The content of the invention
It is an object of the invention to provide a kind of environment-friendly water-based inner wall polyurethane emulsion paint, the film forming matter of use is aqueous poly-
Urethane dispersion is prepared by condensation polymerization.Need not add coalescents can in 5 DEG C of film forming, and coating surface it is smooth,
Spot-resistant performance and contaminated resistance are excellent, and the absolute VOC content of inner wall polyurethane emulsion paint that the present invention is provided is extremely low, with nothing
Smell, health environment-friendly, scrub performance are excellent, soft handle, the advantage for decorating excellent performance.
The present invention also provides a kind of production method of the environment-friendly water-based inner wall polyurethane emulsion paint.
To realize above technical purpose, the present invention is adopted the following technical scheme that:
A kind of environment-friendly water-based inner wall polyurethane emulsion paint, it includes:Based on the total restatement of emulsion paint,
It is preferred that, emulsion paint of the present invention, including:Based on the total restatement of emulsion paint,
Polyurethane in aqueous polyurethane dispersion of the present invention is the product prepared comprising following components:
(a1) 10wt%-35wt%, preferably 15wt%-35wt% polyisocynate monomer,
(a2) 50wt%-85wt%, preferably 60wt%-80wt% polyalcohol,
(a3) 0.1wt%-8wt%, preferably 0.1wt%-6wt% chain extender,
(a4) 0.1wt%-5wt%, preferably 0.1wt%-3wt% non-ionic hydrophilic monomer,
(a5) 0.1wt%-5wt%, preferably 0.5wt%-3wt% ionic hydrophilic monomer;Each component content is based on
The weight of the polyurethane of (a) aqueous polyurethane dispersion is calculated.
The nonvolatile matter composition of aqueous polyurethane dispersion of the present invention is that the content of polyurethane is 30wt%-
70wt%, remaining composition is water.
Polyisocynate monomer of the present invention is in aromatic series, araliphatic, aliphatic and alicyclic polyisocyanates
One or two or more;The example of suitable polyisocynate monomer has 1,6- hexamethylene diisocyanates (HDI), different
Isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), double-(4,4 '-isocyanatocyclohexyl) methane
(HMDI), 4,4 '-methyl diphenylene diisocyanate (MDI).
The one kind or two of polyalcohol of the present invention in PPG, PEPA and polycarbonate polyol
Plant or a variety of.The polyalcohol has more than 2 degrees of functionality, and molecular weight is 500-5000.
It is preferred that, polyalcohol of the present invention is in polyester diol, polyether Glycols and PCDL
It is one or two or more kinds of.
One or both of the preferred polyethylene glycol of polyether Glycols, polypropylene glycol and PTMG or
It is a variety of.
The polyester diol is made with diol reaction or prepared by lactone, institute by dicarboxylic acids or dicarboxylic acid anhydride
State lactone and be preferably but not limited to caprolactone.
It is preferred that, the polyester diol is based on adipic acid, phthalic acid, M-phthalic acid and terephthalic acid (TPA) and neighbour
One or both of phthalate anhydride or a variety of and ethylene glycol, 1,4- butanediols, 1,3 butylene glycol, 1,6-HD and new penta
One or both of glycol or a variety of preparations.
It is furthermore preferred that polyalcohol of the present invention is the polyester prepared based on adipic acid, 1,6- hexylene glycols and neopentyl glycol
The mixture of dihydric alcohol (PNHA) and PTMG, wherein described be based on adipic acid, 1,6- hexylene glycols and new penta 2
The number-average molecular weight 500-3000 of polyester diol prepared by alcohol, preferably 1000-2000, the number of PTMG is divided equally
Son amount is 500-3000, preferably 1000-2000;The polyester two prepared based on adipic acid, 1,6-HD and neopentyl glycol
The mass ratio of first alcohol and PTMG is 9:1-1:1, preferably 9:1-7:3.
It is further preferred that new in the polyester diol prepared based on adipic acid, 1,6- hexylene glycols and neopentyl glycol
Pentanediol consumption is 1,6- hexylene glycols and the 5wt%~100wt%, preferably 10wt%~80wt% of neopentyl glycol gross mass.
PEPA of the present invention can effectively improve paint film strength, and provide good feel, be based on simultaneously
Asymmetrical neopentyl glycol is introduced in the polyester diol of adipic acid, 1,6- hexylene glycols and neopentyl glycol, structure, effectively reduction is poly-
The interaction of soft segment structure itself, lifts itself and pigment, the combination of filler in the symmetry of ester structure, reduction polyurethane.Together
When, PTMG cohesive force is small, and hydrolysis resistance is strong, effectively the durability of lifting paint film.PTMG two
Alcohol and the special ratios of polyester diol are used in mixed way, and can further reduce the interaction between polyalcohol, enhancing polyurethane with
The combination of pigment, filler, effectively the lifting durability of emulsion paint, cracking resistance effect and and scrub performance, ensureing emulsion paint
While environmental-protecting performance, the overall applicability performance of emulsion paint is lifted.
The one kind or two of chain extender of the present invention in low molecular polylol, low molecule polyamine and low molecule hydramine
Plant or a variety of;The example of suitable chain extender has 1,3- propane diols, 1,4- butanediols (BDO), neopentyl glycol, a contracting diethyl two
Alcohol, 1,6-HD, 1,4 cyclohexane dimethanol, ethylenediamine, hexamethylene diamine, five methylene diamine, diethylenetriamines,
IPD, 4,4 '-diphenylmethanediamiand, MEA, diethanol amine.
It is preferred that, chain extender of the present invention is selected from least one low molecular polylol and at least one low molecule polyamine.
Non-ionic hydrophilic monomer of the present invention, there is the degree of functionality of isocyanate-reactive group to be 1 or 2, institute for it
State and be selected from hydroxyl, amino etc. with isocyanate-reactive group.
It is preferred that, non-ionic hydrophilic monomer of the present invention is selected from simple function polyalkylene oxide and/or contains polyalkylene oxide
The bifunctionality molecule of side chain.
The preferred main chain carbon number of bifunctionality molecule containing polyalkylene oxide sidechain of the present invention is 2-20, and side chain contains
PEO ether or the molecule containing oxirane segment, the number of the bifunctionality molecule of the polyalkylene oxide sidechain are divided equally
Son amount is 200-2000, and preferred number average molecular weight is 500-1500.
Simple function polyalkylene oxide preferred number average molecular weight of the present invention is 200-3000 terminal hydroxy group PEO list
Methyl ether and/or Amino End Group PEO monomethyl ether.
Ionic hydrophilic monomer of the present invention is one in dihydric alcohol, diamine and hydramine containing hydrophilic stability group
Plant or two or more, the hydrophilic stability group is selected from carboxyl, sulfonic group, phosphate groups, tertiary amine group or quaternary ammonium group
Group.
It is preferred that, ionic hydrophilic monomer of the present invention be selected from dihydromethyl propionic acid (DMPA), 1,3- dihydroxy butane-
1- carboxylic acids, 1,2- dihydroxy butane -1- sulfonic acid, 1,3- dihydroxy butyl-trimethylammonium chloride andOne or both of or it is a variety of, wherein m, n is separate for 1-
20 natural number;More preferablyWherein m, n are separate for 1-6's
Natural number;The sodium salt and/or N- (2- amino-ethyls) -2- aminopropans of further preferred N- (2 amino-ethyl)-Tau
The sodium salt of sulfonic acid.
The preparation technology of the aqueous polyurethane dispersion comprises the following steps:Proportionally, by polyalcohol, polyisocyanic acid
Ester monomer, low molecular polylol chain extender and non-ionic hydrophilic monomer are reacted at 60~100 DEG C in acetone, during supervise
The isocyanate radical content of reaction system is controlled, to judge reaction end;Reduction reaction temperature adds acetone to 30~50 DEG C afterwards
Reacted with low molecule polyamine chain extender and ionic hydrophilic monomer to terminating.After the completion of reaction, in rapid mixing conditions
Lower that water is gradually added into system, phase reversal forms dispersion, disperseed, and removes acetone, forms particle diameter in 50~1000nm
Aqueous polyurethane dispersion.
Need to use acetone as solvent in aqueous polyurethane dispersion building-up process, obtained in the last removing acetone of production
Obtain aqueous polyurethane dispersion.For traditional product, acetone residue amount therein is in thousands of ppm or higher content.For
VOC content effectively in control emulsion paint, it is desirable to content of acetone≤200ppm in aqueous polyurethane dispersion.
Pigment of the present invention is titanium dioxide.
One kind in talcum powder, coarse whiting, fine particle calcium carbonate, mica powder, diatomite and kaolin of filler of the present invention or
Two or more.
Emulsion paint of the present invention can also contain 0-10wt%, preferably 1-8wt% opacity polymer;Described cover is gathered
Compound preferably is selected from particle diameter 200-600nm polystyrene hollow microballoons, the Unihub E hollow polymer microspheres of more preferably DOW chemistry.
Auxiliary agent of the present invention, including following component:Based on the total restatement of emulsion paint, dispersant 0.1wt%-3wt%, profit
Humectant 0.1wt%-0.5%, thickener 0.1wt%-2.0wt%, preservative 0-0.5wt%, defoamer 0.1wt%-
1.5wt%, pH adjusting agent 0-0.5wt%.
Dispersant of the present invention be selected from one or both of polyacrylamide, equal polycarboxylate, co-poly carboxylic acid salt or
A variety of, preferably acrylic acid and other monomer copolymers, sodium salt, the sylvite of maleic anhydride and other monomer copolymers can assign painting
The more preferable patience of layer and environmental protection characteristic.Example including but not limited to:The Orotan of Nuo Puke SN5040, SN5027, DOW chemistry
1124th, Orotan fast easily, Orotan 731A, Vesmody C20, BYK the company DISPERBYK-182 of ten thousand China's chemistry etc..
Wetting agent of the present invention can be that polyphosphate or nonionic surfactant are one or two kinds of or many
Kind.The preferred hydrophobic side carbon number of nonionic surfactant in 8-20, water-wet side be PEO or oxirane with
The copolymer of expoxy propane.Example including but not limited to:Calgon, Triton CF10, the Triton CF- of DOW chemistry
405、Triton BD-109;Ke Laien LCN407, Nuo Pu sections SN-WET990, SN-WET991, wetting agent PE100 etc..
Thickener of the present invention is in cellulose ethers thickener, alkali swelling type thickener and polyurethane-type thickener
One or two or more.The alkali soluble type thickener that rises can select simple alkali soluble to rise type thickener or hydrophobically modified
Alkali soluble rises type thickener, and the cellulose ethers thickener can select the product of different molecular weight size or hydrophobically modified.
Example including but not limited to:Cellulose ethers thickener is as pressed the HEC classes across hydroxyethyl cellulose 250HBR, the DOW chemistry of dragon
Cellulose ethers thickener;The non-swelling thickener of alkali is such as DOW chemistry
Ten thousand China's chemistryDeng;Polyurethane-type thickener is such as ten thousand China's chemistryDOW chemistry Deng.
Heretofore described preservative is not specifically limited, as long as the goal of the invention to the present invention does not produce limitation,
Example is including but not limited to 1,2- benzisothiazole-3-ketones, methylisothiazolinone, 5- chloro-2-methyl -4- isothiazolines -3-
Ketone, KATHON LXE of ROHM AND HAAS etc..
Defoamer of the present invention is selected from mineral oil defoaming agent, organic silicon defoamer and organic silicon modified by polyether froth breaking
One or both of agent etc. is a variety of, preferably is selected from polysiloxane-polyether copolymer type of latex type, polypropylene glycol-hydrophobic solid-poly-
Mixture of siloxanes class, polyethylene glycol-hydrophobic solid-one or both of polysiloxane mixture class and mineral oil base class or
It is a variety of.Example including but not limited to:Nuo Puke NXZ, the high Tego1488 of enlightening, 825, BYK BYK-028, the DC-65 of DOW CORNING
Deng.
PH adjusting agent of the present invention is preferably sodium hydroxide and/or potassium hydroxide.
The present invention also provides a kind of preparation method of environment-friendly water-based inner wall polyurethane emulsion paint, comprises the steps of:
(1) preparation of slurry
Water, dispersant, wetting agent, thickener, preservative, defoamer, pH adjusting agent, pigment, filler, screening are weighed in proportion
Lid polymer, stirs, and slurry is made standby;
(2) preparation of emulsion paint
Slurry, aqueous polyurethane dispersion, thickener, defoamer made from step (1) are weighed in proportion, after stirring
Discharging obtains environment-friendly water-based inner wall polyurethane emulsion paint.
Emulsion paint of the present invention is not required to addition coalescents can be in 5 DEG C and temperatures above good filming, and paint film is dry and comfortable
Do not glue, soft handle, and scrub performance is excellent, spot-resistant performance and contaminated resistance are excellent, and low-temperature stability is good, definitely
Organic volatile gas (including boiling point is less than, the small molecule organic volatile equal to 250 DEG C and higher than 250 DEG C) content is less than
500ppm, preferably shorter than 300ppm, odorlessness belong to Green Product decoration excellent performance, easy construction.