CN109627409A - A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method - Google Patents
A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method Download PDFInfo
- Publication number
- CN109627409A CN109627409A CN201811566688.4A CN201811566688A CN109627409A CN 109627409 A CN109627409 A CN 109627409A CN 201811566688 A CN201811566688 A CN 201811566688A CN 109627409 A CN109627409 A CN 109627409A
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- parts
- added
- dumb light
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to the technical fields of high molecular material, more particularly to a kind of aqueous polyurethane, including the following raw material: polynary amino alcohol, isocyanic acid, thermoplastic polyurethane elastomer, chain extender, neutralizer, deionized water and hydrazine hydrate, polynary amino alcohol is diethylaminoethanol, 3- amino -1,2- propylene glycol or 3- lignocaine -1- propyl alcohol, the dosage of neutralizer is that the pH of control mixed liquor is 7.5-9, has the advantages that wear-resisting, water resistance is good and wellability is good；The aqueous polyurethane that castor oil is added is additionally provided, the wellability of aqueous polyurethane is further improved；Additionally provide the preparation method of dumb light aqueous polyurethane after two kinds of aqueous polyurethanes to be added to flatting silicas and preparation method thereof and two kinds of aqueous polyurethanes, the dumb light aqueous polyurethane made, while improving leather surface gloss, delustering agent can be made not to be stripped out from film, extend the effective acting time of flatting silica.
Description
Technical field
The present invention relates to the technical fields of high molecular material, and in particular to a kind of aqueous polyurethane, dumb light aqueous polyurethane
And preparation method.
Background technique
A large amount of leathers are used in automobile, luggage and shoe-making field, to improve leather surface aesthetics, corrosion resistance and wear-resisting
Performance often uses coating and carries out top finishing.
Synthetic Leather is the most promising natural leather substitute after artificial polyvinyl chloride leather.Synthetic Leather
It compensates for artificial polyvinyl chloride leather and substrate adhesive fastness is poor, be easy to peel off, the disadvantages of feel is stiff has gloss naturally soft
With, adhesive property is good, it is wear-resistant the advantages that.
Existing low gloss leather finishing agent mostly uses greatly waterborne polyurethane resin, and aqueous polyurethane is a kind of plastic particle
Evenly dispersed thinlyfluid in water forms the sequential like being evenly distributed by fusion between polymer particles and applies when in use
Film；When film forming, show especially with the volatilization of solvent, the thinning silica dioxide granule for shrinking, being suspended in resin of film in film item
Layer forms a micro-roughened surface, which can make incident light, thus obtain low gloss effect with
Soft sense of touch.But it is monomer that current aqueous polyurethane, which mostly uses polyether polyol, water resistance is poor with wearability；And its
Wellability is poor, although can obtain low gloss effect by the delustering agent for adding such as silica etc, with pushing away for time
It moves, these duller particles are easy to be stripped out from film, thus bring to the weatherability of film and ultraviolet-resistant performance
Negative effect.
Summary of the invention
In view of the deficienciess of the prior art, the first purpose of this invention is that providing one kind has wear-resisting, water resistance
The good aqueous polyurethane of energy.
The first purpose of this invention is achieved through the following technical solutions:
A kind of aqueous polyurethane, the raw material including following parts by weight: polynary amino alcohol 40-60 parts, 35-55 parts of isocyanic acid, thermoplastic
15-30 parts of polyurethane elastomer of property, 8-15 parts of chain extender, neutralizer, 5-15 parts of deionized water and 1-3 parts of hydrazine hydrate are described more
First amino alcohol is diethylaminoethanol, 3- amino -1,2-PD or 3- lignocaine -1- propyl alcohol, the dosage of the neutralizer
It is 7.5-9 to control the pH of mixed liquor.
By using above-mentioned technical proposal, diethylaminoethanol (English name Diethylaminoethanol) also known as 2-
(diethylin) ethyl alcohol [2- (diethylamino)-Ethano1].It is colourless liquid under room temperature, has ammonia taste, there is hygroscopicity.It is main
To be used as sour gas in medicine intermediate, softening agent, emulsifier, curing agent etc. and organic synthesis raw material and natural gas
Scavenger.3- amino -1,2-PD (3-Amino-1,2-propanediol) is used as emulsifier, organic intermediate.3- bis-
Ethylamino -1- propyl alcohol, nickname N, N- diethylpropanolamine, 3- diethyl amino -1- propyl alcohol, 3- (lignocaine) -1- propyl alcohol are colourless
To yellow liquid.Hydrazine hydrate is also known as hydrazine hydrate, is a kind of important fine chemical material.Thermoplastic polyurethane elastomer is also known as
Thermoplastic polyurethane rubber, with the comprehensive performance that high intensity, high tenacity, wear-resisting, oil resistant etc. are excellent, processing performance is good.Pass through
Polynary amino alcohol and isocyanate reaction obtain polyurethane, compared to using polyether polyol as the polyurethane of monomer, water resistance with
Wear-resisting property is greatly improved.And the introducing of hydrazine hydrate, by the polymer of polynary amino alcohol and isocyanate reaction with
High-intensitive, high tenacity and the crosslinking of the thermoplastic polyurethane elastomer of wear-resisting property mix, and have the two by chemical bond
Machine combines, and further improves the wear-resisting property of aqueous polyurethane.
Preferably, the chain extender is 1-4- butanediol or 2,2- dihydromethyl propionic acid.
By using above-mentioned technical proposal, chain extender is also known as chain extender, and being can be with the functional group on linear polymer chain
The substance for reacting and increasing strand extension, molecular weight.It is usually used in improving the mechanical property and work of the products such as polyurethane, polyester
Skill performance.2,2- dihydromethyl propionic acids are both chain extender in aqueous polyurethane manufacture and make polyurethane obtained from emulsibility
Can, it can be made into the self-emulsifying aqueous polyurethane of excellent in stability.
Second object of the present invention is to provide a kind of preparation method of the aqueous polyurethane of first goal of the invention, packet
Include following operating procedure:
Isocyanic acid is added after polynary amino alcohol is carried out vacuum dehydration processing, at 75-85 DEG C, reacts 1-3h；Chain extender is added,
At 80-90 DEG C, 2-4h is reacted；Add neutralizer at salt, deionized water and hydrazine hydrate is added, is dispersed with the revolving speed of 2000r/min
3-5min is stirred, later at 20-50 DEG C, reacts 30-40min；It is down to 20-25 DEG C, stirs 40-60min, stands 30-
48h obtains aqueous polyurethane.
Third object of the present invention is to provide a kind of wearability and the high aqueous polyurethane of wetting property.
Third object of the present invention is achieved through the following technical solutions:
A kind of aqueous polyurethane, the raw material including each parts by weight in first goal of the invention further include 5-15 parts of castor oil.
By using above-mentioned technical proposal, castor oil is the polyol compound of natural reproducible, longer non-in component
Polarity aliphatic chain has good hydrophobic effect, can further improve the water resistance and flexibility of water-base polyurethane material.And
And it further can make aqueous polyurethane preferably spread in substrate surface, to further increase the infiltration of aqueous polyurethane
Property, to improve the wear-resisting property of film.
Fourth object of the present invention is to provide a kind of preparation method of the aqueous polyurethane of third goal of the invention, wrap
Include following operating procedure:
Isocyanic acid and castor oil is added after polynary amino alcohol is carried out vacuum dehydration processing, at 80-85 DEG C, reacts 1-3h；Add
Enter chain extender, at 80-90 DEG C, reacts 2-4h: neutralizer being added to be neutralized into salt, deionized water and hydrazine hydrate is added, with 2000r/
The revolving speed dispersion stirring 3-5min of min reacts 30-40min later at 20-50 DEG C；It is down to 20-25 DEG C, stirs 40-
60min stands 30-48h, obtains aqueous polyurethane.
Fifth object of the present invention is to provide a kind of dumb light aqueous polyurethanes, for that can make leather in leather paint
The softer beauty of the gloss on surface, and cooperate the aqueous polyurethane in the present invention, remove delustering agent will not from film
Out.
5th purpose of the invention is realized by following technical solution:
A kind of dumb light aqueous polyurethane, the raw material including following parts by weight: first or third goal of the invention aqueous polyurethane
85-95 parts, 20-40 parts of deionized water, 1-3 parts of flatting silica, 5-10 parts of thermoplastic polyurethane elastomer, 0.1-1 parts of levelling agent, profit
0.1-1 parts of hygroscopic water powder, 0.1-1 parts of defoaming agent and 0.5-1.5 parts of thickener.
It is good with the high-wearing feature, high waterproofness and wetting property prepared in the present invention by using above-mentioned technical proposal
Aqueous polyurethane, flatting silica and auxiliary agent in addition, to obtain the leather finishing agent with photoextinction；Due to the present invention
Aqueous polyurethane wetting property it is good, duller particle can be very good infiltration in finally obtained film, to be not easy
It is stripped out from film, to realize the delustring treatment effect to leather products surface long term.
Preferably, the flatting silica is the silica that partial size is 5-10 μm.
By using above-mentioned technical proposal, the fineness of silica is controlled, improves its square dispersing uniformity in film, from
And further avoid it and detached from film, improve the delustring stability of dumb light aqueous polyurethane.
Of the invention the 6th is designed to provide a kind of preparation side of the dumb light aqueous polyurethane of 5th goal of the invention
Method, including following operating procedure: the aqueous polyurethane in first or third goal of the invention, deionized water are sufficiently mixed
It is even, flatting silica is added and stirs 25-35min, thermoplastic polyurethane elastomer is added and stirs 25-35min, levelling agent, wetting is added
Dispersing agent stirs 15-20min, and defoaming agent is added and thickener stirs 5-15min, obtains dumb light aqueous polyurethane.
In conclusion the invention has the following beneficial effects:
(1) polymer for obtaining polynary amino alcohol and isocyanate reaction, cooperation hydrazine hydrate and high-intensitive, high tenacity and wearability
The thermoplastic polyurethane elastomer crosslinking of energy mixes, and the polymer and thermoplastic polyurethane elastomer is made to pass through chemical bond
It organically combines, while improving the wetting property of aqueous polyurethane, further improves the wear-resisting property of aqueous polyurethane；
(2) by the way that the polyol compound castor oil of natural reproducible is added, obtained it is a kind of have better water resistance and
Flexible water-base polyurethane material；The material can make aqueous polyurethane preferably spread in substrate surface, to further mention
The wellability of high aqueous polyurethane；
(3) by the way that two kinds of above-mentioned aqueous polyurethanes are added upper flatting silica and auxiliary agent, obtain having the leather of photoextinction to apply
Agent is adornd, since the wetting property of two kinds of aqueous polyurethanes is good, duller particle can be very good infiltration in finally obtained painting
In film, to be not easy to be stripped out from film, to realize the delustring treatment effect to leather products surface long term.
Specific embodiment
Each raw material and chemical reagent used in the present invention are commercial product.Wherein thermoplastic polyurethane elastomer is selected
Polyester-type spherical particle.Wetting dispersing agent is nonionic surface active agent, and nonionic surface active agent, which can improve, to be helped
Agent dispersion performance, the present invention in wetting dispersing agent select Air Prod & Chem, the U.S. the trade mark be Surfynol 104 table
Face activating agent.Defoaming agent selects silicone emulsion, and thickener selects hydroxypropyl methyl cellulose.
Embodiment 1
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, be heated under vacuum conditions 110 DEG C be carried out dehydrating 1.5h (dehydration for this
The conventional technical means in field), isocyanic acid 35g is then added, at 75 DEG C, reacts 1h, obtains mixed liquor A；
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 80 DEG C, reacts 2h, obtains
To the mixed liquid B of polymerization reaction；
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 7.5, and deionized water 5g, hydrazine hydrate is added
1g, and be dispersed with stirring under the mixing speed of 2000r/min, emulsify 3min, then at 20 DEG C, 30min is reacted, is mixed
Liquid C；
(4) by mixed liquor C at 20 DEG C, the mixing speed of 2400r/min stirs 40min, stands 30h and is hardened, obtains water
Property polyurethane.
Embodiment 2
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, it is heated to 110 DEG C under vacuum conditions and is carried out dehydrating 2h (dehydration is ability
The conventional technical means in domain), isocyanic acid 35g is then added, at 80 DEG C, reacts 2h, obtains mixed liquor A；
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 85 DEG C, reacts 3h, obtains
To mixed liquid B；
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 8.5, and deionized water 5g, hydrazine hydrate is added
1g, and the stirring and emulsifying 5min under the mixing speed of 2000r/min react 40min, obtain mixed liquor C then at 35 DEG C；
(4) by mixed liquor C at 25 DEG C, the mixing speed of 4000r/min stirs 50min, stands 48h, obtains aqueous poly- ammonia
Ester.
Embodiment 3
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, be heated under vacuum conditions 110 DEG C be carried out dehydrating 1.5h (dehydration for this
The conventional technical means in field), isocyanic acid 35g is then added, at 85 DEG C, reacts 3h, obtains mixed liquor A；
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 90 DEG C, reacts 4h, obtains
To mixed liquid B；
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 9, and deionized water 5g, hydrazine hydrate is added
1g, and the stirring and emulsifying 4min under the mixing speed of 2000r/min react 30min, obtain mixed liquor C then at 50 DEG C；
(4) by mixed liquor C at 25 DEG C, the mixing speed of 5000r/min stirs 60min, stands 48h, obtains aqueous poly- ammonia
Ester.
Embodiment 4
Embodiment 4 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: 3-
Amino -1,2-PD 50g, isocyanic acid 40g, thermoplastic polyurethane elastomer 25g, 2,2- dihydromethyl propionic acid 10g, deionization
Water 10g and hydrazine hydrate 2g.
Embodiment 5
Embodiment 5 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: 3-
Lignocaine -1- propyl alcohol 55g, isocyanic acid 45g, thermoplastic polyurethane elastomer 20g, methyl pyrrolidone 12g, deionized water
13g and hydrazine hydrate 2.5g.
Embodiment 6
Embodiment 6 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: two
Ethylaminoethanol 45g, isocyanic acid 50g, thermoplastic polyurethane elastomer 25g, methyl pyrrolidone 15g, deionized water 15g and water
Close hydrazine 3g.
Embodiment 7
Embodiment 7 is identical as the operating procedure of embodiment 1, and difference is only that, in step (1), while isocyanic acid is added, adds
Enter 5g castor oil, at 80 DEG C, reacts 1h, obtain mixed liquor A；Remaining is same as Example 1.
Embodiment 8
Embodiment 8 is identical as the operating procedure of embodiment 2, and difference is only that, in step (1), while isocyanic acid is added, adds
Enter 5g castor oil, remaining is same as Example 2.
Embodiment 9
Embodiment 9 is identical as the operating procedure of embodiment 3, and difference is only that, in step (1), while isocyanic acid is added, adds
Enter 5g castor oil, remaining is same as Example 3.
Embodiment 10
Embodiment 10 is identical as the operating procedure of embodiment 4, and difference is only that, in step (1), while isocyanic acid is added,
8g castor oil is added, remaining is same as Example 4.
Embodiment 11
Embodiment 11 is identical as the operating procedure of embodiment 5, and difference is only that, in step (1), while isocyanic acid is added,
12g castor oil is added, remaining is same as Example 5.
Embodiment 12
Embodiment 12 is identical as the operating procedure of embodiment 6, and difference is only that, in step (1), while isocyanic acid is added,
15g castor oil is added, remaining is same as Example 6.
Embodiment 13
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared
85g, deionized water 20g are sufficiently mixed uniformly, and the 1g silica that partial size is 5-10 μm, the revolving speed stirring of 1000r/min is added
Thermoplastic polyurethane elastomer 5g is added in 25min, stirs 25min, and carboxymethyl cellulose 0.1g, wetting dispersing agent 0.1g is added,
15min is stirred, defoaming agent 0.1g and thickener 0.5g is added, 5min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 14
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared
90g, deionized water 30g are sufficiently mixed uniformly, and the 2g silica that partial size is 5-10 μm, the revolving speed stirring of 1300r/min is added
Thermoplastic polyurethane elastomer 8g is added in 30min, stirs 30min, and carboxymethyl cellulose 0.5g, wetting dispersing agent 0.5g is added,
15min is stirred, defoaming agent 0.5g and thickener 1g is added, 10min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 15
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared
95g, deionized water 40g are sufficiently mixed uniformly, and the 3g silica that partial size is 5-10 μm, the revolving speed stirring of 1500r/min is added
Thermoplastic polyurethane elastomer 10g is added in 35min, stirs 35min, and carboxymethyl cellulose 1g, wetting dispersing agent 1g is added, stirs
20min is mixed, defoaming agent 1g and thickener 1.5g is added, 15min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 16
Embodiment 16 and the difference of embodiment 13 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation
Example 13 is identical.
Embodiment 17
Embodiment 17 and the difference of embodiment 14 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation
Example 14 is identical.
Embodiment 18
Embodiment 18 and the difference of embodiment 15 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation
Example 15 is identical.
Comparative example 1
Comparative example 1 and the difference of embodiment 5 are do not have thermoplastic polyurethane elastomer in the raw material in comparative example 1, remaining with
Embodiment 5 is identical.
Comparative example 2
Comparative example 2 and the difference of embodiment 5 are do not have hydrazine hydrate in the raw material in comparative example 2, remaining is same as Example 5.
Comparative example 3
Comparative example 3 and the difference of embodiment 5 are do not have polynary amino alcohol and isocyanic acid in the raw material in comparative example 3, also without
The operation step of the two, remaining is same as Example 5.
Comparative example 4
Comparative example 4 and the difference of embodiment 17 are do not have thermoplastic polyurethane elastomer in the raw material in comparative example 4, remaining
It is identical as embodiment 17.
Performance test
According to following test method to embodiment 1-18, comparative example the 1-4 aqueous polyurethane prepared or dumb light aqueous polyurethane into
Row test, test result are shown in Tables 1 and 2.Wherein blank group is the sample without smearing any leather finishing agent.
Film rub resistance: according to GB/T8949-2008 " polyurethane dry method artificial leather " in Scott type rubbing test machine
Upper measurement.Experimental method is as follows: unidirectional 2 pieces of sample cloth covers being overlapped, being then charged into grip separation is 30mm's
In rubbing test machine clamp.The distance for gradually reducing fixture applies load, spacing contracting after contacting the cloth cover of 2 pieces of samples gently
It is small to load be 1kg until.It is 120 times/min in frequency, under conditions of stroke 50mm, reciprocal 1000 times, observes artificial leather table
Face whether there is or not glossiness variation, crackle, damage or Bu Ji and apply UF membrane phenomena such as.If there is having above-mentioned phenomenon on 1 piece of sample, then
The rub resistance for sentencing the sample is unqualified.Experimental sample is in (23 ± 2) DEG C, the standard environment and one of relative humidity (50 ± 10) %
As carry out the sample status adjustment of no less than 4h in deviation range, and tested with this condition.
Film wearability: carrying out according to QB/T2537-2001 " leather color fastness test reciprocating friction color fastness ", this mark
Standard is equal to ISO11640.The wear-resisting property of film is with leather surface colour fastness test tester to the resistance to dry of each finished leather film
Wet rubbing is tested, and then determines its grade by regulation with gray scale.Experiment condition is 20 DEG C of temperature, relative humidity 80%,
Measuring head gross mass is 1000g, and xerotripsis number is 50 times, and wet rubbing number is 200 times.
Water-resistance property of coating: materialsing 2 pieces, is put into the water that temperature is 25 DEG C, and water all submerges sample, if sample floating is difficult
Then apply external force with submergence to guarantee in sample immersion water.Observe variation of the sample in 72h.
Apply it is film modified after leather glossiness: with the daylight light irradiation specimen surface of 30W, observe gloss.
The performance test results of each aqueous polyurethane of table 1
The performance test results of each dumb light aqueous polyurethane of table 2
By Tables 1 and 2 it is found that aqueous polyurethane prepared by the present invention and dumb light aqueous polyurethane all have good wearability
And water resistance, and rub resistance can be strong, it, can be right using the aqueous polyurethane and dumb light aqueous polyurethane in the present invention
Leather and fur products plays preferable protective effect, and the raising of wear-resisting property can further improve the defect that flatting silica is easily detached from.
And the wear-resisting property for being added to the aqueous polyurethane of castor oil is better than un-added.By comparative example 1-3 in table 1 it is found that
Thermoplastic polyurethane elastomer, hydrazine hydrate, polynary amino alcohol and isocyanic acid have water resistance, wear-resisting property very big in the present invention
Influence；Lack three's any component, then will lead to it is water-fast, wear-resisting property substantially reduce or even effect is equal to blank group,
Prove that thermoplastic polyurethane elastomer in the present invention, hydrazine hydrate, polynary amino alcohol and isocyanic acid mutual cooperation play synergistic effect,
Improve the wear-resisting and water resistance of aqueous polyurethane of the present invention.As shown in Table 2, the delustring of dumb light aqueous polyurethane of the invention
Effect is obvious, can effectively improve the appearance and gloss of product using leather and fur products.By comparative example 4 in table 2 it is found that the present invention
Thermoplastic polyurethane elastomer in dumb light aqueous polyurethane has the wear-resisting and waterproof performance of dumb light aqueous polyurethane very big just
To effect.
Above-mentioned specific embodiment is only explanation of the invention, is not limitation of the present invention, art technology
Personnel can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as
All by the protection of Patent Law in scope of the presently claimed invention.
Claims (8)
1. a kind of aqueous polyurethane, which is characterized in that the raw material including following parts by weight: polynary amino alcohol 40-60 parts, isocyanic acid
35-55 parts, 15-30 parts of thermoplastic polyurethane elastomer, 8-15 parts of chain extender, neutralizer, 5-15 parts of deionized water and hydrazine hydrate
1-3 parts, the polynary amino alcohol be diethylaminoethanol, 3- amino -1,2-PD or 3- lignocaine -1- propyl alcohol, it is described
The dosage of neutralizer is that the pH of control mixed liquor is 7.5-9.
2. aqueous polyurethane according to claim 1, it is characterised in that: the chain extender is 1-4- butanediol or 2,2- bis-
Hydroxymethyl propionic acid.
3. a kind of preparation method of aqueous polyurethane of any of claims 1 or 2, which is characterized in that including following operating procedure:
Isocyanic acid is added after polynary amino alcohol is carried out vacuum dehydration processing, at 75-85 DEG C, reacts 1-3h；Chain extender is added,
At 80-90 DEG C, 2-4h is reacted；Add neutralizer at salt, deionized water and hydrazine hydrate is added, is dispersed with the revolving speed of 2000r/min
3-5min is stirred, later at 20-50 DEG C, reacts 30-40min；It is down to 20-25 DEG C, stirs 40-60min, stands 30-
48h obtains aqueous polyurethane.
4. aqueous polyurethane according to claim 1, it is characterised in that: further include 5-15 parts of castor oil.
5. a kind of preparation method of aqueous polyurethane as claimed in claim 4, which is characterized in that including following operating procedure:
Isocyanic acid and castor oil is added after polynary amino alcohol is carried out vacuum dehydration processing, at 80-85 DEG C, reacts 1-3h；Add
Enter chain extender, at 80-90 DEG C, reacts 2-4h；Add neutralizer to be neutralized into salt, deionized water and hydrazine hydrate is added, with 2000r/
The revolving speed dispersion stirring 3-5min of min reacts 30-40min later at 20-50 DEG C；It is down to 20-25 DEG C, stirs 40-
60min stands 30-48h, obtains aqueous polyurethane.
6. a kind of dumb light aqueous polyurethane, which is characterized in that the raw material including following parts by weight: claim 1 or 4 it is aqueous poly-
85-95 parts of urethane, 20-40 parts of deionized water, 1-3 parts of flatting silica, 5-10 parts of thermoplastic polyurethane elastomer, levelling agent 0.1-1
Part, 0.1-1 parts of wetting dispersing agent, 0.1-1 parts of defoaming agent and 0.5-1.5 parts of thickener.
7. dumb light aqueous polyurethane according to claim 6, it is characterised in that: the flatting silica is that partial size is 5-10 μm
Silica.
8. a kind of preparation method of dumb light aqueous polyurethane as claimed in claim 6, which is characterized in that including operating step as follows
It is rapid: the aqueous polyurethane of claim 1 or 4, deionized water being sufficiently mixed uniformly, flatting silica is added and stirs 25-35min, adds
Enter thermoplastic polyurethane elastomer stirring 25-35min, levelling agent is added, wetting dispersing agent stirs 15-20min, addition defoaming agent
5-15min is stirred with thickener, obtains dumb light aqueous polyurethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811566688.4A CN109627409A (en) | 2018-12-20 | 2018-12-20 | A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811566688.4A CN109627409A (en) | 2018-12-20 | 2018-12-20 | A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109627409A true CN109627409A (en) | 2019-04-16 |
Family
ID=66076068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811566688.4A Pending CN109627409A (en) | 2018-12-20 | 2018-12-20 | A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109627409A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112297554A (en) * | 2019-08-02 | 2021-02-02 | 李海燕 | Hot-pressing color-changing laminated structure |
| CN114040836A (en) * | 2019-06-28 | 2022-02-11 | 科慕·三井氟产品株式会社 | Method for producing molded product with suppressed surface gloss |
| CN115851056A (en) * | 2022-12-21 | 2023-03-28 | 江苏德威涂料有限公司 | Water-based acrylic coating and preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6001906A (en) * | 1997-08-04 | 1999-12-14 | Golumbic; Harvey J. | Water based plasticizer free poly urethane-wax coating & repair composition & method |
| US20040122202A1 (en) * | 2002-12-20 | 2004-06-24 | Meltzer A. Donald | Organometallic-free polyurethanes having low extractables |
| CN102007156A (en) * | 2008-04-18 | 2011-04-06 | 拜尔材料科学股份公司 | Aqueous polyurethane solutions for polyurethane systems |
| CN102066447A (en) * | 2008-04-18 | 2011-05-18 | 拜尔材料科学股份公司 | Single-component polyurethane systems composed of aqueous or water-soluble polyurethanes |
| US20110117359A1 (en) * | 2009-11-16 | 2011-05-19 | De Santos Avila Juan M | Coating composition, coated article, and related methods |
| CN103015220A (en) * | 2012-12-20 | 2013-04-03 | 陕西科技大学 | Preparation method of thermoplastic polyurethane synthetic leather |
| CN103881361A (en) * | 2014-03-31 | 2014-06-25 | 石狮市德采化工科技有限公司 | Preparation technology of water-based PU (Polyurethane) glue substituting solvent type printing ink TPU (Thermoplastic Polyurethane) |
| CN104119491A (en) * | 2013-04-24 | 2014-10-29 | 上海金汤塑胶科技有限公司 | Soybean protein modified polyurethane, and preparation method and application thereof |
| CN104893529A (en) * | 2015-06-16 | 2015-09-09 | 合肥吉科新材料有限公司 | Polymer coating and preparation method thereof |
| CN105131565A (en) * | 2015-07-22 | 2015-12-09 | 东莞市雄林新材料科技股份有限公司 | High-color-fastness thermoplastic polyurethane, thermoplastic polyurethane artificial leather and preparation method of same |
| CN105968289A (en) * | 2015-03-12 | 2016-09-28 | 东曹株式会社 | Ultraviolet light absorber resistance polyurethane composition and coating material using the same |
| CN106752840A (en) * | 2016-11-15 | 2017-05-31 | 合肥齐飞信息技术有限公司 | A kind of modified polyurethane paint and preparation method thereof |
-
2018
- 2018-12-20 CN CN201811566688.4A patent/CN109627409A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6001906A (en) * | 1997-08-04 | 1999-12-14 | Golumbic; Harvey J. | Water based plasticizer free poly urethane-wax coating & repair composition & method |
| US20040122202A1 (en) * | 2002-12-20 | 2004-06-24 | Meltzer A. Donald | Organometallic-free polyurethanes having low extractables |
| CN102007156A (en) * | 2008-04-18 | 2011-04-06 | 拜尔材料科学股份公司 | Aqueous polyurethane solutions for polyurethane systems |
| CN102066447A (en) * | 2008-04-18 | 2011-05-18 | 拜尔材料科学股份公司 | Single-component polyurethane systems composed of aqueous or water-soluble polyurethanes |
| US20110117359A1 (en) * | 2009-11-16 | 2011-05-19 | De Santos Avila Juan M | Coating composition, coated article, and related methods |
| CN103015220A (en) * | 2012-12-20 | 2013-04-03 | 陕西科技大学 | Preparation method of thermoplastic polyurethane synthetic leather |
| CN104119491A (en) * | 2013-04-24 | 2014-10-29 | 上海金汤塑胶科技有限公司 | Soybean protein modified polyurethane, and preparation method and application thereof |
| CN103881361A (en) * | 2014-03-31 | 2014-06-25 | 石狮市德采化工科技有限公司 | Preparation technology of water-based PU (Polyurethane) glue substituting solvent type printing ink TPU (Thermoplastic Polyurethane) |
| CN105968289A (en) * | 2015-03-12 | 2016-09-28 | 东曹株式会社 | Ultraviolet light absorber resistance polyurethane composition and coating material using the same |
| CN104893529A (en) * | 2015-06-16 | 2015-09-09 | 合肥吉科新材料有限公司 | Polymer coating and preparation method thereof |
| CN105131565A (en) * | 2015-07-22 | 2015-12-09 | 东莞市雄林新材料科技股份有限公司 | High-color-fastness thermoplastic polyurethane, thermoplastic polyurethane artificial leather and preparation method of same |
| CN106752840A (en) * | 2016-11-15 | 2017-05-31 | 合肥齐飞信息技术有限公司 | A kind of modified polyurethane paint and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 方禹声，等: "《聚氨酯泡沫塑料》", 31 August 1994, 化学工业出版社 * |
| 饶舟，等: "蓖麻油改性阳离子型水性聚氨酯的合成及性能", 《涂料工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114040836A (en) * | 2019-06-28 | 2022-02-11 | 科慕·三井氟产品株式会社 | Method for producing molded product with suppressed surface gloss |
| CN112297554A (en) * | 2019-08-02 | 2021-02-02 | 李海燕 | Hot-pressing color-changing laminated structure |
| CN115851056A (en) * | 2022-12-21 | 2023-03-28 | 江苏德威涂料有限公司 | Water-based acrylic coating and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109627409A (en) | A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method | |
| CN105273557B (en) | A kind of aqueous woodware paint and preparation method thereof | |
| KR100822641B1 (en) | Textile coating method with water urethane emulsion | |
| CN107254248A (en) | Multi-functional high-strength compound textile coating agent, coating and preparation method and application | |
| CN104109442B (en) | One exempts from aqueous primer surfacer and preparation method thereof of polishing | |
| CN109610183B (en) | Aqueous polyurethane coating adhesive for textiles and fabric treatment method | |
| CN105926308A (en) | Formula and technology for producing synthetic leather from graphene modified waterborne polyurethane | |
| GB1099676A (en) | Improvements in or relating to microporous sheet material | |
| CN106675269B (en) | A kind of aqueous antique artistic paint and preparation method thereof | |
| CN109722119A (en) | A kind of single-component water-based crackle paint and preparation method thereof | |
| CN104119483A (en) | Preparing method of modified acrylate emulsion | |
| CN104530330A (en) | Leather finishing agent and preparation method thereof | |
| CN109232851A (en) | Water-based aliphaic polyurethane dispersion and the aqueous dry-pasting glue of use for synthetic leather including it | |
| CN106223058A (en) | A kind of light aging resisting and the manufacture method of wear-resisting waterborne suede super fiber leather | |
| CN110029506A (en) | A kind of waterproof coating glue and waterproof cloth treatment method | |
| CN106280682A (en) | A kind of environmental protection leather aqueous stamp-pad ink and preparation method thereof | |
| CN107794777A (en) | A kind of preparation method of ventilative moisture absorption PU leather | |
| CN108193506A (en) | A kind of automotive trim graphene superfine fiber chemical leather | |
| CN104963217A (en) | Photochromic rope head, raw materials thereof and preparation method of photochromic rope head | |
| CN108795166A (en) | A kind of high abrasion-resistant environmental protection water-based gloss oil and preparation method thereof | |
| CN103409059A (en) | Polyurethane crack lacquer and preparation method thereof | |
| CN105671221B (en) | Double waterproof layer cattle hide upper leathers and preparation method thereof | |
| CN109913167A (en) | A kind of water-based polyurethane adhesive | |
| EP0086354B1 (en) | Pigment preparations and their use in the pigmentation and/or matting of finishing agents for leather and leather substitutes | |
| WO2017088084A1 (en) | Aqueous skin-touch treatment agent for synthetic leather and preparation method for same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |