CN107828331B - A kind of high solid ordor removing type alcohol acid and polyurethane black finishing coat - Google Patents
A kind of high solid ordor removing type alcohol acid and polyurethane black finishing coat Download PDFInfo
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- CN107828331B CN107828331B CN201710915388.1A CN201710915388A CN107828331B CN 107828331 B CN107828331 B CN 107828331B CN 201710915388 A CN201710915388 A CN 201710915388A CN 107828331 B CN107828331 B CN 107828331B
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/005—Carbon black
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
Abstract
The present invention relates to a kind of high solid ordor removing type alcohol acid and polyurethane black finishing coats, are grouped as by two groups of A, B, A:B=1:0.5~1.2；Component A is made of high solid ordor removing alkyd resin, hydroxy-containing resin, carbon black color slurry, auxiliary agent and solvent；B component is polyurethane curing agent；The present invention also provides a kind of preparation methods of high solid ordor removing alkyd resin；High solid ordor removing type alcohol acid and polyurethane black finishing coat of the invention, solid divide >=80%, VOC≤200g/L, film odorlessness after coating 48h, and limits of harmful substances complies with standard the requirement of GB 18581-2009, HJ 414-2007；With high-solid lower-viscosity, quick-drying, when storage, is not precipitated；Film mirror effect, 140 μm of one-pass film-forming thickness G T.GT.GT, not sagging；With excellent adhesive force, water resistance, chemical-resistant, resistance to marring and mechanical performance；It is widely used in the coatings such as woodenware, metal, glass, concrete.
Description
Technical field
The present invention relates to a kind of polyurethane coating more particularly to a kind of high solid ordor removing type polyurethane black finishing coat,
Belong to technical field of environmental protection paint.
Background technique
Polyurethane coating is a kind of coating more common at present, and bicomponent polyurethane coating is by isocyanate prepolymer and contains
Hydroxy resin two parts composition, commonly referred to as host agent component and curing agent component；It is divided into propylene according to the difference of hydroxy-containing component
The kinds such as sour polyurethane, alcohol acid and polyurethane, polyester-polyurethane, polyether-polyurethane, epoxy polyurethane.Bicomponent polyurethane coating tool
Have that film-forming temperature is low, adhesive force is strong, wearability is good, hardness is big and chemicals-resistant, good weatherability and good mechanical performance etc.,
Woodwork coating, automobile repairing paint, anticorrosive paint, floor paint, electronic paint, sapecial coating, polyurethane water-proof is widely used in apply
Material etc..
Ten thousand tons of VOC1800 of China year discharge at present, wherein wide important topic in paint industry accounts for 1/4, is that out-and-out VOC emission is big
Family.The U.S. in 1966 discloses the regulation of the first in the world control solvent contamination, it is specified that solvent content mustn't be more than in coating
17%；European Union in 2002 promulgated that paint solvent limiting emission enables, it is desirable that reduction solvent discharge amount 50% in 2010；Limitation
Poisonous and harmful solvent is replaced in the solvent usage of wide important topic in paint industry, or with low poison solvent.
On January 26th, 2015, China have put into effect " about the notice for imposing the consumption tax to battery, coating industry ", to construction
Coating of the VOC greater than 420g/L imposes 4% consumption tax under state；European Union, which limits to industrial coating VOC, to be divided to for two phases, i.e., and 2007
VOC limit value will reach 420~450g/L, then drop within 2010 300g/L, then drop to 250g/L within 2015, this is obviously and American-European
National gap is bigger.Domestic over the past two years keep under strict control the tight regulation of system and environmental protection to the VOC emission of coating, raw material are held in addition
It is continuous to go up, promote coatings enterprises hydrotropism coating, powder coating, UV coating and the development of high solid coating technique direction strongly.
High solid coating refers to containing 70% or more parts by weight or 80% with non-volatile point of upper volume a kind of coating, it
A large amount of organic solvent is saved in the discharge that VOC can be significantly reduced, and the film thickness of a coating is the 1~4 of traditional coating
Times, it is possible to reduce construction times are resource-savings, save the energy, low pollution, a kind of development coating with market future.
High solid coating uses the fluoropolymer resin that relative molecular mass is lesser, molecular weight distribution is very narrow, therefore high
Gu the core technology of part coating is the relative molecular mass for trying to reduce conventional resins, viscosity is reduced, the dissolubility of resin is improved,
Cross-linking reaction is generated by effective active group in film forming procedure, guarantees that perfect coating quality reaches traditional solvent type coating
It is horizontal or higher.
In suite room furniture field of coating, perplexing a problem of industry, to be that furniture is sent to anti-when installing in terminal client man
It is big to reflect smell, is pungent unpleasant, many customer requirements return goods or exchange goods.Raising with people to environmental requirement, solvent based coating
It is higher and higher to the sensibility of smell other than having stringent limitation to VOC；Therefore, various regions government has all put into effect solvent in succession
The standard of type ordor removing coating, as " interior decoration decoration ordor removing solvent wood coatings harmful substance limits Guangdong Province's provincial standard
Amount ", Shenzhen's standard " school's floor coatings limits of harmful substances " etc. makes strict rules the smell of coating.It is required that coating 48
Film does not remain excitatory smell after hour, reaches ordor removing requirement.
Chinese patent CN104710928A discloses a kind of environmentally friendly ordor removing type scratch-resistant polyurethane matt black finish for woodware, by
First component and second part polyurethane curing agent composition, the weight proportion of the first and second components are 1:0.5；First component is by ordor removing type scratch resistance
Alkyd resin, flatting silica, dispersing agent, carbon black color slurry, modified levelling agent, defoaming agent, anti-settling agent and solvent composition；Ordor removing alcohol used
It is 70% that acid resin contains admittedly；Dumb light black finish benzene-free ketone-free made from the invention is free of heavy metal, and film reaches after coating 48h
Ordor removing requirement；But the solid under it is constructed divides < 55%, VOC > 450g/L.
Chinese patent CN104710929A discloses a kind of environmentally friendly ordor removing type scratch-resistant polyurethane woodenware light black finish, by
First component and second part polyurethane curing agent composition, the weight proportion of the first and second components are 1:0.5；First component is by ordor removing type scratch resistance
Alkyd resin, acrylic resin, aldehyde ketone resin, carbon black color slurry, auxiliary agent and solvent composition；Ordor removing alkyd resin used contains admittedly is
70%.Light black finish benzene-free ketone-free made from the invention is free of heavy metal, and film reaches ordor removing requirement after coating 48h；But its
Solid under construction divides < 57%, VOC > 430g/L.
Ordor removing alkyd resin molecular chain length used, molecular weight are high in above-mentioned patent, viscosity is big, hydroxyl value is lower, and solid point
< 70%, it is difficult to prepare the coating of high solid.
Summary of the invention
The high solid ordor removing type alcohol acid and polyurethane black finishing coat, the present invention use 93 ± 2% high solids, molecule
It measures relatively small and distribution is very narrow, viscosity is low, hydroxyl value is high, the ordor removing type alkyd resin of benzene-free ketone-free.
The ordor removing type alkyd resin of the high solid is exactly to try to reduce the viscous of resin in resin synthesis process
The activity (hydroxy radical content) of degree, the molecular weight of control resin and raising resin, but be difficult to if the molecular weight of resin is too small
Film forming, therefore the control of alkyd resin molecular weight is between 2000~3000；Reduce resin viscosity must control strand growth,
Increase the active group of resin and improves dissolubility.
The ordor removing alkyd resin of high solid 93 ± 2% is obtained, the present invention is adjusted using benzoic acid as modifying agent
Degree of functionality controls the growth of polyester chain, and the molecular weight of needs is obtained with this；Being re-introduced into tertiary carbonic acid glycidyl ester both can be improved hydroxyl
Base content increases activity, and can reduce resin viscosity and acid value, while also can increase adhesive force, improves chemical-resistant, and
The dissolubility of resin is greatly improved.
In addition it cannot make reflux solvent with dimethylbenzene, the present invention uses environmental protection without aromatic hydrocarbon reflux solvent, by diformazan basic ring
The hydrogenation dearomatization solvent D40 (156~200 DEG C of boiling range) of alkane (118~122 DEG C of boiling range) and colorless and odorless is prepared by a certain percentage
It forms, boiling range is close with dimethylbenzene, forms azeotropic mixture with water energy, has reflux at 125~160 DEG C, meet alkyd resin
Manufacturing technique requirent.
To improve the ordor removing after alkyd resin film forming, controlled first by the ratio of benzoic acid, polyalcohol and dihydric alcohol
The molecule branched structure and degree of functionality of resin processed, second step introduce tertiary carbonic acid glycidyl and are more distributed in branch by hydroxyl
Upper: on the one hand, resin viscosity can be effectively reduced by increasing active group, obtain the molecular weight of needs；On the other hand, on branch
Hydroxyl steric hindrance is small, and reactivity is high, makes effective crosslinking points, forms reticular structure, improves film performance；Simultaneously
The plexiglas temperature of synthesis is higher, to accelerate the convection current of film internal solvent, is conducive to solvent release, thus in film
Ordor removing requirement can be reached after coating 48h.
The high solid ordor removing alkyd resin, by weight percentage meter, ingredient are as follows: vegetable fatty acids 20.0%~
30.0%, organic acid anhydride 25.0%~45.0%, benzoic acid 2.0%~8.0%, polyalcohol 20.0%~30.0%, esterification are urged
Agent 0.2%~0.6%, C10Tertiary carbonic acid glycidyl ester 6.0%~15.0%, reflux solvent 2.0%~8.0%, solvent
2.0%~8.0%.
Wherein, the vegetable fatty acids are one of refined soybean oil, castor oil, tall oil, coconut oil or several
The combination of kind.
The organic acid anhydride is phthalic anhydride, M-phthalic acid (acid anhydride), terephthalic acid (TPA) (acid anhydride), cis-butenedioic anhydride, maleic anhydride, two
The combination of one or more of acid and derivative or decanedioic acid and derivative.
The polyalcohol is glycerol, trimethylolpropane, trimethylolethane, neopentyl glycol, 1,3- propylene glycol, second
The combination of one or more of glycol, 1,4- butanediol, 1,6-HD, diethylene glycol, dipropylene glycol.
The esterification catalyst is at least one of organotin catalysts or rare earth catalyst.
The described reflux solvent composition are as follows: the de- fragrant solvent of dimethyl thiacyclohexane 65.0%~80.0%, D40 20.0%~
35.0%.
The present invention provides a kind of preparation method of high solid ordor removing alkyd resin, and has applied for patent；The Gao Gu
Body divides ordor removing alkyd resin, and preparation process is as follows:
A), by weight percentage, successively vegetable fatty acids, organic acid anhydride, part polyalcohol are added in reaction kettle,
It begins to warm up, after the complete melting of material in kettle, is passed through N2, start to stir and be warming up to 120 DEG C, esterification catalyst be added, so
After be warming up to 165 DEG C~180 DEG C, benzoic acid and reflux solvent, 2~3h of insulation reaction is added, and remove back flow reaction and bring out
Moisture content, and the reflux solvent to cool down is transported at the top of packed tower with circulating pump；
B), when the water separated is seldom, remaining polyalcohol and C is added10Tertiary carbonic acid glycidyl ester is warming up to 190 DEG C
Insulation reaction 1h, then 200 DEG C of insulation reaction 1h are warming up to, then it is warming up to 210 DEG C of 1~3h of insulation reaction；
C), sample, after the assay was approved, stopping is passed through N2, be cooled to 150 DEG C hereinafter, be added diluted solvent, stir 20min,
It filters and packages, obtains the ordor removing alkyd resin of 93 ± 2% high solid.
The high solid ordor removing alkyd resin number-average molecular weight Mn is 2200~3000, and benzene-free ketone-free, solid are divided into
93 ± 2%, viscosity (format pipe/25 DEG C) < 10s, acid value≤8mgKOH/g, hydroxyl value >=135mgKOH/g.
The present invention is intended to provide a kind of high solid ordor removing type alcohol acid and polyurethane black finishing coat.
High solid ordor removing type alcohol acid and polyurethane black finishing coat of the present invention, is grouped as, A, B component by two groups of A, B
Weight proportion be 1:0.5~1.2；Wherein, by weight percentage, component A composition are as follows: high solid ordor removing alcohol
Acid resin 60.0%~85.0%, hydroxy-containing resin 0%~25.0%, carbon black color slurry 5.0%~20.0%, delustering agent 0%~
6.0%, dispersing agent 0%~3.0%, defoaming agent 0.1%~0.5%, levelling agent 0.1%~0.5%, thickening anti-settling agent 0.2%
~1.0% and solvent 3.0%~10.0%；The B component is TDI tripolymer, HDI trimer, IPDI tripolymer, MDI tri-
Aggressiveness, TDI-HDI mixed trimer, TDI/TMP addition product or HDI biuret polyurethane curing agent to less than one kind, it is described
Polyurethane curing agent be free isocyanate monomer content≤0.5%, solid point >=70% environment-friendly curing agent.
The hydroxy-containing resin is Hydroxylated acrylic resin, urea formaldehyde, polyester resin, epoxy resin or organosilicon tree
Rouge.
Carbon black color slurry fineness≤10 μm；By weight percentage, consisting of: carbon black 8.0%~30.0%,
High solid ordor removing alkyd resin 15.0%~25.0%, mill base dispersing agent 6.0%~20.0%, defoaming agent 0.2%~
0.5%, thicken anti-settling agent 0.5%~3.0%, remaining be solvent.
Wherein, the carbon black be REGAL400R, Monarch1300, Monarch900, Special black 4,
Special black 6、Special black 550、FW18、FW285、FW200、 MA-7、MA-100、MA#40、
Raven3500, Raven1255 or Raven3600's is any.
The carbon black color slurry, preparation step are as follows: pressing formulation weight ratio, solvent and high solid are added in dispersion bucket
Point ordor removing alkyd resin is simultaneously uniformly dissolved, and mill base dispersing agent, defoaming agent is added, stirs evenly, is slowly added to carbon black toner, then
In 30~45min of high shear of 1000~1200r/min, move on to sand mill circular grinding 3~4 times, it is thin until mill base
Degree partial size reaches≤10 μm, the deaeration in paint mixing bucket, and thickening anti-settling agent tune is added and glues, filters and packages, obtains the carbon black color slurry.
Isoamyl acetate can improve the dissolubility of alkyd resin, the solvent, and composition includes at least 15.0%~
30.0% isoamyl acetate, other ingredients are butyl acetate, sec-Butyl Acetate, propylene glycol monomethyl ether, propandiol butyl ether, carbonic acid two
At least one of methyl esters.
The resin, auxiliary agent, curing agent all aromatic-free class, glycol ether and its esters, ketone, alkyl chloride hydro carbons are molten
Agent.
High solid alcohol acid and polyurethane black finishing coat produced by the present invention, weight solid >=80%, VOC under construction
Film odorlessness after≤200g/L, coating 48h, and limits of harmful substances meets national compulsory standard GB/T 18581-
2009, the requirement of professional standard HJ414-2007 and provincial standard " ordor removing solvent wood coatings ".
High solid ordor removing type alcohol acid and polyurethane black finishing coat produced by the present invention, high-solid lower-viscosity, when storage, are not precipitated；?
Solvent volatilizees in film forming procedure, and fast, rate of drying is fast, and film levelability, good, 140 μm of the one-pass film-forming thickness G T.GT.GT of the transparency, no
Generate sagging；And film has excellent adhesive force, water resistance, chemical-resistant, wearability, resistance to marring and mechanicalness
Energy；It is widely used in the surface protections such as furniture, musical instrument, metal, concrete and decoration.
Specific embodiment
The present invention with the following Examples does the preparation of the high solid ordor removing type alcohol acid and polyurethane black finishing coat
It further describes.
Embodiment 1
A kind of high solid ordor removing alkyd resin A, preparation process are as follows:
A), by weight percentage, successively by 23.5 parts of castor oil, 7.2 parts of M-phthalic acid, 26.5 parts of phthalic anhydride, hexanedioic acid
3.0 parts, 10.0 parts of glycerol, 5.0 parts of trimethylolpropane, 4.5 parts of 1,4-butanediol be added in reaction kettle, begin to warm up, when
In kettle after the complete melting of material, it is passed through N2, start to stir and be warming up to 120 DEG C, be added 0.5 part of organotin catalysts, then rise
Temperature is added 6.0 parts and 3.5 parts of reflux solvent, 2~3h of insulation reaction of benzoic acid to 165 DEG C~180 DEG C, and removes back flow reaction
6.2 parts of the water brought out, and the reflux solvent to cool down is transported at the top of packed tower with circulating pump and returns to reaction kettle；
B), when the water separated is seldom, C is added10It 10.0 parts and 3.5 parts of Isosorbide-5-Nitrae-butanediol of tertiary carbonic acid glycidyl ester, rises
Temperature is to 190 DEG C of insulation reaction 1h, then is warming up to 200 DEG C of insulation reaction 1h, is then warming up to 210 DEG C of 2~3h of insulation reaction；
C), sample, after the assay was approved, stopping is passed through N2, 150 DEG C are cooled to hereinafter, 3.0 parts of diluted solvent of addition, stirring
20min is filtered and packaged, and obtains the high solid ordor removing alkyd resin A.
Embodiment 2
A kind of high solid ordor removing alkyd resin B, preparation process are as follows:
A), by weight percentage, successively by 25.0 parts of soybean oil, 18.0 parts of phthalic anhydride, 12.0 parts of hexanedioic acid, maleic anhydride
4.5 parts, 12.0 parts of glycerol, 5.2 parts of trimethylolpropane, 4.0 parts of neopentyl glycol be added in reaction kettle, begin to warm up, work as kettle
After the interior complete melting of material, it is passed through N2, start to stir and be warming up to 120 DEG C, be added 0.4 part of rare earth catalyst, then heat to
165 DEG C~180 DEG C, 6.0 parts and 3.2 parts of reflux solvent, 2~3h of insulation reaction of benzoic acid are added, and remove back flow reaction and take out of
5.8 parts of water come, and the reflux solvent to cool down is transported at the top of packed tower with circulating pump and returns to reaction kettle；
B), when the water separated is seldom, C is added10It 8.0 parts and 3.5 parts of diethylene glycol of tertiary carbonic acid glycidyl ester, is warming up to
190 DEG C of insulation reaction 1h, then 200 DEG C of insulation reaction 1h are warming up to, then it is warming up to 210 DEG C of 1~2h of insulation reaction；
C), sample, after the assay was approved, stopping is passed through N2, 150 DEG C are cooled to hereinafter, 4.0 parts of diluted solvent of addition, stirring
20min is filtered and packaged, and obtains the high solid ordor removing alkyd resin B.
To the high solid ordor removing alkyd resin in the embodiment of the present invention, detected according to relevant criterion, technology refers to
Mark is as shown in table 1.
Table 1: high solid ordor removing alkyd resin technical indicator
| Detection project | Resin A | Resin B |
| Color (Fe-Co colorimetric), number | ≤3 | ≤3 |
| Solid content, % | 93.0 | 92.2 |
| Viscosity (format pipe/25 DEG C), s | 10.0 | 8.0 |
| Acid value, mgKOH/g | 7.5 | 7.8 |
| Hydroxyl value, mgKOH/g | 142 | 138 |
| Molecular weight Mn | 2650 | 2760 |
Embodiment 3
A kind of carbon black color slurry, preparation process are as follows:
By formulation weight ratio, A21.5 parts of 47.7 parts of solvent and high solid ordor removing alkyd resin is added simultaneously in dispersion bucket
It is uniformly dissolved, 12.0 parts of EFKA-4320 mill base dispersing agent, 0.3 part of defoaming agent is added, stirs evenly, is slowly added to Special
18.0 parts of 6.0 carbon black of biack moves on to sand mill circulation then in 30~45min of high shear of 1000~1200r/min
Grinding 3~4 times, until the fineness partial size of mill base reaches≤10 μm, 0.5 part of anti-settling agent tune of thickening is added in the deaeration in paint mixing bucket
It is viscous, it filters and packages, obtains the color to contain the carbon black color slurry for being 50% for 18%, non-volatile content.
Embodiment 4
A kind of high solid ordor removing type alcohol acid and polyurethane black matte finishing coat:
Component A: A78.5 parts of high solid alkyd resin, 10.0 parts of carbon black color slurry, 4.6 parts of delustering agent, dispersing agent 1.2
Part, 0.3 part of levelling agent, 0.2 part of defoaming agent, 0.5 part of anti-settling agent and 4.7 parts of solvent；B component: 75% solid divides HDI trimer；
Paint is matched by A:B=1:1, the requirement that appropriate diluent meets airless spraying is added.
Embodiment 5
A kind of high solid ordor removing type alcohol acid and polyurethane black light top coat top coat:
Component A: 80.0 parts of high solid alkyd resin B, 5.0 parts of 80% Hydroxylated acrylic resin, 9.0 parts of carbon black color slurry,
0.3 part of levelling agent, 0.2 part of defoaming agent, 0.5 part of anti-settling agent and 5.0 parts of solvent；B component: 75% solid divides TDI/TMP addition
Object；Paint is matched by A:B=1:1.05, the requirement that appropriate diluent meets airless spraying is added.
According to relevant national standard, to high solid ordor removing type alcohol acid and polyurethane black finishing coat made from the embodiment of the present invention
Performance detected, test result is as shown in table 2.
Table 2: high solid ordor removing type alcohol acid and polyurethane black finishing coat performance indicator
Although the present invention has described it in detail and cited embodiments, but for those of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (10)
1. a kind of high solid ordor removing type alcohol acid and polyurethane black finishing coat, which is characterized in that the high solid ordor removing type alkyd
Polyurethane black finishing coat is grouped as by two groups of A, B, A, B component weight proportion be 1:0.5~1.2；By weight percentage,
The component A composition are as follows: high solid ordor removing alkyd resin 60.0%~85.0%, hydroxy-containing resin 0%~25.0%, carbon
Black slurry 5.0%~20.0%, delustering agent 0%~6.0%, dispersing agent 0%~3.0%, defoaming agent 0.1%~0.5%, levelling
Agent 0.1%~0.5%, thickening anti-settling agent 0.2%~1.0% and solvent 3.0%~10.0%；The B component is TDI trimerization
Body, HDI trimer, IPDI tripolymer, MDI tripolymer, TDI-HDI mixed trimer, TDI/TMP addition product or HDI biuret
At least one of polyurethane curing agent, the polyurethane curing agent are free isocyanate monomer content≤0.5%, solid point
>=70% environment-friendly curing agent；
Wherein, the high solid ordor removing alkyd resin, number-average molecular weight Mn are 2200~3000, benzene-free ketone-free, solid point
For 93 ± 2%, format pipe viscosity/25 DEG C < 10s, acid value≤8mgKOH/g, hydroxyl value >=135mgKOH/g；
The high solid ordor removing alkyd resin, by weight percentage meter, material composition are as follows: vegetable fatty acids 20.0%~
30.0%, organic acid anhydride 25.0%~45.0%, benzoic acid 2.0%~8.0%, polyalcohol 20.0%~30.0%, esterification are urged
Agent 0.2%~0.6%, C10Tertiary carbonic acid glycidyl ester 6.0%~15.0%, reflux solvent 2.0%~8.0% and solvent
2.0%~8.0%；Its preparation step is as follows:
A), by weight percentage, successively vegetable fatty acids, organic acid anhydride, part polyalcohol are added in reaction kettle, started
Heating is passed through N after the complete melting of material in kettle2, start to stir and be warming up to 120 DEG C, esterification catalyst be added, then rises
Benzoic acid and reflux solvent, 2~3h of insulation reaction is added to 165 DEG C~180 DEG C in temperature, and removes the water that back flow reaction is brought out
Point, and the reflux solvent to cool down is transported at the top of packed tower with circulating pump；
B), when the water separated is seldom, remaining polyalcohol and C is added10Tertiary carbonic acid glycidyl ester is warming up to 190 DEG C of heat preservations
1h is reacted, then is warming up to 200 DEG C of insulation reaction 1h, is then warming up to 210 DEG C of 1~3h of insulation reaction；
C), sample, after the assay was approved, stopping is passed through N2, 150 DEG C are cooled to hereinafter, solvent thinning is added, and stirring 20min is filtered
Packaging, obtains the high solid ordor removing alkyd resin；
The hydroxy-containing resin is Hydroxylated acrylic resin, urea formaldehyde, polyester resin, epoxy resin or silicone resin；It is described
Resin, auxiliary agent, curing agent all aromatic-free, glycol ether and its ester, ketone, chlorinated paraffin solvent.
2. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 1, which is characterized in that the plant
Fatty acid oil be one of Refined Soybean fatty acid oil, Castor Oil Fatty Acid, ready denier oil acid or coco-nut oil fatty acid or
Several combinations.
3. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 1, which is characterized in that described organic
Acid anhydrides is phthalic anhydride, M-phthalic acid (acid anhydride), terephthalic acid (TPA) (acid anhydride), cis-butenedioic anhydride, hexanedioic acid and derivative or decanedioic acid and derivative
One or more of combination.
4. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 1, which is characterized in that the esterification
Catalyst is at least one of organotin catalysts or rare earth catalyst.
5. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 1, which is characterized in that described polynary
Alcohol is glycerol, trimethylolpropane, trimethylolethane, neopentyl glycol, 1,3- propylene glycol, ethylene glycol, 1,4- butanediol, 1,6-
The combination of one or more of hexylene glycol, diethylene glycol or dipropylene glycol.
6. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 1, which is characterized in that the reflux
Solvent group becomes: the de- fragrant solvent 20.0%~35.0% of dimethyl thiacyclohexane 65.0%~80.0%, D40.
7. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 1, which is characterized in that the Gao Gu
Body divides ordor removing type alcohol acid and polyurethane black finishing coat, after weight solid >=80%, VOC≤200g/L under constructing, coating 48h
Film odorlessness.
8. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 1, which is characterized in that the carbon black
Mill base fineness≤10 μm；By weight percentage, consisting of: carbon black 8.0%~30.0%, high solid ordor removing alkyd resin
15.0%~25.0%, mill base dispersing agent 6.0%~20.0%, defoaming agent 0.2%~0.5%, thickening anti-settling agent 0.5%~
3.0%, remaining is solvent；
Its preparation process is as follows: pressing formulation weight ratio, solvent and high solid ordor removing alkyd resin and molten are added in dispersion bucket
Solution uniformly, is added mill base dispersing agent, defoaming agent, stirs evenly, carbon black toner is slowly added to, then in 1000~1200r/min
30~45min of high shear, move on to sand mill circular grinding 3~4 times, until the fineness partial size of mill base reaches≤10 μm,
The deaeration in paint mixing bucket is added thickening anti-settling agent tune and glues, filters and packages, obtain the carbon black color slurry.
9. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 8, which is characterized in that the carbon black
For REGAL400R, Monarch1300, Monarch900, Special black 4, Special black 6, Special
In black 550, FW18, FW285, FW200, MA-7, MA-100, MA#40, Raven3500, Raven1255 or Raven3600
It is any.
10. high solid ordor removing type alcohol acid and polyurethane black finishing coat according to claim 1 or 8, which is characterized in that described
Solvent, composition include 15.0%~30.0% isoamyl acetate, and other ingredients are butyl acetate, sec-Butyl Acetate, propylene glycol
At least one of methyl ether, propandiol butyl ether or dimethyl carbonate.
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| CN112280461A (en) * | 2020-11-22 | 2021-01-29 | 湖南省金海科技有限公司 | High-hardness high-brightness yellowing-resistant super-black mirror finish paint capable of being used for surface of high-grade sound box in polished mode |
| CN112662285A (en) * | 2020-12-18 | 2021-04-16 | 力同化工(佛山)有限公司 | Nano environment-friendly pure black coating |
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| CN105176361A (en) * | 2015-07-23 | 2015-12-23 | 三棵树涂料股份有限公司 | Low-VOC polyurethane high-light varnish |
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| CN107033772A (en) * | 2017-05-27 | 2017-08-11 | 广东美涂士建材股份有限公司 | A kind of anti-soft scratch clear finish of low smell height and preparation method thereof |
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2017
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| CN104710927A (en) * | 2013-12-13 | 2015-06-17 | 合众（佛山）化工有限公司 | Preparation method of benzene-free low-peculiar smell scratch-resistant polyurethane brilliant black finish for woodenware |
| CN105176361A (en) * | 2015-07-23 | 2015-12-23 | 三棵树涂料股份有限公司 | Low-VOC polyurethane high-light varnish |
| CN105255356A (en) * | 2015-10-21 | 2016-01-20 | 三棵树涂料股份有限公司 | Low-VOC (volatile organic component) polyurethane matte varnish and preparation method thereof |
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| CN107033772A (en) * | 2017-05-27 | 2017-08-11 | 广东美涂士建材股份有限公司 | A kind of anti-soft scratch clear finish of low smell height and preparation method thereof |
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