CN105400410A - Water-based UV paint used for artificial leather, and preparation method thereof - Google Patents
Water-based UV paint used for artificial leather, and preparation method thereof Download PDFInfo
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- CN105400410A CN105400410A CN201510954031.5A CN201510954031A CN105400410A CN 105400410 A CN105400410 A CN 105400410A CN 201510954031 A CN201510954031 A CN 201510954031A CN 105400410 A CN105400410 A CN 105400410A
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- leatheroid
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic 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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double 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
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a water-based UV paint used for artificial leather. The water-based UV paint comprises waterborne polyurethane resin, waterborne fluorinated polyurethane-acrylic acid resin, water, a photosensitive initiator, a delustering powder, a levelling agent, an antifoaming agent, and a dispersing agent. The water-based UV paint is preferably applied to roller painting of artificial leather, and can be taken as a painting decoration paint of automotive interior and exterior decoration; obtained paint films possess high crosslinking density, high adhesive force, small odour, and excellent acid and alkali resistance, is friendly to the environment, and is capable of saving energy.
Description
Technical field
The present invention relates to a kind of waterborne UV coating, be specifically related to a kind of waterborne UV coating being applied to leatheroid and preparation method thereof.
Background technology
UV coating and ultraviolet-curing paint, be applied to furniture, Floor Industry the earliest, has the advantages such as curing speed is fast, less energy-consumption, low stain.Along with coating science and technology is growing, UV coating is applied on the materials such as plastics, paper, timber, metal, leather gradually, becomes the important selection of decorative paint in many industries.Along with the theory of energy-saving and emission-reduction and Environmental Safety is rooted in the hearts of the people gradually, the UV coating of waterborne UV coating and the solid part of height presents the trend of the oiliness UV coating replacing organic solvent class gradually.
On automobile interior exterior decorations, many producers have not re-used corium decoration, but the leatheroid adopting more environmental protection inexpensive, as PVC artificial leather.Leatheroid use UV coating carry out decoration much, utilize organic UV coating of the prior art often to there is following key issue: one, odor problem, most oil paint due to dissolvent residual or reaction not exclusively often there is irritating smell; Two, environmental issue, all there is the discharge of VOC in the preparation process of oil paint and use procedure, solvent can be made especially to come out during solidification heating; Three, cross-linking density, the cross-linking density of oil paint is lower slightly.Under comparing, waterborne UV coating odorlessness problem, without environmental protection risk, as long as promote its cross-linking density, waterborne UV coating just can reach effect and the performance of conventional oil-based coating.
Summary of the invention
For the deficiencies in the prior art part, the invention provides that a kind of cross-linking density is high, environmental protection and energy saving, smell is little, acid-proof alkaline the is good waterborne UV coating being applied to leatheroid.
Technical problem to be solved by this invention is achieved by the following technical programs:
The component and the mass percentage that are applied to the waterborne UV coating of leatheroid described in the present invention are as follows:
Waterborne polyurethane resin 40-60%
Aqueous fluorine-containing polyurethane-acrylic resin 10-30%
Water 10-20%
Photoinitiator 5-10%
Dumb light powder 3-5%
Flow agent 1-2%
Defoamer 1-2%
Dispersion agent 1-2%
Described photoinitiator is polyethylene oxygen ethyl cinnamate or polyparaphenylene diacrylate.
Described flow agent is conventional commercially available water-based flow agent.Described defoamer is the one in polysorbas20, polysorbate40, polysorbate60, tween 80.Described dispersion agent is trolamine.
Described dumb light powder uses commercially available dumb light powder, not only can regulate viscosity and the color of the UV coating in the present invention, also can play a supporting role simultaneously.
Waterborne polyurethane resin in the present invention adopts commercially available matured product as the basic resin of waterborne UV coating formula in the present invention, forms the basic framework of solidifying product.Simultaneously in order to promote the fundamental property of the rear product rete of solidification further, as hardness, snappiness, sticking power, light fastness, acid-proof alkaline etc., a kind of homemade aqueous fluorine-containing polyurethane-acrylic resin is added in the present invention, this water-base resin has hydrophilic radical so good water solubility, both high strength, wear-resisting, tear resistance containing urethane resin, possess again the snappiness of acrylic resin, excellent resistance to deterioration.Simultaneously; fluoro-containing group in aqueous fluorine-containing polyurethane-acrylic resin can be enriched on the interface of polymkeric substance and air; provide protection is formed to main chain and interior molecules, makes the emulsion of this resin formation more stable, yet further enhances snappiness and the sticking power of paint film simultaneously.
The preparation method of described aqueous fluorine-containing polyurethane-acrylic resin is:
(1) methyl methacrylate, lauryl methacrylate(LMA), Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate are mixed with mass ratio 1:1:0.2:0.4, above-mentioned mix monomer being dissolved in quality is in the N-BUTYL ACETATE of mix monomer total mass 5 times, then mixed solution is placed in the benzoyl peroxide dripping mix monomer total mass 6% after reactor is warming up to 120 DEG C, in reaction process, continued mechanical stirs, reaction 3-5 hour, obtains fluoroacrylic resin.
(2) fluoroacrylic resin obtained in (1), dibutyl tin laurate, dehydrated alcohol are mixed in reaction vessel with mass ratio 50:2:8, after stirring, reaction vessel is warming up to 80-85 DEG C, then the isophorone diisocyanate of fluoroacrylic resin quality 5% is added, react and cool the temperature to 55 DEG C after 0.5-1 hour, add the dimethylolpropionic acid of fluoroacrylic resin quality 10%, react and be warming up to 80 after 1 hour
DEG C, then add the Hydroxyethyl acrylate of fluoroacrylic resin quality 20%, be incubated 4 hours, i.e. obtained fluorochemical urethane-acrylic resin containing hydrophilic radical-COOH.
(3) what obtain in (2) has the fluoroacrylic resin of hydrophilic group interpolation ammoniacal liquor to resin system pH value to be 7-7.5, then in high speed dispersor, disperse 1.5-2 hour with the rate of dispersion of 3500-4500r/min after adding the deionized water mixing of resin system equal in quality, obtain aqueous fluorine-containing polyurethane-acrylic resin emulsion.
The monomer adopting methyl methacrylate different with lauryl methacrylate(LMA) these two kinds in the present invention and Hexafluorobutyl mathacrylate, these two kinds of fluorochemical monomers of dodecafluoroheptyl methacrylate react and generate fluoroacrylic resin under the effect of initiator benzoyl peroxide.Then on the basis of fluoroacrylic resin, first by isocyanic ester and dimethylolpropionic acid grafting, prepare intermediate, then carry out by Hydroxyethyl acrylate fluorochemical urethane-acrylic resin that end-blocking prepares water-based, finally by ammoniacal liquor adjust ph, then by dispersion steps, gained resin is made emulsion.
The preparation method being applied to the waterborne UV coating of leatheroid in the present invention is as follows:
Being mixed according to formula by all raw materials is placed in high speed dispersor, with the rate of dispersion of 2000-3000r/min dispersion 1-2 hour.
The waterborne UV coating being applied to leatheroid in invention preferably uses the method for roller coat to carry out application.
The present invention has following beneficial effect:
1, the waterborne UV coating in the present invention can be applicable to leatheroid external coating decoration, and this crosslinking coatings density is high, strong adhesion, environmental protection and energy saving, smell is little, acid-proof alkaline good.
2, the waterborne UV coating preparation technology in the present invention and coating process simply, are applicable to suitability for industrialized production.
Embodiment
Below by embodiment, content of the present invention is conducted further description.
1, the preparation of aqueous fluorine-containing polyurethane-acrylic resin
Step 1: methyl methacrylate, lauryl methacrylate(LMA), Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate are mixed with mass ratio 1:1:0.2:0.4, above-mentioned mix monomer being dissolved in quality is in the N-BUTYL ACETATE of mix monomer total mass 5 times, then mixed solution is placed in the benzoyl peroxide dripping mix monomer total mass 6% after reactor is warming up to 120 DEG C, in reaction process, continued mechanical stirs, react 4 hours, obtain fluoroacrylic resin.
Step 2: fluoroacrylic resin obtained in step 1, dibutyl tin laurate, dehydrated alcohol are mixed in reaction vessel with mass ratio 50:2:8, after stirring, reaction vessel is warming up to 80 DEG C, then the isophorone diisocyanate of fluoroacrylic resin quality 5% is added, react and cool the temperature to 55 DEG C after 0.5 hour, add the dimethylolpropionic acid of fluoroacrylic resin quality 10%, react and be warming up to 80 after 1 hour
DEG C, then add the Hydroxyethyl acrylate of fluoroacrylic resin quality 20%, be incubated 4 hours, i.e. obtained fluorochemical urethane-acrylic resin containing hydrophilic radical-COOH.
Step 3: what obtain in step 2 has the fluoroacrylic resin of hydrophilic group interpolation ammoniacal liquor to resin system pH value to be 7-7.5, then in high speed dispersor, disperse 2 hours with the rate of dispersion of 4500r/min after adding the deionized water mixing of resin system equal in quality, obtain aqueous fluorine-containing polyurethane-acrylic resin emulsion.
2, the preparation of waterborne UV coating
In embodiment the component of coating and mass percentage as shown in the table, corresponding numerical value is the mass percentage of corresponding component.
The photoinitiator used in embodiment is polyethylene oxygen ethyl cinnamate, and flow agent is water-based flow agent BYK333, and defoamer is polysorbate40, and dispersion agent is trolamine.The dumb light powder adopted uses commercially available prod, and powder size selects comparatively fine and smooth product, and solid particulate granularity is less than 5 μm.
In embodiment, the preparation method of waterborne UV coating is as follows:
Being mixed according to formula by all raw materials is placed in high speed dispersor, disperses 2 hours, namely obtain required coating after cooling with the rate of dispersion of 2500r/min.
Adopt commercially available can be used for PVC artificial leather oiliness UV coating and the present embodiment in coating carry out test comparison.Surveyed coating roll is applied on PVC artificial leather sample, after ultraviolet lamp effect 5-10min photocuring, carries out RCA paper tape wearability test, resistance to acids and bases test and smell test until coating.
The method of resistance to acids and bases test is will be coated with and leatheroid sample after solidifying to be soaked in the hydrochloric acid and aqueous sodium hydroxide solution that concentration is 2.5wt% 24 hours respectively, observation paint film state.
The testing method of " the car room component Odor Examination " of the method reference Volkswagen of smell test: the beaker leatheroid sample of 3 × 3mm being placed in 1 liter, put into 200g deionized water by its submergence, then the water in beaker is heated to 80 DEG C of insulations 4 hours, in insulating process, beaker mouth is closed.Select 5 people to carry out hearing the smell in beaker, oder levels is divided into taste and tasteless, and wherein have taste to be subdivided into again: B level refers to there is pleasant smell, C level is bad smell, and D level is difficult by smell, and E level is felt sick smell.Tasteless: A level.Experimental result judges standard: result obtains 4 more than A and then meets the requirement of automotive trim to smell.5 people carrying out smell test before testing through the training of smell test, can objectively effectively need judge oder levels.
Test result is as follows:
From the test result of embodiment, when the waterborne UV coating in the present invention is applied on the decoration of leatheroid, not only there is no smell, and resistance to acids and bases, wear resistance are good.
Finally it should be noted that, above embodiment is only in order to illustrate the technical scheme of the embodiment of the present invention but not to be limited, although be described in detail the embodiment of the present invention with reference to preferred embodiment, those of ordinary skill in the art is to be understood that and still can modifies to the technical scheme of the embodiment of the present invention or equivalent replacement, and these are revised or be equal to the scope that replacement also can not make amended technical scheme disengaging embodiment of the present invention technical scheme.
Claims (8)
1. be applied to a waterborne UV coating for leatheroid, it is characterized in that the component of described coating and mass percentage as follows:
Waterborne polyurethane resin 40-60%
Aqueous fluorine-containing polyurethane-acrylic resin 10-30%
Water 10-20%
Photoinitiator 5-10%
Dumb light powder 3-5%
Flow agent 1-2%
Defoamer 1-2%
Dispersion agent 1-2%
Described photoinitiator is polyethylene oxygen ethyl cinnamate or polyparaphenylene diacrylate.
2. be applied to the waterborne UV coating of leatheroid as claimed in claim 1, it is characterized in that the preparation method of described aqueous fluorine-containing polyurethane-acrylic resin is:
(1) methyl methacrylate, lauryl methacrylate(LMA), Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate are mixed with mass ratio 1:1:0.2:0.4, above-mentioned mix monomer being dissolved in quality is in the N-BUTYL ACETATE of mix monomer total mass 5 times, then mixed solution is placed in the benzoyl peroxide dripping mix monomer total mass 6% after reactor is warming up to 120 DEG C, in reaction process, continued mechanical stirs, reaction 3-5 hour, obtains fluoroacrylic resin;
(2) by fluoroacrylic resin obtained in (1), dibutyl tin laurate, dehydrated alcohol mixes in reaction vessel with mass ratio 50:2:8, after stirring, reaction vessel is warming up to 80-85 DEG C, then the isophorone diisocyanate of fluoroacrylic resin quality 5% is added, react and cool the temperature to 55 DEG C after 0.5-1 hour, add the dimethylolpropionic acid of fluoroacrylic resin quality 10%, react and be warming up to 80 DEG C after 1 hour, add the Hydroxyethyl acrylate of fluoroacrylic resin quality 20% again, be incubated 4 hours, i.e. obtained fluorochemical urethane-acrylic resin containing hydrophilic radical-COOH,
(3) it is 7-7.5 that obtained in (2) fluoroacrylic resin containing hydrophilic group adds ammoniacal liquor to resin system pH value, then in high speed dispersor, disperse 1.5-2 hour with the rate of dispersion of 3500-4500r/min after adding the deionized water mixing of resin system equal in quality, obtain aqueous fluorine-containing polyurethane-acrylic resin emulsion.
3. be applied to the waterborne UV coating of leatheroid as claimed in claim 1, it is characterized in that: described flow agent is water-based flow agent.
4. be applied to the waterborne UV coating of leatheroid as claimed in claim 1, it is characterized in that: described defoamer is the one in polysorbas20, polysorbate40, polysorbate60, tween 80.
5. be applied to the waterborne UV coating of leatheroid as claimed in claim 1, it is characterized in that: described dispersion agent is trolamine.
6. be applied to the waterborne UV coating of leatheroid as claimed in claim 1, it is characterized in that: described in be applied to the waterborne UV coating roller coat of leatheroid method carry out application.
7. be applied to the waterborne UV coating of leatheroid as claimed in claim 1, it is characterized in that: described in be applied to leatheroid the waterborne UV coating preparation of adoring for automobile interior exterior.
8. prepare a method for the waterborne UV coating being applied to leatheroid as described in claim 1-5, it is characterized in that: all raw materials are mixed according to formula and is placed in high speed dispersor, with the rate of dispersion of 2000-3000r/min dispersion 1-2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510954031.5A CN105400410B (en) | 2015-12-18 | 2015-12-18 | It is a kind of applied to waterborne UV coating of artificial leather and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510954031.5A CN105400410B (en) | 2015-12-18 | 2015-12-18 | It is a kind of applied to waterborne UV coating of artificial leather and preparation method thereof |
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| CN105400410A true CN105400410A (en) | 2016-03-16 |
| CN105400410B CN105400410B (en) | 2017-11-07 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651583A (en) * | 2018-11-28 | 2019-04-19 | 韶关市合众化工有限公司 | A kind of fluororesin modified ester-polyurethane resin emulsion of the acrylic acid that high rigidity is water-fast |
| CN112175162A (en) * | 2019-07-05 | 2021-01-05 | 万华化学（宁波）有限公司 | Modified waterborne polyurethane resin, preparation method and application thereof |
| CN113062125A (en) * | 2021-04-01 | 2021-07-02 | 昆山阿基里斯新材料科技有限公司 | Preparation method of hydrophobic artificial leather |
| CN115213072A (en) * | 2021-12-09 | 2022-10-21 | 广州汽车集团股份有限公司 | Stain-resistant light-color leather automobile seat fabric |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651583A (en) * | 2018-11-28 | 2019-04-19 | 韶关市合众化工有限公司 | A kind of fluororesin modified ester-polyurethane resin emulsion of the acrylic acid that high rigidity is water-fast |
| CN112175162A (en) * | 2019-07-05 | 2021-01-05 | 万华化学（宁波）有限公司 | Modified waterborne polyurethane resin, preparation method and application thereof |
| CN113062125A (en) * | 2021-04-01 | 2021-07-02 | 昆山阿基里斯新材料科技有限公司 | Preparation method of hydrophobic artificial leather |
| CN115213072A (en) * | 2021-12-09 | 2022-10-21 | 广州汽车集团股份有限公司 | Stain-resistant light-color leather automobile seat fabric |
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| Publication number | Publication date |
|---|---|
| CN105400410B (en) | 2017-11-07 |
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