CN101544728A - Water paint base, preparation method thereof and water paint containing same - Google Patents
Water paint base, preparation method thereof and water paint containing same Download PDFInfo
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- CN101544728A CN101544728A CN200910038095A CN200910038095A CN101544728A CN 101544728 A CN101544728 A CN 101544728A CN 200910038095 A CN200910038095 A CN 200910038095A CN 200910038095 A CN200910038095 A CN 200910038095A CN 101544728 A CN101544728 A CN 101544728A
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Abstract
The invention provides a water paint base which has at least one of the structures as shown in formula (I), formula (II) and formula (III), wherein F is selected from acrylic ester group, hydroxide group, epoxy group, carbamide group and carboxyl, and R1, R2, R3, R4, R5 and R6 are same or different alkanes or aromatic hydrocarbons with at most 36 carbon atoms. The invention also provides a preparation method of the water paint base and a water paint containing the same. The water paint can be effectively uniformly absorbed on the surface of an object through the action of an electrostatic field and can form into a coating with high compactness, high lustrousness, high rigidity after being dried and solidified.
Description
Technical field
The present invention relates to water-borne coatings base-material and preparation method thereof, be specifically related to use the water-borne coatings base-material of two key hydroxyls of band or the preparation of carboxyl functional group monomer.The invention still further relates to the water-borne coatings that also has described base-material.
Background technology
Along with the pay attention to day by day of people to environment protection, conventional solvent based coating is progressively replaced by water-borne coatings.Water-borne coatings is with water as solvent, and the possibility of presence of fire has reduced atmospheric pollution when having eliminated construction, and it only adopts a small amount of hypotoxicity alcohol ethers organic solvent, has improved operating environmental condition.General water-borne coatings organic solvent (accounting for coating) between 10%～15%, to reduce to pollute, to save resource impact remarkable.And water-borne coatings can directly apply construction in wet surface and wet environment, material surface is had excellent adaptability, and coating adhesion is strong, and coating tool can wash by water, and significantly reduces the consumption of cleaning solvent.
Yet the coating process that existing water-borne coatings is suitable for is limited, can not satisfy user's needs well.Therefore, be necessary to provide a kind of novel aqueous coating, it can use more kinds of methods to be coated with, and can form high-quality coating.
Summary of the invention
Therefore, one object of the present invention is to provide a kind of water-borne coatings base-material, and it has the structure shown at least a formula (I), formula (II) and the formula (III):
F---R
1---F formula (I)
Formula (II)
Wherein F is selected from acrylate-based, hydroxyl, epoxy group(ing), carbimide base and carboxyl; R
1, R
2, R
3, R
4, R
5And R
6Be to have 36 carbon atoms, identical or different at the most alkane or aromatic hydrocarbons.
Another object of the present invention is to provide a kind of preparation method of above-mentioned water-borne coatings base-material, it may further comprise the steps:
(a) with the C of 25-40wt%
8-C
16The C of aromatic hydrocarbons diprotic acid, 30-45wt%
3-C
6The C of dibasic alcohol, 2-5wt%
3-C
8The C of polyvalent alcohol, 15-30wt%
4-C
10The C of aliphatic dibasic acid, 3-5wt%
4-C
36The Lewis acid of unsaturated dibasic acid and 0.05-0.25wt% drops in the reactor, and temperature is risen to 230 ℃-240 ℃ with melting materials capable and carry out esterification, and heat-up rate is for per hour rising 10 ℃-20 ℃, and the control aquifer yield is 15-20%;
(b) in last two hours of reaction, measure acid number, when acid number is lower than 15mg KOH/g, cool the temperature to 180 ℃-190 ℃ and add the trimellitic acid 1,2-anhydride of 2.5-3.5wt%, and under this temperature, react, be lower than 20mg KOH/g, obtain resin I up to acid number;
(c) cool the temperature to 70 ℃-100 ℃, and add the pure ether compound of the 15-25wt% that accounts for resin I;
(d) in the mixture of step (c), add the vinylformic acid mix monomer of the 4-20wt% account for resin I, and continue reaction dischargings after 2-3 hour at 70 ℃-100 ℃, and with pH regulator to 7-8.
In preferred embodiment, the C described in the step (a)
8-C
16The aromatic hydrocarbons diprotic acid is selected from Tetra hydro Phthalic anhydride, m-phthalic acid, a phenylene-diacetic acid, a benzene dipropionic acid, to benzene two butyric acid with to benzene two valeric acids.Described C
3-C
6Dibasic alcohol is selected from propylene glycol, butyleneglycol, neopentyl glycol, hexylene glycol and pentanediol.Described C
3-C
8Polyvalent alcohol is selected from glycerol, tetramethylolmethane, TriMethylolPropane(TMP).Described C
4-C
36Unsaturated acid is maleic acid anhydride or dimerization behenic acid.Described C
4-C
10Aliphatic dibasic acid is selected from Succinic Acid, pentanedioic acid, hexanodioic acid and sebacic acid.Pure ether compound described in the step (c) is selected from propylene glycol monomethyl ether, propylene-glycol ethyl ether and dipropylene glycol methyl ether.Vinylformic acid mix monomer described in the step (d) contains the vinylbenzene of 40-50wt%, the methyl methacrylate of 20-50wt%, the glycidyl acrylate of 3-10wt%, the Hydroxyethyl acrylate of 1-4wt% and the peroxidation organism of 0.5-3wt%.
In preferred embodiment, the Lewis acid described in the step (a) is any suitable Lewis acid, for example tributyl tin and/or triethyl aluminum.Described peroxidation organism can be, for example, and Diisopropyl azodicarboxylate (AIBN) and/or benzoyl peroxide (B.P.O.)
Another purpose of the present invention is to provide a kind of water-borne coatings, and it comprises above-mentioned base-material.
Water-borne coatings provided by the invention can use more kinds of methods to be coated with, for example can use water-borne coatings to be coated with Taic coating device, and the effect by electrostatic field can be adsorbed on article surface effectively, equably, can form the coating of high compactness, high glossiness and high rigidity after drying and the curing.
Embodiment
One, the preparation of the base-material of water-borne coatings
Embodiment 1
Content shown in the component of table 1 pressed uses following condition to mix: m-phthalic acid, neopentyl glycol, TriMethylolPropane(TMP), adipic acid, maleic acid anhydride and tributyl tin are dropped in the reactor, logical nitrogen is warming up to 230 ℃ and carries out esterification, temperature-rise period is controlled the speed of 15 ℃ of risings in per 60 minutes, and aquifer yield is controlled at 15%.Per 30 minutes sampling detecting acid numbers in last two hours of reaction are cooled to 180 ℃ and add the trimellitic acid anhydride reactant when acid number is lower than 15mg KOH/g, be lower than 20mg KOH/g until acid number, obtain resin I.Be cooled to 70 ℃ and add propylene-glycol ethyl ether this moments.Under this temperature, add acrylate mixing monomer (each component and content are as shown in table 2 in the mixture among every 100g), and continue to keep discharging after 2 hours, adjust about pH to 7, obtain required base-material with trolamine.Then, as required, can add an amount of pure water and use high speed dispersor the water dispersion that is various different contents with described base-material phase inversion, for example 10%, 20%, 30%, 40% or the like.
Table 1
| Component | Content (g) |
| TriMethylolPropane(TMP) | 3.9 |
| Neopentyl glycol | 37.9 |
| Hexanodioic acid | 20.0 |
| M-phthalic acid | 32.0 |
| Maleic acid anhydride | 3.0 |
| Tributyl tin | 0.2 |
| Trimellitic acid 1,2-anhydride | 3.0 |
| Propylene-glycol ethyl ether | 12.75 |
| Acrylate mixing monomer | 3.4 |
Table 2
| Component | Content (g) |
| Vinylbenzene | 46 |
| Methyl methacrylate | 46 |
| Glycidyl acrylate | 5 |
| Hydroxyethyl acrylate | 1 |
| AIBN | 2 |
Embodiment 2
Content shown in the component of table 3 pressed uses following condition to mix: will between benzene two valeric acids, propylene glycol, tetramethylolmethane, Succinic Acid, maleic acid anhydride and tributyl tin drop in the reactor, logical nitrogen is warming up to 230 ℃ and carries out esterification, temperature-rise period is controlled the speed of 20 ℃ of risings in per 60 minutes, and aquifer yield is controlled at 15%.Per 30 minutes sampling detecting acid numbers in last two hours of reaction are cooled to 180 ℃ and add the trimellitic acid anhydride reactant when acid number is lower than 15mg KOH/g, be lower than 20mg KOH/g until acid number, obtain resin I.Be cooled to 85 ℃ and add propylene glycol monomethyl ether this moments.Under this temperature, add acrylate mixing monomer (each component and content are as shown in table 4 in the mixture among every 100g), and continue to keep discharging after 2 hours, adjust pH to 8, obtain required base-material with trolamine.Then, as required, can add an amount of pure water and use high speed dispersor the water dispersion that is various different contents with described base-material phase inversion, for example 10%, 20%, 30%, 40% or the like.
Table 3
| Component | Content (g) |
| Tetramethylolmethane | 4.5 |
| Propylene glycol | 32.5 |
| Succinic Acid | 28.9 |
| Between benzene two valeric acids | 26.7 |
| Maleic acid anhydride | 3.8 |
| Tributyl tin | 0.2 |
| Trimellitic acid 1,2-anhydride | 3.4 |
| Propylene glycol monomethyl ether | 12.75 |
| Acrylate mixing monomer | 3.4 |
Table 4
| Component | Content (g) |
| Vinylbenzene | 50 |
| Methyl methacrylate | 42 |
| Glycidyl acrylate | 5 |
| Hydroxyethyl acrylate | 1.5 |
| AIBN | 1.5 |
Embodiment 3
Content shown in the component of table 5 pressed uses following condition to mix: will between benzene dipropionic acid, hexylene glycol, glycerol, sebacic acid, dimerization behenic acid and triethyl aluminum drop in the reactor, logical nitrogen is warming up to 240 ℃ and carries out esterification, temperature-rise period is controlled the speed of 20 ℃ of risings in per 60 minutes, and aquifer yield is controlled at 20%.Per 30 minutes sampling detecting acid numbers in last two hours of reaction are cooled to 190 ℃ and add the trimellitic acid anhydride reactant when acid number is lower than 15mg KOH/g, be lower than 20mg KOH/g until acid number, obtain resin I.Be cooled to 85 ℃ and add propylene glycol monomethyl ether this moments.Under this temperature, add acrylate mixing monomer (each component and content are as shown in table 6 in the mixture among every 100g), and continue to keep discharging after 3 hours, adjust pH to 8, obtain required base-material with trolamine.Then, as required, can add an amount of pure water and use high speed dispersor the water dispersion that is various different contents with described base-material phase inversion, for example 10%, 20%, 30%, 40% or the like.
Table 5
| Component | Content (g) |
| Glycerol | 2.1 |
| Hexylene glycol | 40.3 |
| Sebacic acid | 15.0 |
| Between the benzene dipropionic acid | 35.8 |
| The dimerization behenic acid | 4.1 |
| Triethyl aluminum | 0.2 |
| Trimellitic acid 1,2-anhydride | 2.5 |
| Propylene glycol monomethyl ether | 20.0 |
| Acrylate mixing monomer | 12.0 |
Table 6
| Component | Content (g) |
| Vinylbenzene | 40 |
| Methyl methacrylate | 46.5 |
| Glycidyl acrylate | 8 |
| Hydroxyethyl acrylate | 3 |
| AIBN | 2.5 |
Embodiment 4
Content shown in the component of table 7 pressed uses following condition to mix: Tetra hydro Phthalic anhydride, propylene glycol, tetramethylolmethane, Succinic Acid, dimerization behenic acid and triethyl aluminum are dropped in the reactor, logical nitrogen is warming up to 235 ℃ and carries out esterification, temperature-rise period is controlled the speed of 15 ℃ of risings in per 60 minutes, and aquifer yield is controlled at 18%.Per 30 minutes sampling detecting acid numbers in last two hours of reaction are cooled to 190 ℃ and add the trimellitic acid anhydride reactant when acid number is lower than 15mg KOH/g, be lower than 20mg KOH/g until acid number, obtain resin I.Be cooled to 100 ℃ and add dipropylene glycol methyl ether this moments.Under this temperature, add acrylate mixing monomer (each component and content are as shown in table 8 in the mixture among every 100g), and continue to keep discharging after 2.5 hours, adjust pH to 7, obtain required base-material with diethanolamine.Then, as required, can add an amount of pure water and use high speed dispersor the water dispersion that is various different contents with described base-material phase inversion, for example 10%, 20%, 30%, 40% or the like.
Table 7
| Component | Content (g) |
| Tetramethylolmethane | 3.2 |
| Propylene glycol | 36.35 |
| Succinic Acid | 22.1 |
| Tetra hydro Phthalic anhydride | 30.9 |
| The dimerization behenic acid | 4.7 |
| Triethyl aluminum | 0.15 |
| Trimellitic acid 1,2-anhydride | 2.6 |
| Dipropylene glycol methyl ether | 20.5 |
| Acrylate mixing monomer | 16.4 |
Table 8
| Component | Content (g) |
| Vinylbenzene | 47 |
| Methyl methacrylate | 42 |
| Glycidyl acrylate | 9 |
| Hydroxyethyl acrylate | 3.5 |
| B.P.O. | 0.5 |
Two, the preparation of water-borne coatings
Embodiment 5
Component and content are prepared water-borne coatings of the present invention shown in the according to the form below 9: the preparation method of described water-borne coatings can carry out according to any suitable method well known by persons skilled in the art.For example, it is the water dispersion of 40% or 50% content that any base-material among the foregoing description 1-4 is added an amount of water phase inversion, subsequently this water dispersion, pigment, dispersion agent and part pure water are ground, are dispersed to fineness together to reach≤20 μ m, and under whipped state, add solidifying agent, remaining pure water and flow agent, be mixed with water-borne coatings.Can add various pigment according to the required color of finished product, for example titanium dioxide, ferric oxide series, mica powder series, carbon black, the dark green series of phthalein, serial, the metallic aluminium powder of phthalocyanine blue.Described various auxiliary agent can be selected any auxiliary agent well known by persons skilled in the art for use, and for example: solidifying agent can be selected high methyl ether terpolycyantoamino-formaldehyde resin for use; Dispersion agent can be selected non-ionic type modified fat acid derivative for use; Flow agent can be selected polysiloxane-polyether copolymer for use; Defoamer can be selected non-silicon class organic polymer or the like for use.
Table 9: the component of water-borne coatings and content
| Component | Content (wt%) |
| Any water dispersion of embodiment 1-4 | 55-60 |
| Solidifying agent | 8-10 |
| Dispersion agent | 0.8-2.5 |
| Pigment | 20-25 |
| Flow agent | 0.1-0.4 |
| Defoamer | 0.1-0.2 |
| Pure water | 1.9-16.0 |
Three, coating performance checking
The base-material that will use embodiment 1-4 respectively carries out every experiment shown in the following table 10 by the water-borne coatings that the method for embodiment 5 makes, the result proves the coating that uses base-material of the present invention to make, reach or be higher than national standard, and be coated with by the water-based Taic coating device, can form the coating of high compactness, high glossiness and high rigidity.The partial properties index of this coating is as follows:
Table 10
| Film performance | Example 1 | Example 2 | Example 3 | Example 4 | Desired value |
| Gloss (60 °), % (colored paint) | 85 | 82 | 80 | 84 | ≥80 |
| Sticking power (drawing the circle method), level | 2 | 1 | 1 | 2 | ≤2 |
| Snappiness, mm | 2 | 2 | 1 | 1 | ≤2 |
| Pencil hardness, H | 3 | 2 | 2 | 2 | ≥2 |
| Shock strength, kgcm | 50 | 50 | 50 | 50 | 50 pass through |
| Water tolerance, hr | Qualified | Qualified | Qualified | Qualified | Passed through in 500 hours |
| Resistance to salt water (3%), hr | Qualified | Qualified | Qualified | Qualified | Passed through in 48 hours |
Though the present invention is described with reference to concrete embodiment, those skilled in the art can make conspicuous modification and modification to the present invention by after reading foregoing description, and without prejudice to the intent of the present invention and essence.The present invention comprises these modifications and modification within the scope of the claims intentionally.
Claims (10)
1. water-borne coatings base-material, it has the structure shown at least a formula (I), formula (II) and the formula (III):
F---R
1---F formula (I)
Formula (II)
Formula (III)
Wherein, F is selected from acrylate-based, hydroxyl, epoxy group(ing), carbimide base and carboxyl; R
1, R
2, R
3, R
4, R
5And R
6Be to have 36 carbon atoms, identical or different at the most alkane or aromatic hydrocarbons.
2. method for preparing the water-borne coatings base-material of claim 1, it may further comprise the steps:
(a) with the C of 25-40wt%
8-C
16The C of aromatic hydrocarbons diprotic acid, 30-45wt%
3-C
6The C of dibasic alcohol, 2-5wt%
3-C
8The C of polyvalent alcohol, 15-30wt%
4-C
10The C of aliphatic dibasic acid, 3-5wt%
4-C
36The Lewis acid of unsaturated dibasic acid and 0.05-0.25wt% drops in the reactor, and temperature is risen to 230 ℃-240 ℃ with melting materials capable and carry out esterification, and heat-up rate is for per hour rising 10 ℃-20 ℃, and the control aquifer yield is 15-20%;
(b) in last two hours of reaction, measure acid number, when acid number is lower than 15mg KOH/g, cool the temperature to 180 ℃-190 ℃ and add the trimellitic acid 1,2-anhydride of 2.5-3.5wt%, and under this temperature, react, be lower than 20mg KOH/g, obtain resin I up to acid number;
(c) cool the temperature to 70 ℃-100 ℃, and add the pure ether compound of the 15-25wt% that accounts for resin I;
(d) in the mixture of step (c), add acrylate the mixings monomer of the 4-20wt% account for resin I, and 70 ℃-100 ℃ continue to react 2-3 hour after dischargings, and with pH regulator to 7-8.
3. according to the method for claim 2, it is characterized in that the C described in the step (a)
8-C
16The aromatic hydrocarbons diprotic acid is selected from Tetra hydro Phthalic anhydride, m-phthalic acid, a phenylene-diacetic acid, a benzene dipropionic acid, to benzene two butyric acid with to benzene two valeric acids.
4. according to the method for claim 2, it is characterized in that the C described in the step (a)
3-C
6Dibasic alcohol is selected from propylene glycol, butyleneglycol, neopentyl glycol, hexylene glycol and pentanediol.
5. according to the method for claim 2, it is characterized in that the C described in the step (a)
3-C
8Polyvalent alcohol is selected from glycerol, tetramethylolmethane, TriMethylolPropane(TMP).
6. according to the method for claim 2, it is characterized in that the C described in the step (a)
4-C
36Unsaturated dibasic acid is maleic acid anhydride or dimerization behenic acid.
7. according to the method for claim 2, it is characterized in that the C described in the step (a)
4-C
10Aliphatic dibasic acid is selected from Succinic Acid, pentanedioic acid, hexanodioic acid and sebacic acid.
8. according to the method for claim 2, it is characterized in that the pure ether compound described in the step (c) is selected from propylene glycol monomethyl ether, propylene-glycol ethyl ether and dipropylene glycol methyl ether.
9. according to the method for claim 2, it is characterized in that the acrylate mixing monomer described in the step (d) contains the vinylbenzene of 40-50wt%, the methyl methacrylate of 20-50wt%, the glycidyl acrylate of 3-10wt%, the Hydroxyethyl acrylate of 1-4wt% and the peroxidation organism of 0.5-3wt%.
10. water-borne coatings, it comprises the described base-material of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100380955A CN101544728B (en) | 2009-03-23 | 2009-03-23 | Water paint base and water paint containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100380955A CN101544728B (en) | 2009-03-23 | 2009-03-23 | Water paint base and water paint containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101544728A true CN101544728A (en) | 2009-09-30 |
| CN101544728B CN101544728B (en) | 2011-05-25 |
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| CN2009100380955A Active CN101544728B (en) | 2009-03-23 | 2009-03-23 | Water paint base and water paint containing same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974132A (en) * | 2010-10-22 | 2011-02-16 | 南京长江涂料有限公司 | Modified acrylic resin-based normal temperature quick-drying automobile paint with high fullness and high solid |
| CN103878100A (en) * | 2014-04-01 | 2014-06-25 | 广州励宝新材料科技有限公司 | Electrostatic coating method applicable to water-based paint |
| CN104387938B (en) * | 2014-09-06 | 2017-02-01 | 广东华澜浩宇科技创新有限公司 | Preparation method for automobile chassis protection water-based paint |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4829416B2 (en) * | 2000-03-28 | 2011-12-07 | 関西ペイント株式会社 | Water-based coloring base thermosetting paint and coating film forming method using the same |
| RU2255101C2 (en) * | 2000-05-19 | 2005-06-27 | Акцо Нобель Н.В. | Aqueous cross-linking binding composition and composition for covering, lacquer sealing agent composition comprising such binding composition |
| KR101033626B1 (en) * | 2003-05-28 | 2011-05-11 | 디아이씨 가부시끼가이샤 | Water-base coating material |
-
2009
- 2009-03-23 CN CN2009100380955A patent/CN101544728B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974132A (en) * | 2010-10-22 | 2011-02-16 | 南京长江涂料有限公司 | Modified acrylic resin-based normal temperature quick-drying automobile paint with high fullness and high solid |
| CN101974132B (en) * | 2010-10-22 | 2012-10-03 | 南京长江涂料有限公司 | Modified acrylic resin-based normal temperature quick-drying automobile paint with high fullness and high solid |
| CN103878100A (en) * | 2014-04-01 | 2014-06-25 | 广州励宝新材料科技有限公司 | Electrostatic coating method applicable to water-based paint |
| CN103878100B (en) * | 2014-04-01 | 2016-01-06 | 广州励宝新材料科技有限公司 | A kind of method being applicable to the electrostatic spraying of water paint |
| CN104387938B (en) * | 2014-09-06 | 2017-02-01 | 广东华澜浩宇科技创新有限公司 | Preparation method for automobile chassis protection water-based paint |
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| Publication number | Publication date |
|---|---|
| CN101544728B (en) | 2011-05-25 |
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