the surface coated on object surface
Matter.
Varnish also known as varnish add the coating that forms of solvent by resin for main film forming substance, due to coating and
Film is all transparent, thus also referred to as clear dope.Must possess several functions：1. good appearance：Including plumpness height, light
Damp height, good leveling property, without shrinkage cavity, without prickly heat etc.；2. excellent protective value：Including hardness is good, flexibility is good, good weatherability,
Water-tolerant, salt fog resistance are good etc.；3. excellent application property：It is good including wetability, it is not easy to sagging；4. broad construction window
Mouthful：Including there is good adaptability etc. to temperature and humidity.
Varnish is divided into two class of oil varnish and resin varnish, and lacquer materials are mainly the one-component paint of hot setting：Poly- ammonia
Ester or polyester and the two-component acrylicester class of spontaneous curing.Because oil varnish can be generated in coating process and largely waved
Hair property organic compound (VOCs), can not only cause ecological environment serious pollution, while also bring pole to human health
Big harm.With the improvement of people's environmental awareness, national governments have all put into effect a large amount of relevant regulations to limit VOCs's
Discharge capacity.For the development in the epoch of complying with, the positive environmentally friendly direction transformation of coating, wherein Environmentally friendly coatings include
Water paint, powdery paints, UV be coating material solidified and high solid coating, and water paint with its excellent comprehensive performance takes off grain husk and
Go out, be one kind with fastest developing speed.
Because finishing coat with varnish from ingredient and functionally for be substantially the same, maximum not existing together is only that in coat component
It can show that varnish exists containing mill base, therefore by analyzing the defects of existing finishing coat there are problems that, such as patent
CN105482588A《A kind of environment-friendly type nano metal automobile finishing coat》A kind of automobile finish is disclosed, which is handled by addition
Nano metal powder afterwards coordinates with other materials, finally obtains the finishing coat of function admirable, it is added in usual resins component
Enter metal powder material, step increases, and cost improves, and has certain requirement to metal powder material；Patent CN106800874A《A kind of water
Property two component polyurethane finishing coat and preparation method thereof》It discloses mainly by hydroxy acrylate and isocyanate curing agent as master
Ingredient is wanted, but contains two kinds of polyisocyanate curing agents of hydrophily and hydrophobicity in curing agent simultaneously, and aqueous hydroxyl in component A
Base acrylic acid dispersion content is high, and the resistance to acid and alkali of product is uneven.
And for the varnish as two-component acrylicester class, traditional water-based acrylic resin coating have easy dehydration,
Light absorptive is higher, hot sticky cold crisp, it is environmentally sensitive the defects of, and existing water-based acrylic resin is for oil varnish,
Also there are gaps for the plumpness of paint film, gloss, levelability, application property etc..It is a kind of with good full therefore, it is necessary to develop
Full scale, gloss, the aqueous double-component varnish of levelability and application property.
The content of the invention
In view of insufficient existing for existing water-based acrylic resin coating, it is an object of the invention to provide a kind of aqueous double groups
Part varnish, the aqueous double-component varnish performance is not only suitable with oil paint, and there is no the defects of oil paint.
In order to realize the above-mentioned purpose of the present invention, by a large number of experiments research and unremitting effort, following skill is finally obtained
Art scheme：A kind of aqueous double-component varnish, by two component of A, B with (2.5~3.5)：1 mass ratio is mixed to get, wherein component A
Include the following component according to parts by weight：
B component includes the following component according to parts by weight：
40~60 parts of isocyanate curing agent
0.1~1 part of adhesion promoter
40~60 parts of cosolvent；
The water-based acrylic resin is prepared via a method which：By methyl methacrylate, hydroxy-ethyl acrylate, propylene
Acid in mass ratio 20:25:5 ratio mixing adds 1~2% initiator dibenzoyl peroxide, is uniformly mixed, obtains
Mixed liquor；The epoxy resin of 4~6 parts by weight, middle ring are added in the hexamethylene and the in the mixed solvent of water that parts by weight are 37 parts
The mass ratio of hexane and water is 1:(2~4) flow back at 100~120 DEG C, at the same by mixed liquor be added dropwise to hexamethylene with
The in the mixed solvent of water, 1.6~2h are dripped, and continue to keep the temperature, and react more than 3h, stop heating, are cooled to less than 80 DEG C, are carried out
Vacuum distillation, removes part solvent and unreacted monomer, the distilled water for adding 3~6 parts by weight are diluted, finally with three
It is 7~7.5 that ethamine, which adjusts pH, stirs evenly, obtains water-based acrylic resin.
In the present invention aqueous polyester resin be hydroxyl terminated unsaturated polyester, be in nitrogen atmosphere heat unsaturated acid anhydride and
Saturation acid anhydrides obtains, and is existing conventional techniques means.
It is further preferred that aqueous double-component varnish of the present invention, by two component of A, B with 3：1 mass ratio mixes
It arrives, specific each content of material is as follows in each component：
Wherein component A includes the following component according to parts by weight：
B component includes the following component according to parts by weight：
48~53 parts of isocyanate curing agent
0.5~0.8 part of adhesion promoter
48~55 parts of cosolvent.
It is further preferred that aqueous double-component varnish of the present invention, specific each content of material is as follows in each component：
Wherein component A includes the following component according to parts by weight：
B component includes the following component according to parts by weight：
50 parts of isocyanate curing agent
0.6 part of adhesion promoter
52 parts of cosolvent.
The present invention carries out polymerisation in water-based acrylic resin building-up process using the monomer with different hydrophilic group,
Improve the film forming of resin first, while there is preferable film forming using carboxymethyl chitosan, film is glossy, it is transparent and
The characteristics of flexible, further improves the filming performance of finishing coat entirety, while carboxymethyl chitosan has stronger water imbibition, because
This is with good performance of keeping humidity, and the hot sticky defect for effectively improving acrylic resin is cold short so that finishing coat viscosity substantially constant.
It is further preferred that aqueous double-component varnish of the present invention, base material wetting agent therein is polyether-modified silicon
Oxygen alkane,
It is further preferred that aqueous double-component varnish of the present invention, thickener therein is polyurethane.
It is further preferred that aqueous double-component varnish of the present invention, levelling agent therein for carboxymethyl cellulose or
Polyacrylic acid.
It is further preferred that aqueous double-component varnish of the present invention, cosolvent therein is hydrophobic cosolvent, described
Hydrophobic cosolvent includes propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, dipropylene glycol fourth
Ether, n-amyl alcohol and n-octyl alcohol.
It is further preferred that aqueous double-component varnish of the present invention, isocyanate curing agent is two in the B component
Methylenebis phenyl isocyanate curing agent.
The present invention also provides the preparation methods of above-mentioned aqueous double-component varnish, specifically include following preparation process：
(1) water-based acrylic resin and aqueous polyester resin are uniformly mixed, are slowly added to carboxymethyl chitosan, base material profit
Humectant, levelling agent, antifoaming agent, ultra-violet absorber, fungicide and cosolvent adjust viscosity with thickener, are obtained after filtering and discharging
To component A；
(2) isocyanate curing agent, adhesion promoter and cosolvent are mixed, filtering and discharging obtains component B；
(3) component A and B component are mixed in proportion, obtains aqueous double-component varnish.
It is further preferred that the preparation method of aqueous double-component varnish of the present invention, filtering is filtered using 120-200 mesh
Net is filtered.
The present invention has the following technical effect that compared with the prior art：
The aqueous double-component varnish of the present invention is combined by specific substance, and aids in existing conven-tional adjuvants of arranging in pairs or groups, and is made
Standby obtained varnish, plumpness, gloss, levelability, application property and terms of mechanics performance can reach the performance of oil based coating, high
In existing disclosed water varnish, and there is low VOCs.
Specific embodiment
The specific embodiment of the present invention is described further below, but protection scope of the present invention is not limited only to down
The embodiment stated.
Acrylic resin refers to acrylic acid, acrylic ester monomer is aggregated, is copolymerized, one kind obtained by grafting or blending
Polymer, water-based acrylic resin refer to by be originally be grafted on water-insoluble acrylic resin a certain amount of hydrophilic radical or
By alcoholysis, into water-soluble resin made of the modes such as salt.With being increasingly enhanced for mankind's environmental consciousness, due to water soluble acrylic acid
Resin has many advantages, such as excellent anti-corrosive properties, weatherability, water-fast, alkaline-resisting, good film-forming property, environmentally safe, safe to use, adopts
Main way of the solvent based coating as modern coatings industrial development, common water soluble acrylic acid are replaced with water-based acrylic resin
Resin includes aqueous solution type and water-dispersion type, but all comes with some shortcomings, such as aqueous solution type acrylic resin has film forming
Water-resistant type is poor afterwards, and cannot often form continuous resin film；Water-dispersion type then exists is unable to shape below minimum film formation temperature
Into continuous film so that for the high polymer of glass transition temperature, it is difficult to be formed at room temperature, after water volatilization, resin viscosity
Rapid to rise, film is also easy to produce bubble and pin hole, the coating that the water very big by the use of surface tension to prepare as dispersant, to base
The wetability of material is poor, particularly easily forms rough film when metal surface or frosting are constructed.Consider,
Mainly there are the defects of hot sticky cold crisp for water-based acrylic resin.
An important content for preparing water-based acrylic resin is that oil-soluble polymer how to be enable to be dissolved in water, aqueous
Modificationization method mainly has salt forming method, alcoholysis method, introduces nonionic hydrophilic moieties method, and can improve it by the above method lacks
Fall into, and it is the most frequently used and it is effective be then the nonionic hydrophilic moieties method that introduces, but inventor is on the basis of existing technology,
Different types of nonionic hydrophilic moieties are introduced in water-based acrylic resin polymerization process, the application property of the varnish found
It although makes moderate progress with mechanical property, but the performance of oil paint is still not achieved, therefore inventor is to water soluble acrylic acid tree
On the premise of fat is modified, investigate not by chemical synthesis mode, but physics introduces other high molecular polymers and coordinates with it
It uses, whether see makes varnish effect increase significantly, it turns out that after specific high molecular polymer is added in, hot sticky cold crisp
That is application property scope is significantly expanded, and is also improved in terms of mechanical property.
Water-based acrylic resin is prepared via a method which in following embodiments：By 20 parts by weight of methyl methacrylate,
25 parts by weight of hydroxy-ethyl acrylate, the mixing of the ratio of 5 parts by weight of acrylic acid add the initiator diphenyl peroxide of 1 parts by weight
Formyl is uniformly mixed, obtains mixed liquor, and 4.5 parts by weight are added in the hexamethylene of 37.5 parts by weight and the in the mixed solvent of water
The mass ratio of epoxy resin, hexamethylene He Shui and water is 1：3, it flows back at 110 DEG C, while mixed liquor is added dropwise to hexamethylene
The in the mixed solvent of alkane and water, 2h are dripped, and continue to keep the temperature, and react 3h, are stopped heating, are cooled to 70 DEG C, are evaporated under reduced pressure,
Recycling part solvent and unreacted monomer are removed, adds in the distilled water dilution of 4 parts by weight, it is 7 that triethylamine, which adjusts pH, stirring
30min obtains water-based acrylic resin.
Thickener is polyurethane in the embodiment of the present invention, and levelling agent is carboxymethyl cellulose, isocyanate curing agent two
Methylenebis phenyl isocyanate curing agent, cosolvent are n-amyl alcohol, and adhesion promoter includes silanes adhesion promoter, attachment
Make every effort to promote into resin, adhesion promoter uses silane coupling agent in following embodiments, and above-mentioned each auxiliary agent is object commonly used in the art
Matter.
Embodiment 1
The preparation of aqueous double-component varnish
The formula of aqueous double-component varnish is as shown in table 1, and preparation process is as follows：
(1) put into the water-based acrylic resin of formula ratio successively into container and aqueous polyester resin and be uniformly mixed, it
After be slowly added to carboxymethyl chitosan, substrate wetting agents, levelling agent, antifoaming agent, ultra-violet absorber, fungicide and cosolvent,
Thickener is added, component A is obtained after stirring evenly rear filtering and discharging；
(2) the mixing isocyanate curing agent, adhesion promoter and cosolvent of formula ratio, filtering are added in into container
Discharging obtains component B；
(3) it is 3 according to the mixed proportion of A and B：1 is mixed, and obtains aqueous double-component varnish.
The aqueous double-component varnish of 1 different formulations of table
The aqueous double-component varnish performance detection data of 2 different formulations of table
Meanwhile inventor has detected the performance of commercially available oil varnish and water varnish, wherein commercially available oil varnish model
The beautiful varnish of SW-877 (Ya Tu new high-tech materials Co., Ltd), the poly- ammonia of commercially available water varnish model WB05-01 water soluble acrylic acids
Ester varnish (Beijing Yulin Chemical Co., Ltd.), the results are shown in Table 3 for detection performance.
3 commercially available oil varnish of table and water varnish performance
From table 1, table 2 and table 3, inventive formulation comprehensive performance is suitable with conventional oil-based varnish, considerably beyond tradition
Water soluble acrylic acid varnish, comprehensive and above-mentioned performance, the varnish performance that formula 5 obtains are best.
Embodiment 2
Table 4 is in the case that embodiment 2 ensures that each substance classes are constant in formula, to change feeding intake for each content of material and match somebody with somebody
Side, aqueous double-component varnish is prepared according to the technical process of embodiment 1.
The performance for obtaining aqueous double-component varnish prepared by formula 6~9 is as shown in table 5, is understood with 2 performance comparison of table,
When each substance classes parts by weight of A, B component exceed 1 table scope of disclosure of embodiment, what is obtained obtains aqueous double-component varnish
Various aspects of performance drastically reduces.
The aqueous double-component varnish of 4 different formulations of table
The aqueous double-component varnish performance detection data of 5 different formulations of table
Comparative example 1
Under the premise of 1 preparation process of embodiment and its parameter constant, on the basis of 5 composition of formula and its each content of material,
It has investigated and water-based acrylic resin Hydroxylated acrylic resin, the organosilicon modified crylic acid resin in component A is replaced, and examined
Its performance is surveyed, the wherein specific preparation process of organosilicon-modified acrylic is：Take methyl methacrylate 30ml, butyl acrylate
15ml, 3ml glycidyl methacrylate, 6ml methacrylic acids, 6ml vinyl silicone oils are uniformly mixed, and are added in mixed liquor
Enter 100ml deionized waters, 2h, 200W ultrasonic echography 15min are stirred with 900r/min, add in 2g initiators 2,2 ,-azo two
Isobutyl amidine dihydrochloride under nitrogen atmosphere, is heated to 75 DEG C, keeps the temperature 1h, continues to be heated to 85 DEG C of heat preservation 3h, is cooled to room
Temperature, discharging, obtains organosilicon-modified acrylic emulsion.
6 different formulations varnish performance of table
Comparative example 2
Since carboxymethyl chitosan is the common substances such as medicine, field of textiles in inventive formulation, in the art not
It is common, therefore inventor has been investigated based on the formula of embodiment 15, after not adding carboxymethyl chitosan, the property of obtained substance
Can, the results are shown in Table 7.
Table 7 is not added with the varnish performance that carboxymethyl chitosan obtains
Claims (10)
1. a kind of aqueous double-component varnish, it is characterised in that by two component of A, B with (2.5~3.5)：1 mass ratio is mixed to get,
Wherein component A includes the following component according to parts by weight：
B component includes the following component according to parts by weight：
40~60 parts of isocyanate curing agent
0.1~1 part of adhesion promoter
40~60 parts of cosolvent；
The water-based acrylic resin is prepared via a method which：Methyl methacrylate, hydroxy-ethyl acrylate, acrylic acid are pressed
Mass ratio 20:25:5 ratio mixing adds 1~2% initiator dibenzoyl peroxide, is uniformly mixed, is mixed
Liquid；The epoxy resin of 4~6 parts by weight, cyclohexane are added in the hexamethylene and the in the mixed solvent of water that parts by weight are 37 parts
Mass ratio with water is 1:(2~3) flow back at 100~120 DEG C, while mixed liquor is added dropwise to hexamethylene and water
In the mixed solvent, 1.6~2h are dripped, and continue to keep the temperature, and react more than 3h, are stopped heating, are cooled to less than 80 DEG C, are depressurized
Distillation, it is 7~7.5 that triethylamine, which adjusts pH, obtains water-based acrylic resin.
2. aqueous double-component varnish according to claim 1, it is characterised in that by two component of A, B with 3：1 mass ratio mixing
It obtains, it is as follows that each substance accounts for respective components by weight：
Wherein component A includes the following component according to parts by weight：
B component includes the following component according to parts by weight：
48~53 parts of isocyanate curing agent
0.5~0.8 part of adhesion promoter
48~55 parts of cosolvent.
3. aqueous double-component varnish according to claim 2, it is characterised in that：
Wherein component A includes the following component according to parts by weight：
B component includes the following component according to parts by weight：
50 parts of isocyanate curing agent
0.6 part of adhesion promoter
52 parts of cosolvent.
4. aqueous double-component varnish according to claim 1, it is characterised in that：The base material wetting agent is polyether-modified silica
Alkane.
5. aqueous double-component varnish according to claim 1, it is characterised in that：The thickener is polyurethane.
6. aqueous double-component varnish according to claim 1, it is characterised in that：The levelling agent is carboxymethyl cellulose or poly-
Acrylic acid.
7. aqueous double-component varnish according to claim 1, it is characterised in that：The cosolvent is hydrophobic cosolvent, described
Hydrophobic cosolvent includes propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, dipropylene glycol fourth
Ether, n-amyl alcohol and n-octyl alcohol.
8. aqueous double-component varnish according to claim 1, it is characterised in that：Isocyanates accelerating agent is in the B component
Methyl diphenylene diisocyanate accelerating agent.
9. a kind of preparation method for the aqueous double-component varnish for preparing any one of claim 1-8, it is characterised in that specifically include
Following preparation process：
(1) water-based acrylic resin and aqueous polyester resin are uniformly mixed, are slowly added to carboxymethyl chitosan, base material wetting
Agent, levelling agent, antifoaming agent, ultra-violet absorber, fungicide and cosolvent add thickener, component are obtained after filtering and discharging
A；
(2) isocyanate curing agent, adhesion promoter and cosolvent are mixed, filtering and discharging obtains component B；
(3) obtained component A with B component is mixed in proportion, obtains aqueous double-component varnish.
10. the preparation method of aqueous double-component varnish according to claim 9, it is characterised in that：120-200 is used during filtering
Purpose strainer filtering.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112680051A (en) * | 2021-01-15 | 2021-04-20 | 江阴市荣新塑化有限公司 | High-brightness high-weather-resistance varnish for spraying automobile bumper and preparation method thereof |
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| CN112680051A (en) * | 2021-01-15 | 2021-04-20 | 江阴市荣新塑化有限公司 | High-brightness high-weather-resistance varnish for spraying automobile bumper and preparation method thereof |
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